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JNM-ECA Series JNM-ECX Series JNM-ECS Series

1. 2 85 2 20 5 2 86 PUN CO P Y 2 86 2 20 7 Start Time of M easurement sseeeenmnnn 2 87 S249 Measurement 2 87 SEL PARA 2 88 ELLE TOM enero teens 2 88 Anay Ec E UT 2 95 NM ECA ECX USM 3 2 SPECTROMETER CONTROL gt 2 1 SPECTROMETER CONTROL WINDOW The Spectrometer Control window controls spectrometer connection and NMR measurement 2 1 1 Starting the Spectrometer Control Window Starts the Spectrometer Control window from the Delta onsole window Click on the button in the Delta Console window The Spectrometer C ontrol window opens f you select Acquisition Connect in the menu bar the Spectrometer Control window can also be started In the Delta Console window if you press the key while pushing the key the Spectrometer C ontrol window can start al Spectrometer Control FREE 900 5th BLD OHHED ECK400 R amp D DEHO OHHED ECA500 R amp D DEHO OHHED ECABO0 R amp D OHHED R amp D Basement All Samp Expmnt Fig 2 1 Spectrometer Control window The Spectrometer C ontrol window can control spectrometer function NM ECA ECX USM 3 2 1 2 SPECTROMETER CONTROL 2 1 2 Connecting and Releasing S
2. 2 86 2 20 7 Start Time of M 2 87 2 20 8 M easurement Information eeeennn 2 87 2 88 eel 2 88 dd gc 2 95 3 ADJUSTMENT PARAMETERS 3 1 PURPOSE OF MEASURING PULSE WIDTHS 3 1 3 2 SPECTROMETER RF SYSTEM AND FACTORS AFFECTING PULSE S DTH nies es 3 3 3 3 MEASUREMENT OF PULSE WIDTHS WHEN OUTPUT IS USED AF RALF FO S ER aA 3 5 3 4 CALCULATION OF 90 PULSE WIDTHS AFTER THE ATTENUATOR VALUE IS CHANGED 3 8 35 MEASUREMENT OF PULSE WIDTHS IN 9 3 9 36 CALCULATION OF 90 PULSE WIDTH OF SELECTIVE sare 3 10 3 7 USAGE OF PULSE CALCULATOR TOOL 3 12 4 USAGE OF PULSE SEQUENCES 4 1 EXTENSION SEQUENCES aH Ed 4 3 BELL SUN ILL e aspe RU MUN MER HIDE IMPIUM NIMIRUM DUM NNNM 4 3 RM 4 4 4 5 2 NM ECA ECX USM 3 5 4 6 sip 4 7 4 8 an 4 9 4 10 SNOR TU 4 10 o EE Ned oon dr 4 11 4 2 3 singile pulse
3. 2 23 2 3 EXPERIMENT EDITOR TOOL 2 2 2 3 1 Measurement File Experiment 1 2 28 mu 2 29 2 3 3 Instrument 2 33 2 35 PUISSE ieee een 2 37 24 AUTOMATION TOOL WINDOW eem 2 39 2 4 1 Standard M ode in the Automation Window 2 39 2 4 2 Advanced M ode in the Automation W indow 2 42 25 RUN SAWTOOTH EXPERIMENT WINDOW 2 47 26 VECTOR VIEWER WINDOW eem 2 48 ua ance p on MUN TEN FIRE 2 49 POCEN MEN saika 2 50 27 MAKEA NEW INSTANCE OF A SELECTED JOB COMMAND 2 51 ee DISPLAY 2 52 2 9 DISPLAYING AND CHANGE OF AN INSTRUMENT Pe Pe Gl Et INN EM IRAN 2 53 2 9 1 Display of an Instrument 2 53 2 9 2 Changing an Instrument 2 54 SARATE IEN ER 2 55 2 10 1 How to Display 2 56 2 10 2 Calculation of Pulse Width and ttenuator V
4. 2 5 211 ABNORMAL DISPLAY OF A SPECTROMETER 2 58 elt MAIDEN 2 59 2 12 1 Executing 2 59 l 2 60 2 12 3 Saving Validation Results to a 2 60 215 DISPLAY DF LOG FILE 2 61 a TRU 2 61 El NM 2 62 ELT 2 63 FRE 2 64 PAS PROPRE 2 66 S9M M 2 67 2 16 1 Display of Information for a Specified Nucleus 2 67 2 16 2 Saving Value to the Probe FIG irri visti Ta REP HA Feb RES pei 2 68 e ARIS SIE PUB successio uH ENERO HN 2 69 GBRBIENT DERE 2 71 2 18 1 Outline of the Gradient 5 2 71 1802 Operio nunaa 2 73 4 19 SPECTROMETER CONFIGURATION 2 78 2 00 EXPERIMENT AND QUEUE 2 80 CAE 16 DURER un d ORUM 2 80 P cc 2 82 2 20 3 Restating M easurement GO 2 83 2 20 4 Cancelling M easurement STOP
5. Fig 5 25 chemical shifts NM ECA ECX USM 3 5 33 INDEX 7 Rh chemical shifts 5 30 Ag chemical shifts 5 30 13 d chemical shifts 5 31 196 chemical shifts 5 31 B chemical SHIT BS 5 23 chemical shifts 5 24 E 2 91 VN PN chemical shifts 5 24 MQ chemical shifts 5 25 195 chemical shifts 5 32 1 H chemical shifts 5 32 ME chemical shifts 5 25 10 4 10 HH HUNING 2 88 2 Py chemical 5 5 5 33 A chemical shifts 5 26 Si chemical shifts 5 26 2D 4 36 31 chemical shifts 5 27 33S chemical shifts 5 27 5 chemical shifts 5 28 6 027 chemical shifts 5 28 PAS chemical shifts 5 29 Se chemical shifts 5 29 9 90 pulse width in the observation EDS ERU 3 6 90 pulse width display 2 52 NM ECA ECX USM 3 A A bnormal display of a spectrometer 2
6. 4 34 E ce is MUI DEREN 4 36 4 36 32 JUI LV DOS BUE 4 38 Bu HN LUI 4 40 CHR EE oiii REEF PERIERE MEN 4 42 2I BINE DE OHNE M ROUND MN M MEN M sean 4 44 NM ECA ECX USM 3 4 47 ROI 4 50 438 t csy dec phase 4 52 4 T 4 54 Cem 4 56 TURN 4 58 A 4 60 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES STYLE OF DESCRIPTION This chapter explains various types of NM R measurement in the following format Header 2 T he header indicates the name of an experiment file The directory in which the files are located is shown under the experiment filename 25 The measurement mode standard values of measurement parameters and data processing steps are stored in the experiment file exp c For information on directories refer to the Supplementary notes Directory tree structure Purpose The purpose of measurement is briefly described Pulse sequences The pulse sequences used for this measurement are illustrated schematically The correspondence between the parameters and the timing of pulses is also shown Extension sequences The function of extension sequences from which you can select for examp
7. Power amplifier Receiver Fig 5 2 Block diagram of the multinuclear NMR observation instrument In the multinuclear NMR observation system the oscillator generates radio waves of specific frequencies and the power amplifier amplifies them Then the output power is fed into the probe through the duplexer which allows switching between transmit and receive The probe is provided with the variable capacitors for tuning and matching to the resonance frequency Depending on the observation frequency the small capacitor called the stick may need to be exchanged as one variable condenser can not cover all resonance frequencies 5 4 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 5 2 MULTINUCLEAR NMR MEASUREMENT This section explains the actual procedures needed to measure multinuclear NMR and also the H nucleus as a special case 5 2 1 Multinuclear Observation Probes The probes used for multinuclear NM R measurement are called multinuclear observation probes The following types of multinuclear probes are available e5 mm TH Tunable Probe standard e5 mm TH Tunable FG Probe optional e 5 mm TH Auto Tune Probe optional 5 mm TH Auto Tune FG Probe optional e 10 mm TH Tunable Probe optional e 10 mm TH Auto Tune Probe optional e Low Frequency Tunable Probe optional LF1 TUNE dial LF1 MATCH dial San A LF1 TUNE dial LF1 MATCH dial Stick HF tuning knob HF1 MATCH dial HF1 TUNE di
8. 0 3 0 1 0 1 0 3 0 Itt p 1 i t u d e m FERT f f amp t abundance Ruler State Position inside Pulse Fig 2 43 ShapeViewer window 2 55 2 SPECTROMETER CONTROL 2 10 1 How to Display a Shape 1 Select Tools Shape Viewer in the menu bar of Spectrometer Control window The Shape Viewer window opens 2 Selectthe category to display from FG Shapes RF Shapes and Noise 3 Selecta Shape to display 4 Change Phase and Amplitude with the toggle button aabe Shape Viewer jFGShaps 7 RF Shapes GAUSS Noise NEN Reference 80 0 100 60 0 40 0 avundance i 20 0 D abundance 0 3 0 1 0 1 0 3 0 10 Freq Response Display Bandwidth 41 093 Square Worksheet 90 Pulse us dB State Position inside Pulse KHz Attenuation aabe Shape Viewer LJ FG Shapes 7 RF Shapes GAUSS a ex _ Noise Freq Response Display I Bandwidth 41 093 lt Square Reference Worksheet Power Level PF pepe FAVCHUauoT X Ruler State Position inside Pulse 30 0 60 0 90 0 0 3 0 1 0 1 0 3 0 0 3 0 1 0 1 0 3 0 Fig
9. aabe Automation scc2 nm jeol co jp 172 dC After changing procedure is complete ADVANCED appears in the Automation window Starting automatic measurement l Enter the necessary minimal parameters in the following table Parameter Filename Comment Slot T emp Set T emp State Solvent NM ECA ECX USM 3 explanation Saving file name Comment Slot number of the auto sample changer at auto sample changer use Setting temperature of the unit Setting VT state Solvent 2 43 2 SPECTROMETER CONTROL 2 Setup arbitrary options Typical arbitrary parameter Explanation Notify Transmission place for measurement completion mail Holding transmission place for measurement completion Hold mail Gradient Shim Performing gradient shimming A gradient shimming is performed only when measuring Gradient ptimization first sample or after changing the sample time Enhance Filename A date 15 added to the file name 3 Click on the method button delta automation auto2 125 1 A0 ai Combination 1 Mend 4 NAT ON Gradient DOF cos CAHE Automation Tes Fig 2 36 Set Parameters window 2 44 NM ECA ECX USM 3 2 SPECTROMETER CONTROL In the Set Parameters window the setting range for every group contained in the selected method exists T he range for this group is divided by a blue line M oreover in the range for every group of this the setting range for ever
10. eem 5 11 5 3 2 Selection of Sample UM LUE PEN GAD ORE 5 11 5 3 3 Problems Involved with a Wide Chemical Shift Range 5 12 nage gt 5 13 5 29 Problems with LOW Frequency 5 14 emm 5 14 5 3 7 Calculating the Pulse Width When There Is No Proper Reference vi iP NND 5 15 NM ECA ECX USM 3 54 RELAXATION TIMES OF MU LTINUCLE 5 16 5 4 1 General Tendencies of Relaxation Times of M ultinuclei 5 16 5 4 2 Reference Data for Relaxation Times and M easurement Conditions tmm 5 17 5 5 CHARTSAND MEASUREMENT MODES FOR MULTINUCLEAR 5 19 5 5 1 Relationships Between Nuclear Species and Sticks 5 19 5 0 2 Chemical SIS 5 23 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 5 1 OUTLINE OF MULTINUCLEAR NMR MEASUREMENT This section outlines the basics of multinuclear NMR measurement It includes the definition and features of multinuclear NM R a discussion of sensitivity on the basis of the PC nucleus and a brief description of the hardware composition of the multinuclear observation instrument 5 1 1 About Multinuclear NMR The definition and features of
11. gt 4 1 2 Presaturation Presaturation reduces a signal that would overwhelm the desired peak such as a water signal in an aqueous solution sample making it easy to detect the sample signal B Parameters irr domain tri domain The irradiation nucleus is set to the same as the observation nucleus irr offset tri offset Irradiation position resonance frequency of peak to irradiate The default is 5 ppm irr attenuator tri attenuator Determines RF output for the irradiation pulse for presaturation The default is 40 dB Every time 3 dB is added the RF output is halved 4 4 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES ommum mm 4 1 3 Homo Decouple Used to perform homonuclear spin spin decoupling B Pulse sequences irr domain attenuator ti domain tri attenuator irr offset trr offset Parameters irr domain tri domain The irradiation nucleus is set to the same as the observation nucleus irr offset tri offset Resonance frequency of the peak to be irradiated The default is 5 ppm irr attenuator tri attenuator D etermines RF output for spin decoupling pulses The default is 40 dB Every time 3 dB is added the RF output is halved Supplementary note The multiple splitting of a peak due to spin coupling to the irradiated peak is eliminated by decoupling Thus the peaks having spin spin coupling with each other can be determined NM ECA ECX USM 3 4 5 4 USAGE OF
12. 2 33 EIU 2 22 Liquid helium level 2 12 Liquid nitrogen level 2 12 Loading a 5 2 14 Local 2 28 Lock 2 10 LR aseni 2 22 2 22 Lock signal diSplay 2 26 NM ECA ECX USM 3 Machine LOU 2 62 M 2 50 M agnetic field strength 2 12 M ake a New Instance of a Selected lOD COMI 2 51 anagement of the measurement Ri 2 1 easurement 2 28 M easurement information 2 87 M easurement of pulse widths in 3 9 M easurement of pulse widths when output is used at half power 3 5 M easurement priority scenene 2 86 M enu 1 2 NT 2 2 M ultinuclear NM 5 1 M ultinuclear NMR chemical shifts 5 23 M ultinuclear NM R observation locii ARIETE TT 5 4 M ultinuclear observation probes 5 5 N LER 2 10 NMR lock control button 2 22 NMR lock relation parameter 2 22 NMR Hock 5 2 22 4 6 LES 4 23 noe ld 2
13. menu bar of the Spectrometer Control window aabe Spectrometer Control Probe Tool Shim on FID Gradient Shim Tool Machine Config The Config Autotune Probe window opens 2 64 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 4 aabe Config Autotune Probe Create Dial File IH amp 130 Other Fig 2 53 Config Autotune Probe window 3 Read the dial value of the auto tuning probe and enter a dial value into each input box 4 Click on the 1H amp 13C button The check window of a dial value appears aahe Confirm 9 Ready to save dials file LF Tune 4409 LF Match 3599 HF Tune 2390 HF Match 5466 5 Click on the OK button after confirming that the dial value is set correctly Dial value is saved and PreTuning begins Pre Tuning is performed in the order of Coarse LF and HF The following dialog boxes are displayed during the PreTuning of LF and HF faabe Inform r aahe Inform Tuning coil LF1 to 13C Tuning coil HF1 to 1H probe coarse probe coarse HF prohe tune 4350 probe tune 2396 probe match 3620 probe maich 5450 6 After the dialog box of HF disappears and Pre Tuning is complete click on the Close button in the Config Autotune Probe window to close the window 7 Click on the Connect button in the Spectrometer Control window to return the connection mode to Connect mode NM ECA ECX USM 3 2 65 2 SPECTROMETER CONTRO
14. 2 21 c 4 36 INDEX dic Tar 4 36 00 2 61 D gante presai seines io sate dai p duds 4 3 DIDCBBSDT 1 4 Data 5 1 4 a actinium 1 4 DC 2 50 2 50 DECIDE OB 3 5 4 7 Definition of a chemical shift 5 7 2 82 Delta Console window 1 2 ing HM 4 18 dis o 4 18 difference noeld ex2 4 23 Directory tree lt 4 2 Display of an instrument parameter 2 53 Display of information for a specified 2 67 Display of log 1 2 61 Display of SCM related information 2 12 double 5 2 4 32 double pulse 2 4 34 _ _ 2 4 38 Ejecting 5 2 15 Enhance Filename 2 40 Executing Validation 2 59 Experiment E ditor Tool window 2 27 Experiment as cora e 2 28 Extension 5 4 3 Ext
15. Information of a spectrometer to connect l Select the spectrometer to connect in the Spectrometer Control window using the mouse The name of the selected spectrometer is highlighted 2 Click on the Info button The Info window opens Info for sccz Fig 2 2 Info window before connection 25 The kind of spectrometer magnetic field strength information appearing in machine info for this spectrometer and its probe information are displayed Information of on the connected spectrometer Click on the Info button in the Spectrometer Control window The Info window opens Info for sce 2 DIEE Current User aabe atsushi mi Current Host ecall nm jeol co jp uid 30293 port 6422 Version 4 3 Beta 03 18 04 13 36 ADS ECA 500 NMR Spectrometer Variable Temperature Range 150C to 180C 5mm Broadband Gradient Tunable Fig 2 3 Info window after connection JS n addition to the information before connection user information and informa tion on the connected workstation is displayed NM ECA ECX USM 3 2 5 2 SPECTROMETER CONTROL Display of the available spectrometer Click on the Free button in the Spectrometer Control window The node name and user for all available spectrometers on a network are investi gated and displayed Connection is also canceled at this time pend Queue State OWNED 2 6
16. range de 300 400 500 600 percent spin dm i x ia Ho DOCE eto mer to LO LO 10 2295 72 0 to LO LO 10 32 Yb a NO A no 1431 2 54690 UY 10 LO LO LO 1633 52 sa 72 31d LO LO LO 185 m 63bq0 Ht 10 LO 1375 92 21600 B B C C 99988 72 20300 ew 30 80 NO 3707 52 26x10 DO 6293 52 490 DO os Lo LO LO LO 164 12 LDd0 10101010 161 32 21 ir to to 10 10 32 2000 ir to to 607 32 vao et no wo mi nape 100 1300 E a NO A NO 1684 12 54 CD Hg 2980 12 28930 TINO Pb NO 226 12 mea Poos DO 10 92 rma 5 22 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 5 5 2 Multinuclear NMR Chemical Shifts The main reason to perform multinuclear NMR is to determine chemical shift values Unfortunately it may take a considerable amount of time to find a
17. uw e 23 uto Lock amp Shim Gradient Shim amp Lock The NMR lock is turned on to the H signal included in sample Wide range search of a lock signal is not performed Therefore it is necessary to adjust ZO in the Sawtooth window so that a lock signal may adjust in advance to the position of lock frequency NMR lock is turned off However since the output of the lock oscillator does not stop in addition to Lock OFF instruction it is necessary to change an instrument parameter LOCK OSC STATE to H OSC OFF when observing a H nucleus Refer to the Parameter Tool for changing instrument parameters Wide range search of the lock signal is carried out and if a signal is found the NMR lock will be turned on M oreover the level and gain of the NMR lock will be adjusted automatically The Z1 axis and Z2 axis shim is adjusted automatically after automatical locking Shimming is performed by gradient shim Gradient Shim The execution conditions of the gradient shim are described in gradient solvent2 file of the instrument directory Automatically locking is performed after performing the gradient shimming Optimize Lock The lock signal phase is optimized In order to use this Phase function it is necessary to turn on NMR lock advance B NMR lock relation parameter 2 22 Parameter NMR lock state only display Gain Level Phase Offset Explanation TheNMR lock
18. c 90 s Set Login Params Change Password Shape Viewer Set Default Instrument Status 8 Clear Default Instrument Slot _ Job Submit Time Auto 2 Select Config Machine Config in the menu bar of the Spectrometer Control window The Spectrometer C onfiguration window opens machinepre exp zmachinepre 5532 machine pre exp65533 machinepre exp65534 f 2 78 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 3 Selectthe file to edit from the Configure Files list box 4 Click on the Edit button The Machine Configure window opens M A faabe Machine Configure machine config Value 5 Select the parameter to change from the Parameter list box 6 Seta value in the Value input box 7 Save a file to the Save Configure File updating 5 3 2 79 2 SPECTROMETER CONTROL 2 20 EXPERIMENT AND QUEUE MANAGMENT Queuing performs measurement in this spectrometer That is more than one experiment can be registered to the spectrometer submit and they are performed in the order of registration There are five modes OWNED RUNNING HALTED FREE and WAITING in the spectrometer Queue These modes cannot be changed if there is no console privilege A priority is given the measurement that is recorded in a Queue respectively The priority is ranked with numerical values from 0 minimum to 255 maximum Each users default priority is spec
19. 220 178 5 MULTINUCLEAR NMR MEASUREMENT C 0 100 200 18 CcHs0 sP0 12 34 62 0 80 PCI 0 100 200 ppm Fig 5 13 chemical shifts 0 0 300 230 1 5 2 225197 134 0 2 300 150 USM 3 89 168 261 0 150 300 Fig 5 14 S chemical shifts 5 27 5 MULTINUCLEAR MEASUREMENT 14000 12000 10000 8000 6000 4000 2000 0 ppm 9680 1 50 9100 cons eva 8100 7440 13900 6500 K Co CO 13000 1400 gt 12500 0 14000 12000 10000 8000 6000 4000 2000 0 Fig 5 15 Co chemical shifts 300 200 100 0 100 ppm 1 4 284 0 355 Zn NO 2 300 200 100 0 100 Fig 5 16 Zn chemical shifts 5 28 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 400 200 0 200 400 ppm 217 230 369 206 0 291 0 As KASF 400 200 0 200 400 ppm Fig 5 17 chemical shifts 450 300 150 0 150 ppm 480 411 280 130 0
20. 4 12 4 2 4 single pulse shape SIp eX2 1 4 13 NL ls C M S 4 15 Son 4 16 vp d 0 c M 4 18 fatte 4 21 4 2 9 difference BILL DN 4 23 TP ER 4 25 SAL 10 ODIOSA 4 27 Slc DE D SNO PUER 4 30 Rocke CUNEO ore TC 4 32 4 14 DUSE GPC ONZ 4 34 ABl 4 36 4 36 GEI centena MENERENIERNUR OREMUS ND 4 38 GE TM m 4 40 e flere 4 42 EAT ND OUS Usum MERI MEME TT 4 44 ELS 4 47 4 3 1 dec phase 22 2 4 50 4 3 8 tocsy dec phase 22 2 4 52 4 3 9 inadeguate 20 BOE 4 54 nosse pnas DIOE BIG 4 56 HI 4 58 tesy miev ITO pE siaii 4 60 5 MULTINUCLEAR NMR MEASUREMENT 5 1 OUTLINE OF MULTINUCLEAR NMR MEASUREMENT 5 1 B 5 1 5 1 2 Relative Sensitivity of ultinuclear NM 5 2 5 1 3 Multinuclear Observation 1 5 5 4 5 2 MULTINUCLEAR NMR MEASUREMENT 5 5 5 2 1 M ultin
21. 4 2 2 single pulse dec ex2 Single pulse measurement with heteronuclear decoupling Directory usr delta global experiments 1d Purpose of measurement To carry out measurement using a single pulse sequence with heteronuclear decoupling Pulse sequences x pulse x domain relaxation delay noe time irr domain E Irr atn noe atn dec Extension sequences noe The defaultis TRUE decoupling The defaultis TRUE Parameters x domain Observation nucleus The default is Carbon13 Offset Observation center The default is 100 ppm X sweep Observation range The default is 250 ppm x points Number of points to sample The default is 32K scans Number of scans to accumulate The default is 1000 scans X prescans Number of dummy scans x 90 width 90 pulse width The default is x90 set in the probe file x angle Flip angle The default is 30 deg x atn T he attenuator value xatn set in the probe file x pulse Pulse width computed as x angle x 90 width x ulli 90 relaxation delay Waiting time between repeated pulses The default is 2 s repetition time relaxation x acq time Data processing The standard process list is std carbon autophase list NM ECA ECX USM 3 4 11 4 USAGE OF PULSE SEQUENCES 4 2 3 single pulse shape ex2 Single pulse measurement using shaped pulses Directory usr delta global experiments 1d Purpose of measurement set the 90
22. 4 USAGE OF PULSE SEQUENCES 4 1 EXTENSION SEQUENCES The concept of extension sequences is used for each sequence used in the NMR spectrometer For example to use presaturation to eliminate a solvent signal in a single pulse experiment select Presaturation from the extension functions in the sequence of single pulse ex2 T his section explains the purpose and parameters of these extension sequences which are used in common in the individual sequences 4 1 1 dante presat Dante presaturation reduces a signal that would overwhelm the desired peak such as a Water signal in an aqueous solution sample making it easy to detect the sample signal B Pulse sequences dante attenuator x domain dante pulse dante interval Parameters presat time Duration of presaturation The default is the same as relaxa tion delay Take care not to set a time longer than relaxation delay dante pulse Dante pulse width The default is 2 us dante interval Dante pulse interval The default is 100 us dante attenuator Determines RF output for the dante pulse The default is 40 dB Every time 3 dB is added the RF output is halved dante loop Indicates number of repetitions of the dante pulse Supplementary note Dante presaturation eliminates a signal from the observation center It is appropriate for eliminating a very strong solvent signal such as one from light water NM ECA ECX USM 3 4 3 4 USAGE OF PULSE SEQUENCES
23. Determines RF output for the selective excitation pulse The default is the attenuator value xatn_ soft set in the probe file Every time 6 dB is added the pulse width is halved Resonance position of the peak to be selectively excited The default is the same as x offset W aveform of the selective excitation pulse The default is GAUSS x spinlock pulse 90 pulse width of the spin lock pulse The default is x90 spin set in x spinlock atn delta mix time relaxation delay repetition time mix time loop total mix time grad 1 grad 1 amp grad 2 grad 2 amp grad 3 grad 3 amp grad shape grad recover Data processing the probe file Determines RF output for the spin lock pulse The default is xatn spin set in the probe file W aiting time Mixing time The default is 50 ms W aiting time between repeated pulses The default is 7 s relaxation delay x acq time Number of irradiation times of the spin lock pulse Total mixing time Pulse width of the lst FG pulse PFG1 The default is 1 ms Pulse output of the 1st FG pulse PFG 1 The default is 20 Pulse width of the 2nd FG pulse PFG2 The default is the same as grad 1 Pulse output of the 2nd FG pulse PF G2 The default is 3096 Pulse width of 3rd FG pulse PFG3 The default is the same grad 1 Pulse output of the 3rd FG pulse PFG3 The default is 5 W aveform of the FG pulse Select SQUARE SINE or GAUSS The default is SINE Recovery
24. NO 428 92 sexo INO in NO NO 9572 92 190 00 sn x X X 76 12 20x10 CHjSn 110 2450 sn X X X X 102 2530 CHjSn 10 2450 sb NO NO 5725 52 52x10 sb 4275 72 11bd0 Te NO NO X NO 6 12 13x10 CD NO X X 087 089 C NO 10 52 53010 DO NO X Y 2644 32300 cse 72 26910 CNO DO D LO LO LO 659 32 18 Bak DO 32 44 DO tale 93H 72 3440 tah DO PINO NO x Y 10 52 ipa nafto LO LO LO 118 72 nafto LO LO LO s30 72 0 Lo 10 LO 150 72 00 to 10 t0 138 no 48 52 C B D C 32 sw 64110101010 180 30 233 764110 to LO LO 30 10 32 os io xs se NM ECA ECX USM 3 5 21 5 MULTINUCLEAR MEASUREMENT 1 Sk oo Stick Natural bun
25. mi o os vo w no x wo sor 12 sas von cw 1o fto 955 gt com un no no no 52 sco no xe 7 N scu no x eus cun scu no x v sm sa 205 cun s fno fno m arrar os rea no x x 396 2 canos 60 a wo a a am was se No no no wo 75 in 4 5 ar no no sosa an 22690 war mar no no x 2 mas Wer 00 10 ms foo wo x x x me 2 00 E zr sw 9 220 5 20 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT Sk S k Mmi dign 300 400 500 600 percent spin SOROR 10 LO LO LO 946 52 18 MN NR LO LO LO LO H0 52 156 Rh 15 30 et Ag zT Cd 1275 12 69 Cd CH COO cd NONO 1226 12 76 _ m in
26. x pulse 90 pulse width in the PC observation channel The default is x90 set in the probe file x atn D etermines RF output The default value is xatn set in the probe file Every time 6 dB is added the pulse width is halved irr domain Irradiation nucleus The default is Proton irr offset Irradiation center The defaultis 5 ppm irr pulse 90 pulse width in the tH irradiation channel The default is irr90 set in the probe file irr atn Determines RF output in the irradiation channel The default is irratn set in the probe file Every time 6 dB is added the pulse width is halved selection angle Flip angles 45 90 or 135 of the irradiation pulse The default is 45 deg selection pulse The pulse width in the irradiation channel It is computed as selection angle irr pulsex 90 j constant Value of J The default is 140 Hz relaxation delay Waiting time 1 5 s between repeated pulses This value is 4 5 s for molecular weights about 300 It is about 2 5 for higher molecular weights repetition time relaxation delay x acq time Data processing The standard process list is std dept list 5 3 4 19 4 USAGE OF PULSE SEQUENCES 1 How to interpret the spectrum The appearances and features of signals for the multiplicity of resonance lines are shown Appearances of signals Multiplicity of resonance lines 2 gt C lt lt CH
27. 3 2 7 2 SPECTROMETER CONTROL 2 Select Queue to change the priority A aabe Spectrometer Control 831517193 single pulse 24 OCT 2003 14 22 00 Atsushi Abe 45 171211 single_pulse 24 OCT 2003 14 22 01 Slot Job Submit Time 24 OCT 2003 14 22 01 EZ 3 Change the priority value amp aabe Spectrometer Control dinde Isa 24 OCT 2003 14 22 03 Atsushi_Abe 5 517211 single_pulse 24 OCT 2003 14 22 01 Atsushi Abe 81211103 eS Ee M easurement Queue order is changed when priority value is changed 2 8 NMECA ECX USM 3 2 SPECTROMETER CONTROL 2 1 4 Sample Monitor T he state of the present sample can be displayed in the Spectrometer Control window In the menu bar of the Spectrometer Control window select Options Monitor Params and turn ON the toggle switch 4 aabe Spectrometer Control Queue State OWNED Selected Job UNENOWN 84654575 single pulse 23 OCT 2003 18 10 58 Spinner status Spinning speed of as lot Expected Finish gt spinner Slot number of ASC Sp pores of Temperature Control Current state of the REE meee sample i RIEN gt State of NMR lock Sample Temperature State of shim Estimated time of Measurement completion Lock signal Intensity Remaining number of r
28. 4 25 steno 4 56 noesy phase pfgzz ex2 4 56 ibiq e 2 40 O Observation of nuclei having a resonance frequency close to that of the H nucleus 5 9 Sigo METERS 2 22 Open Automation File 2 41 Operational procedure multinuclear measurement 5 6 Mar VN 2 22 Sind me ENTE 2 31 OWNED mee 2 81 NM ECA ECX USM 3 INDE X P Parameter 1 4 ione AH MONUI IS 4 36 Rc RR 2 22 2 50 xi Hi TERRIER 2 64 Precautions for sample preparation 5 11 Precise PC 2 94 Oli cesser san er tin dts 4 4 Presentation Manager 1 4 2 82 Printing Validation result 2 60 Probe 2 67 Prope 2 66 Probe DUDIE BIO 2 88 Problems involved with wide chemical shift 5 12 Problems with low frequency HP PE 5 14 Process NE 2 31 Process Interactive Global 2 31 Process Interactive Local 2 31 Mors yen tea 2 31 Process Ndimensional 2 31 Processing 2 50 PUN da MENU TU 1 2 Pulse Calculator T ool 3 12
29. 5 cse 450 300 150 0 150 ppm Fig 5 18 chemical shifts NM ECA ECX USM 3 5 29 5 MULTINUCLEAR MEASUREMENT 4000 3000 2000 1000 0 4019 1787 C Mes Rh OCOCH3 2H2O0 n CSM e Rh PM e Ph CI BPh 1797 1000 0 C Mes Rh PMe Ph CIICI 4000 3000 2000 1000 0 Fig 5 19 chemical shifts 600 500 400 300 200 100 0 ppm 55 556 41 CsHsN AgCIO THF 529 258 DMSO H O AgCIO DMF AgClO CH3 CO 600 500 400 300 200 100 0 ppm Fig 5 20 Ag chemical shifts 5 30 NM ECA ECX USM 3 800 600 644 400 490 505 Cd C3H 544 Cd CH3 Cd C2H5 800 600 100 nS 130 7 5 155 7 155 9 100 USM 3 400 5 MULTINUCLEAR NMR MEASUREMENT C 200 0 288 99 1 7 cacy cacio 330 110 0 caso 200 0 Fig 5 21 chemical shifts 74 3 coss 17 5 CH3 Sn t C H 19 5 0 100 200 059 48 7 103 6 151 2 CH SnCl sonent CH3 JSSn CH2CH 35 125 35 80 6 3
30. Magnetic field strength The value of this magnetic field strength is only displayed It cannot be changed in the Sample T ool window The magnetic field strength provides very important information NMR frequency can be calculated from the magnetic field strength and a gyromagnetic ratio ratio The frequency offset of 0 ppm is calculated so that it may become the precise reference point this is TM S for the and nuclei of the scale Using this method any nuclei can perform criterion setting of an axis using an absolute frequency However change of the magnetic susceptibility of a sample produces an error In this case the reference position of an axis is set up using an internal standard Field Strength 1L7473579 T Fig 2 6 Field Strength B Liquid helium level The value of this liquid helium level is only displayed It cannot be changed in the Sample T ool window Helium 87 Fig 2 7 Liquid helium level If it falls below the required amount cautions the background color of the screen turns yellow and warnings the background color of screen turns red will be indicated Liquid nitrogen level The value of this liquid nitrogen level is only displayed It cannot change in the Sample Tool window Nitrogen 891 Fig 2 8 Liquid nitrogen level If it falls below the required amount cautions the background color of the screen turns yellow and warnings the background color of the screen turns red w
31. 1 us 11 81 11 81 11 81 A dB 79 dB 79 dB 79 dB 79 dB 20 us 1 us 11 581 1 us 1 us 7 5 dB 4 79 dB 79 dB 79 dB 79 dB 6Li LF1 19 75 us 79 us 39 5 us 10000 us 11 81 19 0412 dB 19 0412 dB 13 0206 dB 51 23 dB 79 dB 7Li LF1 19 8 us 79 2 us 79 2 us 39 6 us 1 5 1 us 9 dB 21 0412 dB 21 0412 dB 15 0206 dB 79 dB 79 dB 4 gt Fig 2 40 90 pulse width display window 25 This window can only display the contents of a probe file and cannot change the value in the probe file 2 52 NM ECA ECX USM 3 2 SPECTROMETER CONTROL omm 2 9 DISPLAYING AND CHANGE OF AN INSTRUMENT Display and change of an instrument parameter be performed 2 9 1 Display of an Instrument Parameter 1 Select Tools Params in the menu bar of the Spectrometer Control window The Params window opens DELAY RATIO AUTOLOCK LEVEL AUTOSHIM DELAY AUTOSHIM MODE Fig 2 41 Params window 2 Select a parameter to display parameter value with a mouse The selected parameter 15 highlighted and the value of a parameter 15 displayed M tl aabe Parameter Tool scc2 nim AF DELAY RATIO AUTOLOCK LEVEL AUTOSHIM DELAY AUTOSHIM_ MODE AUTOSHIM TRACK CHANGER SAMPLE DEC AMP DEC PWIDTH DEC XMTR OLOCK LEVEL AUT OSHIM MODE AUTOSHIM OFF 4 AUT OSHIM TRACK AUTOSHIM OFF Fig 2 42 Display of the parameter NM ECA E
32. 2 5 2 11 ABNORMAL DISPLAY OF A 2 58 NM ECA ECX USM 3 CONTENTS Guess 2 59 y 2 59 2 12 2 Printing Validation 2 60 21243 Saving Results to 8 FIG 2 60 el 2 61 lok he atti ene en gt 2 61 E RE sic BO EE m CT 2 62 6 A 2 63 NET 2 64 mere 2 66 2 67 2 16 1 Display of Information for a Specified Nucleus 2 67 2 16 2 Saving a Value to the Probe 2 68 Er HIM 2 69 2 18 GRADIENT SHIM TOOL 2 71 cin UIE he Gradient 2 71 2 18 42 Gradient 2 73 2 19 SPECTROMETER CONFIGURATION s stridet ire in 2 78 2 20 EXPERIMENT AND QUEUE 2 80 AUS rS one 2 80 Ter 2 82 2 20 3 Restating M easurement GO 2 83 2 20 4 Cancelling M easurement STOP 2 85 2204 9 Measurement 2 86
33. 3 4 41 4 USAGE OF PULSE SEQUENCES 4 3 4 coloc ex2 H eteronuclear long range shift correlation measurement Directory usr delta global experiments hetcor COLOC is abbreviation of COrrelation spectroscopy range Coupling Purpose To observe correlation signals between peaks having long range spin spin coupling This method is appropriate for the assignment of quaternary carbon Pulse sequences x pulse x 2 x pulse 180 90 delta 1 NE x domain relaxation lt gt 7 _delay y pulse y pulse x2 y pulse 90 180 90 ir atn_dec y domain Extension sequences decoupling The defaultis TRUE Parameters x domain Observation nucleus The default is Carbon13 x Offset Observation center The default is 100 ppm X sweep Observation range The default is 250 ppm X points Number of points to sample along the t axis The default is 1024 scans Number of scans to accumulate a multiple of eight The default is eight scans X prescans Number of dummy scans The default is four scans y domain Observation nucleus of the f axis The default is Proton y offset Observation center of the f axis The default is 5 ppm y sweep Observation range of the f axis The default is 15 ppm y points Number of points to sample along the t axis The default is 128 4 42 NM ECA ECX USM 3 x pulse x atn y pulse y atn long range j delta 1 delta 2
34. Proton and COSY Hetcor Combination 1 Gradient DOF COSY Fig 2 34 Automation window Standard mode NM ECA ECX USM 3 2 39 2 SPECTROMETER CONTROL Start of automatic measurement l Enter the necessary minimal parameters in the following table Parameter Explanation Filename Saving file name Comment Comment Slot Slot number for the auto sample changer at auto sample changer use Temp Set Setting temperature for the VT unit Temp State Setting the VT state Solvent Solvent 2 Setup arbitrary options Typical arbitrary parameter Explanation Notify Transmission place for the measurement completion e mail Hold Holding transmission place of measurement completion e mail Gradient Shim Performing gradient shimming Gradient shimming is performed only when measuring the first sample or after changing the sample time Enhance Filename A date is added to the file name 3 Click on the method button Proton Method 25 method can be continuously recorded like as a measurement Queue However the order of measurement is the same order recorded to the meas urement Queue a new measurement Queue is taken from the Experiment Tool window during automatic measurement it will interrupt after the Queue of the present experiment finishes 2 40 NM ECA ECX USM 3 2 SPECTROMETER CONTROL m Automation window icons Open A utomation File The present
35. The default is 250 ppm Number of points to sample The default is 32K Number of scans to accumulate The default is 1000 times Number of dummy scans Flip angle The default is 45 deg 90 pulse width The default is x90 set in the probe file Pulse width computed as x 90 width 19 Indicates 180 pulse width x 90 width 2 Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved Value of gt The default is 140 Hz relaxation delay Waiting time between repeated pulses The default is 1 s repetition time 4 16 relaxation delay x acq time NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES irr domain Irradiation nucleus The default is Proton irr pwidth Pulse width irr90 hi of the decoupling pulse that is set in the probe file irr offset Irradiation center The defaultis 5 ppm irr noise D ecoupling pulse mode The defaultis WALTZ irr atn dec Determines RF output for decoupling The default is the attenuator valueirratn hi set in the probe file Every time 3 dB is added the RF output is halved Data processing The standard process list is std apt list How to interpret the spectrum The appearances and features of signals for the multiplicity of resonance lines are shown below Appearance of signal patterns Multiplicity of the resonance lines Singlet Doublet Triplet Quartet NM ECA ECX USM 3 4 17 4 USAGE OF PUL
36. e tis recommended that you stop spinning the sample tube during measurement 4 46 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 3 6 hmqc pfg ex2 PFG H observation heteronuclear shift correlation HM QC measurement Directory usr delta global experiments hmqc LS is the abbreviation of Pulsed Field Gradient HM QC 15 the abbreviation of H eteronuclear M ulti Quantum Coherence Purpose To observe correlation signals between directly coupled H and PC Since H is observed this measurement enhances the S N ratio compared with PC observation heteronuclear shift correlation measurement Pulse sequences x pulse x pulse x2 90 180 x domain relaxation delay y pulse y pulse 90 90 Y irr atn dec y domain grad 1 grad 2 grad 3 FG channel grad 1 amp grad 3 amp grad 2 amp 1 2 constant t 1 2 xj constant grad 3 Extension sequences decoupling The defaultis TRUE presat timing default is the same as relaxation delay dante presat The defaultis FALSE tri mode Select Off Presaturation or Homo Decouple default is Off Parameters x domain Observation nucleus of the 1 axis The default is Proton x Offset Observation center of the 1 axis The default is 5 ppm X Sweep Observation range of the 1 axis The default is 15 ppm X points Number of points to sample along the 5 axis The default is 1024 NM ECA ECX US
37. max y points 4 USAGE OF PULSE SEQUENCES 90 pulse width of the observation channel C of the f axis The default is x90 in the probe file Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 90 pulse width of the observation channel H on the f axis The default is y90 in the probe file Attenuator value yatn set in the probe file Every time 6 dB is added the pulse width is halved Value of the long range The default is 10 Hz W aiting time When y points 2 x y sweep gt 1 2 x long range set delta 1to y points 2x y sweep When points 2 x sweep lt 1 2 long range set delta 1to 1 2 xlong range W aiting time 1 3 x long range j M aximum value of y points relaxation delay Waiting time between repeated pulses The default is 1 5 s Data processing The standard process list is 2d hetcor abs list How to interpret the spectrum The long range correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and f axis cross NM ECA ECX USM 3 4 43 4 USAGE OF PULSE SEQUENCES 4 3 5 hmbc pfg ex2 PFG H observation heteronuclear long range shift correlation HM BC measurement absolute value type Directory usr delta global experiments hmbc 27 is the abbreviation of Pulsed Field Gradient HM BC isthe abbreviation of H eteron
38. peak to be eliminated The default is 5 ppm X sweep Observation range The default is 15 ppm X_points Number of points to sample The default is 4K scans Number of scans to accumulate The default is 16 times X_prescans Number of dummy scans 5 3 4 21 4 USAGE OF PULSE SEQUENCES 0 x pulse 90 pulse width x90 set in the probe file x atn D etermines RF output The default attenuator value is xatn set in the probe file Every time 6 dB is added the pulse width is halved watergate selection Select the water gate excitation characteristic The default is W 5 wgh x pulse Pulse width of water gate The default is the 90 pulse width x90 set in the probe file wgh null W ater gate excitation range default is 5000 Hz wgh tau Indicates the water gate pulse interval wgh grad Pulse width of the PFG pulse The default is 1 ms wgh grad amp Output of the PFG pulse The default is 20 grad shape Waveform of the PFG pulse The default is SQUARE wgh grad recover Recovery time after the PFG pulse The default is 0 1 ms relaxation delay Waiting time between repeated pulses The default is 3 s repetition time relaxation delay x acq time Data processing The standard process list is std proton list Supplementary note Due to the water gate excitation characteristic the bigger the number the better the selectivity However the measurement is easily influenced
39. shaped pulse width when obs sel atn is used Pulse sequences obs sel pulse obs sel atn x domain relaxation delay Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple T he defaul is Off tri mode Select Off Presaturation or Homo Decouple he defaul is Off Parameters x domain Observation nucleus The default is Proton offset Observation center The default 15 5 ppm X sweep Observation range The default is 15 ppm x points Number of points to sample The default is 16K scans Number of scans to accumulate The default is 16 scans X prescans Number of dummy scans obs sel pulse 90 pulse width of the shaped pulse The default is the pulse width X90 soft set in the probe file obs sel atn Determines RF output for the selective excitation pulse The default 15 the attenuator value xatn soft set in the probe file Every time 6 dB is added the pulse width is halved obs sel shape Waveform of the selective excitation pulse The default is GAUSS relaxation delay Waiting time between repeated pulses default is 5 s repetition time relaxation _delay x acq time Data processing The standard process list is std proton list 4 12 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 4 single pulse shape slp ex2 Selective excitation measurement using shifted laminate pulses Directory usr delta global experiments 1d Purp
40. 2 44 Change Phase and Amplitude using the toggle button 2 56 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 10 2 Calculation of Pulse Width and Attenuator Value Calculate and display the pulse width and the attenuator value of a shaped pulse in the Shape Viewer window Only RF Shapes provides a target for calculation ERE _ FG Shapes RF Shapes Noise FrepRepone Tip 41 093 Square Reference Worksheet Power Level dB dB Attenuation E ET 60 0 80 0 40 0 0 0 abundance 2 In p 1 1 t u d POET f f amp t 0 3 0 1 0 1 0 3 0 0 abundance Ruler State Position inside Pulse l Enter a value into Reference of 90 Pulse and Power Level 2 Enter a value into Worksheet of 90 Pulse or Power Level The remaining value is calculated from the entered value and the Reference value NM ECA ECX USM 3 2 57 2 SPECTROMETER CONTROL 2 11 ABNORMAL DISPLAY A SPECTROMETER Select Tools Status in the menu bar of the Spectrometer Control window The situation of the alarm of a spectrometer is investigated and the result is dis played Delta Console 4 4 Delta File Processors Viewers Tools Analysis Acquisition INFO NO Instrument Alarms are Fig 2 45 Display of the spectrometer alarm on Delta C onsole 25 A transitional error may be reported if this check button is
41. 200 0 100 Fig 5 9 O chemical shifts 0 50 100 150 200 ppm 765 119 159 80 119 4 7 7 1239 cese 168 Ber 185 cHE cF 210 8 200 ppm 64 892 113 1373 Cicer CH 0 50 100 150 Fig 5 10 chemical shifts NM ECA ECX USM 3 5 25 5 MULTINUCLEAR MEASUREMENT 150 100 50 0 80 0 Atom aoe 50 0 1 7 arom p 75 20 Ac Nc 7 95 40 100 105 150 100 50 0 Fig 5 11 AI chemical shifts 60 40 20 0 20 40 23 5 2 3 26 5 13 9 5 30 5 18 5 rossi 4 5 20 5 cHalsSicsHs enses 33 9 17 0 18 5 60 40 20 0 Fig 5 12 20 40 2961 chemical shifts 5 26 50 34 AI CH3CN 46 50 60 53 5 50 60 NM ECA ECX USM 3 200 100 97 Pr 112 5 P O 140 220 143 CHs NPF 200 100 293 esso
42. 5 23 5 MULTINUCLEAR MEASUREMENT 200 207 3 178 3 192 8 200 400 388 378 383 160 120 80 149 8 123 5 135 5 4 129 4 123 4 77 1 148 2 bibi CDCI 128 0 4 co 128 5 77 2 CF COOH cots chet Eom 116 5 CF COOD 130 5 127 7 67 4 132 6 ds 0 n 160 120 80 Fig 5 7 chemical shifts 300 200 100 180 113 153 100 205 108 HCONH 185 116 73 o NHoCsHaN ese NH COCH 40 0 30 3 ili C220 39 5 5 20 6 CH4COOH 49 8 e TMS 40 ppm 0 0 ppm 93 85 0 visco 30 NH NO3 NO 400 5 24 300 200 100 Fig 5 8 4N DN chemical shifts NH 0 ppm NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 600 500 400 300 200 m 0 100 ppm 600 340 13 5 338 130 15 CH CHCOOCH C2H5 20 269 19 6 242 0 286 6 254 70 371 204 0 600 500 400 300
43. 6 dB is added the pulse width is halved 4 38 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES ae relaxation delay Waiting time between repeated pulses The default is 1 5 s repetition time relaxation delay x acq time y pl correction Value to be entered in the first order term P1 for the phase correction of the t axis Data processing The standard process list is 2d cosy phase autophase list How to interpret the spectrum B oth the axis and the f axis represent H chemical shift The correlation signal appears at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross The correlation signal does not appear at the points between signals having coupling NM ECA ECX USM 3 4 39 4 USAGE OF PULSE SEQUENCES 4 3 3 hetcor ex2 eteronuclear shift correlation measurement Directory usr delta global experiments hector HETCOR is abbreviation of H ETeronuclear COR relation Purpose To observe correlation signals between the directly coupled heteronuclear peaks Pulse sequences x pulsex2 x pulse 190 90 x domain relaxation delay y pulse y pulse 90 90 irr domain A T irr_atn_dec 1 2 xj constant t 1 4 constant Extension sequences decoupling The default is TRUE Parameters x domain Observation nucleus default is C arbon13 x Offset Observation center The defau
44. 65 Priority input 2 20 6 Slot The Slot input box is specified when using an auto sample changer 2 86 NM ECA ECX USM 3 2 SPECTROMETER CONTROL m 2 20 7 StartTime of Measurement Although measurement is usually added to a Queue after recording an experiment the start time of the added measurement can be delayed However since an error can occur at this time it differs from the time when measurement actually starts tens of seconds to1 minute l Select measurement 2 Specify time to the J ob Start Time input box 4 14 aabe Spectrometer Control Tools Config Queue Machine Options 84495216 single pulse 17 DEC 2003 13 45 42 Atsushi 8414905233 single pulse 17 DEC 2003 13 45 43 C17 DEC 2003 13 45 43 e ss upon 8 2 I CR EZUR 197 4 2 Mum ICI 99 s RG Fig 2 66 Input of measurement start time 2 20 8 Measurement Information If you double click on the experiment displayed on the Spectrometer Control window the J ob Info window that displays information about measurement opens dA aabe Job Info for scc2 nm jeol co jp 00 043 single pulse ex Atsushi Abe single pulse 5314052186 Fig 2 67 Job Info NM ECA ECX USM 3 2 87 2 SPECTROMETER CONTROL 2 21 APPENDIX 2 21 1 Probe Tuning The tuning method of the TH5AT F G2 probe will be explained as an example W hen turning on the power supply of the auto tuning unit the TH5AT F
45. 90 1 where PW 1 90 pulse width when the attenuator value is ATT1 PW 2 90 pulse width when the attenuator value is ATT2 For example when the RF power is half power that is the attenuator value 15 ATT1 3 dB and the 90 pulse width is 12 ws the attenuator value for the 90 pulse width of 200 5 with the Gaussian waveform is given by ATT 3 041064 27 19 7 dB NM ECA ECX USM 3 3 11 3 ADJUSTMENT PARAMETERS 3 7 USAGE OF PULSE CALCULATOR TOOL The Delta software includes the Pulse Calculator tool You can calculate a pulse width from an attenuator value and vice versa using this tool This section explains how to use it B Starting Pulse Calculator tool Select Tools Pulse Calculator from the Experiment Tool window m aabe Experiment Tool single pulse ex2 Ec ED sample id com mer t force E scc2 nmjeol co jp Total Collection Time 00 01 03 The Pulse Calculator window opens 15 aahe Pulse Calculator Reference Fig 3 4 Pulse Calculator window Using the Pulse Calculator tool For example when 90 pulse width which attenuator value 15 8 dB is 10 4s in order to calculate the attenuator value for 90 pulse width of 20 ws carry out following operation l Input 10 us to 90 Pulse of Reference 2 Input 8 dB to Power Level of Reference 3 12 NM ECA ECX USM 3 3 ADJUSTMENT OF NMR PARAMFTFRS
46. CH Singlet Doublet Triplet Quartet LIT Features e The spectrum corresponding to each carbon group can be created from spectra 0 to e Signals of quaternary carbon deuterated solvent do not appear e Thesensitivity is almost the same as that of the INEPT method e Pulses can be repeated after the relaxation time T 4 20 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 8 wgh ex2 easurement using water gate pulse sequence for eliminating solvent signal Directory usr delta global experiments 1d Purpose To reduce a signal that would overwhelm the desired signal such as a water signal in an aqueous solution sample Pulse sequences x pulse W5 wgh x pulse x 6 x domain relaxation delay wghgrad ah grad FG channel paigad amp wgh_grad_recover grad recover W1 6 90 90 W2 0 45 135 45 135 W3 0 20 8 62 2 131 6 131 6 62 2 20 8 W4 0 410 4 29 4 60 5 132 8 132 8 60 5 29 4 10 4 W5 0 47 8 18 5 37 2 70 134 2 134 2 70 37 2 18 5 7 8 Extension sequences raw suppression Select Off Raw or Rawscuba The default is Off dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple The default is Off tri mode Select Off Presaturation or Homo Decouple default is Off B Parameters x domain Observation nucleus The default is Proton x Offset Observation center
47. Example x 90 width parameters ly aca Glos To enter numerical values varied with a constant interval in a range the format is y_acq start value gt stop value step size D Cc To enter a parameter having a unit enter the unit with at least one numerical value If you specify only one unit the unit 15 applied to all numerical values At the end of input press the key or move the mouse pointer outside the window If an error is detected in the array parameters a message 15 displayed To change the numerical values in the parameter input box move the mouse pointer into the input box and correct them using the arrow keys or the backspace key To enter a long array scroll the end of the window To return to the beginning after scrolling use the You can use both acq and z acq simultaneously In this case first the y acq array is executed using the z parameter values then the y acq array is executed with the increment of the z parameter and these steps are repeated resulting in pseudo 3D data 2 96 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Using the array parameter window The procedure for setting the scans parameter is described as an example 1 Double click on the scans button of the Experiment Tool window The array parameter window opens ital aahe Set scans Fig 2 70 Array parameter window 2 Selectthe Y check button by clicking on it 3 Enter the parameter values on
48. G2 probe can be tuned automatically W hen turning off the power supply of the auto tuning unit and removing the flexible shaft the TH5AT F G2 probe tuning can be performed as follows H tuning in normal measurement To set the H measurement conditions 1 Click on the Expmnt button in the Delta Console window The Open Experiment window appears 2 Click on the Global Directory button The contents of the Global Experiment directory are displayed 3 Click on the measurement mode single pulse ex2 to highlight it 4 Click on the Ok button The Experiment Tool window appears 5 Set each parameter for normal measurement in sequence in the Header Instrument Acquisition and Pulse sections in the Experiment Tool window Tuning the probe 1 Click on the force tune check box in the Header section aabe Experiment Tool single pulse ex2 Get Acq View z Pulse 2 74 2 c 301 3 av Total Collection Time 00 01 03 2 88 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 Click on the Submit button The tuning message is displayed as shown below At this time the probe has already been set to tuning Wem Please tune coil to Proton and notify when complete probe tune 2477 probe match 4115 3 Setthe tuning sensitivity If the LEVEL METER on the head amplifier chassis moves too much or too little a
49. NMECA ECX USM 3 2 SPECTROMETER CONTROL ve 2 1 3 Management of the Measurement Queue In the Spectrometer Control window the Queue measurement can be managed Starting measurement Queue This is the starting method for the measurement Queue in the hold state Click on the Go button in the Spectrometer Control window M easurement Queue starts in the H old state 25 n normal measurement if you click on the Submit button in the Experiment T ool window since the measurement Queue starts automatically it is not necessary to start the measurement by the button Canceling measurement Queue This is the canceling method of measurement Queue l Select the measurement queue to cancel from the measurement Queue list box displayed by the mouse T he selected measurement Queue is highlighted 2 Click on the STOP button in the Spectrometer Control window T he selected measurement Queue is canceled Changing Queue priority Changing the priority value attached to each Queue can change the Queuing order The priority value is 0 to 255 Higher priority carries a greater value The default priority is 32 l Change the connection mode to Console mode aabe Spectrometer Control Config Queue Machine Options Slot Watcher v View Log Files E Job Submit Time 6 Close g Aea MEME n He N2 eee 5
50. PULSE SEQUENCES 4 3 2 cosy phase ex2 Phase sensitive double quantum filtered COSY measurement Directory usr delta global experiments dqf cosy 25 COSY isthe abbreviation of COrrelation SpectroscopY Purpose To observe correlation signals between J coupled peaks Using the double quantum filter signals having no J coupling with singlet signals such as solvent or isolated group are eliminated The method is appropriate for observing correlation signals located near the diagonal signals Pulse sequence x pulse x pulse 90 90 x2 Purge pulse demam relaxation delay Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple T he default is Off tri mode Select Presaturation or Homo Decouple T he default is Off Parameters x domain Observation nucleus The default is Proton x offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample along the t axis The default is 1024 y points Number of points to sample along the t axis The default is 256 scans Number of scans to accumulate The default is 16 scans X prescans Number of dummy scans The default is four scans x pulse 90 pulse width of the observation channel H The default is the x90 value set in the probe file x atn Attenuator value xatn set in the probe file Every time
51. PULSE SEQUENCES B 4 1 4 noe The NOE Nuclear Overhauser Effect arises from carrying out irradiation in the irradiation channel during waiting time enhancing the S N ratio Parameters irr atn noe Determines RF output for NOE irradiation The default is the attenuator value to which irratn lo is set in the probe file Every time 3 dB is added the RF output is halved noe time NOE irradiation time The default is the same as relaxation delay irr pwidth Pulse width for NOE irradiation The default is the pulse width irr90 hi set in the probe file irr domain Irradiation nucleus The default is Proton irr offset Irradiation position resonance frequency of the peak to be irradiated The default is 5 ppm irr noise Decoupling mode The default is WALTS 4 6 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES gt 4 1 5 decoupling U sed to perform heteronuclear spin spin decoupling Parameters irr atn dec Determines RF output for decoupling The default is the attenuator value to which irratn hi is set in the probe file Every time 3 dB is added the RF output is halved irr pwidth Pulse width of the decoupling pulse The default is the pulse width irr90 hi set in the probe file irr domain Irradiation nucleus The default is Proton However in some cases such as when it is the same nucleus as y domain there is no input box irr offset Resonance frequency of the peak to be irradiat
52. PULSE WIDTH OF SELECTIVE EX CITATION PULSES mmm 3 10 3 7 USAGE OF Attenuator Calculator TOOL s 3 12 NM ECA ECX USM 3 3 ADJUSTMENT OF NMR PARAMFTFRS 3 1 PURPOSE OF MEASURING PULSE WIDTHS This section explains the significance and principle of measurement of pulse widths and general precautions About pulse width When an RF pulse having the magnetic field strength B is applied to the magnetization M in arotating frame the magnetization will precess about the axis along the direction of the applied RF pulse with the angular velocity yB rad s where 7 15 the magnetogyric ratio ib angle 20 m Y RF pulse Fig 3 1 Precession of magnetization in the rotating frame As a consequence if the RF pulse width the duration of the RF pulse is At s the magnetization after the pulse is then related to the magnetization after the pulse by the flip angle thus Flip angle 78 4 rad In the NMR terminology the RF pulse width resulting in a flip angle X is called the X pulse width and the pulse itself the X pulse To carry out precise NMR measurement it is essential for you to know the magnetic field strength of the RF pulse However in the pulsed NM R spectrometer it is more convenient to use the 90 pulse width than to use the field strength B directly so that when the magnetic field strength of the RF pulse is referred to gener
53. PUSS SECON 2 37 Pulsa WiU 3 1 pulse widths in the irradiation sans E E T 3 7 Q duete LO 2 63 Queue 2 82 Queue pull down 2 82 Queue state 2 80 R DUE ESSA RN T 4 9 Reading shim 2 25 Recall DUWO 2 26 Reference data for relaxation times and measurement conditions of principal nuclei 5 17 Reference 5 8 Refresh 2 26 Relationships between nuclear species and 5 5 19 INDEX Relative sensitivity of multinuclear NER oin decet 5 2 Relaxation times of multinuclei 5 16 Release of spectrometer 2 4 Reschedule 2 82 Reset 2 26 Restating measurement 2 83 a 4 27 roesy 1 2 4 2 Run 2 41 Run Sawtooth E xperiment Dijon Mew TTE 2 47 RUNNING 2 81 5 Sample 2 9 Sample spinning 2 16 2 13
54. Pulse width of the second pulse It is computed as 90 width mn 90 delta Waiting time for long range coupling measurement T default is 0 ms relaxation delay Waiting time between repeated pulse sequences The default is 1 5 s repetition time relaxation delay x acq time grad 1 Pulse width of the first FG pulse PFG 1 The default is 1 ms grad 1 amp Pulse output of the first FG pulse PFG 1 The default is 5 grad 2 Pulse width of the second FG pulse PFG2 The default is the same as grad 1 grad 2 amp Pulse output of the second FG pulse PF G2 The default is the same as grad 1 grad shape type Waveform of the FG pulse Select GAUSS SINE or SQUARE The default is SINE grad recover Recovery time after the FG pulse The default is 0 1 ms Data processing The standard process list is std cosy abs list How to interpret the spectrum B oth the axis and the f axis represent H chemical shift The correlation signal appears at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross Supplementary note e Setting the second pulse width pulse 2 to a 45 pulse makes it easy to observe correlation signals near the diagonal signal This measurement also gives information on the relative sign of J coupling e Set the parameters as follows PFGl grad 1xgrad 1 amp PFG2 grad 2x grad 2 amp lt 1 1 NM ECA ECX USM 3 4 37 4 USAGE OF
55. To hold down the left mouse button while moving the mouse To drag an item you point to an item on the screen and then drag it using the mouse NM ECA ECX USM 3 5 1 FUNDAMENTALS OF DELTA EI 1 1 1 2 DELTA CONSOLE 1 2 1 2 1 menu bar in the Delta Console window 1 2 1 2 2 Bar in the Delta Console 1 4 2 SPECTROMETER CONTROL 2 1 SPECTROMETER CONTROL 2 1 2 11 Starting the Spectrometer Control Window 2 1 2 1 2 Connecting and Releasing 56 2 2 2 1 3 Management of the easurement 2 7 ERAS 2 9 22 SAMPLE TOOL WINDOW enn 2 10 2 2 1 Starting the Sample T ool 2 11 2 2 2 Display of SCM Related 1 2 12 2 2 3 Loading Ejecting Sa DID assessor dd rn Fm EH A ERA 2 13 2 16 2 2 5 Variable Temperature 2 17 2 2 6 Selecting the Deuterated 50 2 20 OF ME VU CEPR 2 21
56. View Log File View Cryogen Log in the menu bar of the Spectrometer Control window The Cryogen L og window opens Start _ End 8 MOV 2005 8 DEC 2003 Le 9 Fig 2 48 Cryogen L og window 25 display can be selected from Month Quarter and Y ear The display can be changed by selecting M onth Quarter or Y ear selecting View from the menu bar in the C ryogen L og window 4S The front screen or the following screen can be displayed by clicking on the arrow button Plotting log Click on the Plot Cryogen Graph button in the Cryogen Log window to plot the graph NM ECA ECX USM 3 2 61 2 SPECTROMETER CONTROL 2 13 2 Machine Log Select Tools View Log File View Current Machine Log in the menu bar of the Spectrometer Control window The View machine log window opens aabe View machine log Fig 2 49 View machine log window Display of an old Machine log Select Tools View Log File View Old Machine Log in the menu bar of the Spectrometer Control window The View machine log old window opens vi aabe View machine er old S DEC 2003 10 13 55 WARNING No SMTP SERVER specified Usin f 5 2003 10 13 55 INFO Parsed machine wiring successfully DEC 2003 10 13 57 INFO BBP software Version 1 001 Fig 2 50 View window B Plotting log A log can be printed by clicking on the Print button in the View machine log window or the
57. automatic measurement template is deleted and a new automatic measurement template is read Include Automation File A new automatic measurement template is added to the present automatic measurement template The Queue display window for automatic measurement is opened Hide Queue The Queue display window for automatic measurement is closed A utomation E ditor The A utomation Editor window is opened Run Experiment Click on this button when performing an experiment a check window indicating when measurement is performed will appear Refer to the AUTOMATIC MEASUREMENT of a separate volume for details on automatic measurement NM ECA ECX USM 3 2 41 2 SPECTROMETER CONTROL 2 4 2 Advanced Mode in the Automation Window In Advance mode you can change measurement conditions such as number of scans to accumulate and repetition time 4 aabe Automation 5 2 Slot En E Temp State TEMP OFF E Solvent Em OROFORM D Proton and D JF COSY Proton and TOCSY Flock Gradient COSY Gradient Fig 2 35 Automation window Advanced mode 2 42 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Change to Advanced mode When ADVANCED is not displayed in the Automation window Standard mode is in operation Change to A dvanced mode using the following procedures Select File Advanced Mode in the menu bar of the Automation window
58. carried out immediately after starting the system Perform recheck after carrying out loading of a sample lock and measurement 2 58 NM ECA ECX USM 3 2 SPECTROMETER CONTROL a nr 2 12 VALIDATION This verifies whether software 15 correctly installed in the spectrometer control computer 2 12 1 Executing Validation 1 Select Tools Validation in the menu bar of the Spectrometer Control window The Delta Installation Validation window opens 4 4 aabe Delta Installation Validation scc nm jeol co jp Fig 2 46 Delta Installation Validation window 2 Click on the Go button The check of a file is performed and the result is displayed 4 4 Delta Installation Validation 2 Atsushi Abe aabe Date B DEC 2003 16 39 36 Product NMR Instrument Control Software Version vl 3 Beta 12 04 03 09 11 AIX Instrument 1 Model No gt JNM ECASOO Serial No NMLOS60001 Files Passed fe delay Files Failed 0 Files Not Found 0 Total Files BU PASSED control Fig 2 47 Display of Validation result NM ECA ECX USM 3 2 59 2 SPECTROMETER CONTROL 2 12 2 Printing Validation Result Click on the Print the results button in the Delta Installation Validation window The Validation result is printed to the default printer 4 aabe Delta Installation Validation scczZ nm je
59. in the RAW sequence The default is 100 ms NM ECA ECX USM 3 4 9 4 USAGE OF PULSE SEQUENCES 4 2 10 MEASUREMENT 4 2 1 single pulse ex2 Simplest single pulse measurement Directory usr delta global experiments 1d B Purpose of measurement To carry out measurement using a single pulse sequence B Pulse sequences x pulse x domain relaxation delay Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple T he default is Off tri mode Select Off Presaturation or Homo Decouple default is Off Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X Sweep Observation range The default is 15 ppm X points Number of points to sample The default is 16K Scans Number of scans to accumulate The default is 8 scans prescans Number of dummy scans x 90 width 90 pulse width The default is x90 set in the probe file x angle Flip angle The default is 45 deg x atn T he attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved x pulse Pulse width computed as x 90 widths 2191 ua 90 relaxation delay Waiting time between repeated pulses The default is 5 s repetition time relaxation delay x acq time Data processing The standard process list is std proton autophaselist 4 10 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES
60. is performed the sample tube gives rise to the background signals that are independent of the sample signals under investigation Therefore when it is difficult to distinguish the background signals from the sample signals a sample tube made of materials which do not contain the nucleus must be prepared For example sample tubes made of polymers such as Teflon should be used for Si NMR and sample tubes made of a polymer or quartz should be used for NMR There is no problem in using a glass sample tube for a solution as the line widths of the sample signals are narrow when compared with the background signals from the glass NM ECA ECX USM 3 5 11 5 MULTINUCLEAR MEASUREMENT 5 3 3 Problems Involved with a Wide Chemical Shift Range Some signal peaks appear in wide chemical shift ranges in multinuclear NMR for example 15000 ppm and Pt 5000 ppm The theory behind measurement of such nuclei differs from that of H and PC observations The problems involved are explained below and in 5 3 4 Chemical shift range The frequency range where the peaks of the nucleus to be observed appear is called the chemical shift range here The chemical shift range becomes clear with experience for every nucleus Generally the bigger the atomic number and the more d orbital and f orbital electrons the nucleus possesses the wider the chemical shift range For the chemical shift ranges of the typical nuclei ref
61. jp Processing Thousands 1 0 Current Spin 02 0 3 0 4 0 5 14 Hz Me me LE SHIM Zi 4 SHIM 72 d SHIM 73 SHIM_ 74 4 5734 7 20727 EE NMECA ECX USM 3 2 69 2 SPECTROMETER CONTROL 3 In order to display processed data click on the Process Vector button A aabe Shim On FID scc2 nm jeol co jp Processing 0 10 20 30 40 5 0 Current Spin que Spin SHIM Zi m SHIM 72 74 Ec 207 271 207 271 4S For contents of processing place a check mark next to the processing item in Processing the menu bar 4 Click on the Go button Data acquisition begins Data is continuously updated 5 Selecting the shim axis to display by Shim Group 6 Adjust the resolution while viewing a spectrum 7 Click on the Stop button after resolution adjustment is complete U pdating the data stops 8 Close the Shim ON FID window 2 70 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 18 GRADIENT SHIM TOOL 2 18 1 Outline of the Gradient Shim The resolution adjustment shim adjustment is carried out to adjust the current running through the multiple shim coils inside the SCM so that the magnetic field applied to the sample becomes uniform Each shim coil produces a magnetic field of a differ
62. linearity you can obtain the pulse width simply by calculation as described below To calculate the pulse width from the attenuator value W hen you change the attenuator value you can obtain the pulse width according to the following equation P Woo P Woo 10 2 2 1 PW 1 90 pulse width when the attenuator value is ATT1 gt 90 pulse width when the attenuator value is ATT2 For example when the RF power is half power that is the attenuator value is ATT1 23 dB and the 90 pulse width is 12 us the 90 pulse width for the attenuator value ATT2 15 dB is given by PW 12x1095053 2 24 us To calculate the attenuator value from the pulse width The attenuator value can also be determined from the pulse width according to the following equation P Woo 2 2 1 20 109 P Woo 1 W here PW 1 90 pulse width when the attenuator value is ATT1 PW 2 90 pulse width when the attenuator value is ATT2 For example when the RF power is half power that is the attenuator value is ATT1 23 dB and the 90 pulse width is 12 ws the attenuator value for the 90 pulse width 24 usis given by ATT 3 20xlogy lt gt 9 dB 3 8 NMECA ECX USM 3 3 ADJUSTMENT OF NMR PARAMFTFRS R 3 5 MEASUREMENT OF PULSE WIDTHS IN DEPT90 To eliminate both and CH in DEPT effectively inhomogeneity of B affe
63. processing If you specify a file name 1D Processor or nD Processor window opens according to the number of Data processor dimensions of data in the specified file lt gt Refer to the separate PROCESSING USER S MANUAL for details on the 1D Processor and nD Processor window A data slate is a multipurpose NMR data display viewer 1D 2D and 3D data can be displayed single window Moreover it can produce a print of two or more spectra on the one chart lt gt For details refer to the separate PROCESSING USER S MANUAL The data viewer 15 the tool provided for the display of multi dimensional NMR data The contents of the window displayed change with the numbers of dimensions of the data This is used for obtaining both the projection and the cross section of multi dimensional NM data This is a tool for saving and managing the directory that is used in the Delta program and a file that is stored in the directory If this tool is File manager used not only can it easily reference a file in the directory but it can perform the copy edit deletion change of name and data conversion of a file Presentation presentation manager is a tool for customizing the plot format of NM manager data A parameter viewer is a tool that displays information such as a data set parameter report sequence processing history and an electronic signature A spreadsheet is a tool that displays inf
64. sample into the probe W hen you want to measure a pulse width under normal conditions use the standard sample W hen you want to measure a pulse width under special conditions such as at high temperature or using a special solvent select a sample which can be measured under the same conditions 2 Carry outtuning 3 Enhance the resolution 4 Observe spectra using single pulse ex2 or observe spectra using single pulse dec ex2 5 Set a peak which can be used as a mark to the center of the observation range Select as the mark a broad peak having a relatively short relaxation time If the relaxation time is too long you may not obtain the 90 pulse successfully a Select Copy position to buffer from the Cursor Tool Pick mode and click on the top of the mark peak to copy it A X seconds single pulse 18 200 0 300 0 400 0 100 0 Millions 4 67129 ppm l a clea 1 4 72 4 71 47 4 69 468 4 67 4 66 465 4 64 4 63 A parts per Million 1H b Click the middle mouse button on x offset parameter in the measurement mode to paste the copied position on it 6 Setx angle to 90 deg 7 Setx 90 width to Array measurement 8 Click on the Submit button T he pulses are generated starting measurement f the Inform window appears click on the GO button 3 6 NMECA ECX USM 3 3 ADJUSTMENT 5 9 Carry out the Linearize processing on the obtained dat
65. sensitivity of multinuclear When multinuclear NMR is observed the detection sensitivity depends substantially on the nucleus The relative sensitivity as compared to the standard PC nucleus is used to estimate the degree of difficulty and the necessary time for measurement T he following figure shows the relation between the relative sensitivity and the resonance frequency of different nuclei Relative sensitivity 104 933Np7AI 10 127 in 2Na Li di H 1996 1 PRb 31 207 T 75 As Pb Cy 123Sb 25M g 35 195pt 7 pm ATTI 14 FOU Cd 109 Ag 39K 37 13 1 N 2961 Mn 63Cy 125Te T V3Rh 5 70 536 15 10 t9Fe DN H TUNABLE FREQUENCY RANGE si 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 380 390 400 Frequency ECA400 MHz Observation range using an optional low frequency tunable module Observation range using a low frequency tunable probe Monitor range using a tunable probe Fig 5 1 Relative sensitivity of multinuclear observation Refer to the tables in Section 5 5 1 for information on natural abundance nuclear spins and relative sensitivities of nuclei NM ECA ECX USM 3 5 3 5 MULTINUCLEAR MEASUREMENT 1 5 1 3 Multinuclear NMR Observation Instrument A block diagram of the basic composition of the multinuclear NMR observation instrument is shown below Oscillator
66. state at present is displayed Red is lock off yellow is during the search for the lock signal and green is lock on This is a gain of the lock receiver The amplification rate of a lock signal is adjusted Usually the value described in solvent def file is set up In case of an auto lock a gain is adjusted automatically and NMR lock signal 15 detected This is the output level of the lock channel Usually the value described in the solvent def file is set up In case of an auto lock the level is adjusted automatically and an NMR lock signal is detected This is the lock signal phase The value described in the shim file is set up A lock phase depends on RF filter in the mainly used probe and the lock channel Moreover if the dielectric constant of a sample and an ion concentration changes greatly the lock phase may change This is the offset lock frequency Usually the value described in the solvent def file is set up It is the frequency offset required in order to set TMS asto 0 ppm NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 2 8 Shim Control The Sample T ool window controls shimming In the Sample T ool window a shim of four axes is displayed as one group a shim group In order to change a display group select the shim group to display from the Shim Groups list box or select it from the list box in the display shim axis Lock level meter Shim group Fig 2 15 Shim control part Eac
67. 0 3 109 CoHs Sns 5 20 2 1025 51 8 66 3 crs SnMn CO 26537 101 2 5 05 2 9 65 1 0 86 4 0 100 200 Fig 5 22 Sn chemical shifts 5 31 5 MULTINUCLEAR MEASUREMENT 0 1000 2000 3000 4000 1860 1522 1190 HePtcl Br 882 H PtCl Br 579 H PtCI Br 248 0 1622 H PtCI K PtCI 0 1000 2000 3000 4000 Fig 5 23 chemical shifts 500 0 500 1000 1500 2000 820 1180 240 640 1150 1440 _ n C3H Hg 0 330 840 1290 930 500 0 500 1000 1500 2000 Fig 5 24 chemical shifts 5 32 5000 ppm 5000 ppm 2500 ppm 2500 ppm NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 600 300 0 300 358 3 0 CH3CH CH CH PbOCOCH CH3CH CH CH Pb 371 CHCl 308 CH3CH PbOCOCH Pb OCOCH s 300 0 300 600
68. 11 Using a solid sample 5 11 V Tand 2 59 Variable 2 17 NM ECA ECX USM 3 Vector Viewer window 2 48 LE NE RR 2 19 ET ON oce 2 18 WAITING 2 81 NM ECA ECX USM 3 wet SUDO iier 4 8 0 2 4 21 2 E A 2 50 Zero fill 4 2 50
69. 3 Input 20 us to 90 Pulse of Worksheet Calculation result is displayed in Power L evel of Worksheet and B 1 4 aabe Pulse Calculator Power Level 8 00 14 02 dB Close 12500 00 Hz NMECA ECX USM 3 3 13 USAGE OF PULSE SEQUENCES Bl 4 1 EI S 4 3 BELL tt 4 3 ona 4 4 E 4 5 CEN gt 4 6 EL 4 7 BECOME dE coc PERDER 4 8 RCRUM 4 9 MN INE FINEM IM 4 10 ete crete nies MK MOD 4 10 4 2 2 single pulse GSC 4 11 Aoc SIME ees 4 12 4 2 4 single pulse shape 4 13 2195 SINGE PUDE a 4 15 4 16 4 18 4 4 21 4 23 DUE paran tse E HIER eee 4 25 4 2 11 rosy 10 DIES 4 27 UNDAE OTO PR T UU T M 4 30 DUIS EI 4 32 4 2 14 double pulse dec ex2
70. 58 TRITT TET 2 50 1 3 ACQUISITION 2 35 dvanced 2 42 eerie 4 16 qM REPE 4 16 Array 2 95 Array Parameter window 2 97 RUD LESE oo edixit decret 2 22 Auto Lock eer rixae bis 2 22 PANG STS DURON oaov iir rs eek 2 26 Automation 2 41 Automation Tool window 2 39 B Block diagram of the RF system 3 3 C Calculation of 90 pulse width of selective excitation pulses 3 10 Calculation of 90 pulse widths after the attenuator value is changed 3 8 Calculation of pulse width and attenuator 2 57 oi rer tha 4 27 Canceling measurement Queue 2 7 Cancelling measurement 2 85 Change to Advanced mode 2 43 Changing a 015 2 49 Changing an instrument parameter 2 54 Changing Queue priority 2 7 Chemical shift range 5 12 IIE DICH E 4 42 iliam E 4 42 COMMEN 2 40 2 2 Connecting to spectrometer 2 2 Connection 1 4 Soci DT 2 2 Control the NMR lock
71. 9 18 24 000 00 33 Fig 2 39 Vector View window The Vector View window has the function which displays a spectrum on real time as the data monitor during measurement If you click on the View button in the Vector View window the present data is transmitted from the spectrometer to the screen In addition a transmission interval is an interval specified by mod return in the Acquisition section of the Experiment window For example if the value of mod return is set to 2 data is transmitted for every two accumulations A load for a network increases when you shorten the updating interval of the data So try to set a suitable value Updating time for a spectrum in the Vector View window lasts until an accumulation is terminated from the state where the View button was clicked If the updating time of a spectrum exceed 5 minutes the View button turns OFF auto matically This is for reduces the load to a network Once again if you click on the View button an updating spectrum is restarted 4S Even if the parameter specified to the mod return parameter is 1 when data points are too many or Acquisition time and relaxation delay are extremely short or when the load of a network is large an updating spectrum cannot be performed at the interval specified 2 48 NM ECA ECX USM 3 2 SPECTROMETER CONTROL e 2 6 1 Changing a Display This is the method of changing a FID display and a processed data display in the V
72. C is the abbreviation of Heteronuclear Single Quantum Coherence TOCSY isthe abbreviation of TOtal Correlation SpectroscopY Purpose To observe correlation signals between not only directly coupled and PC nuclei but also H nuclei which belong to the spin network containing that By observing the H nucleus the S N ratio is enhanced compared with that achieved using the observation heteronuclear TOCSY method B Pulse sequences Total mix time e pulse x pulse x 2 x pulse x pulse x 2 x pulse x pulsex 2 90 180 90 180 90 180 relaxation x domain delay MLEV 17 y pulse y pulse gt gt x 240 90 x 240 90 trim trim ulse ulse y pulse y pulse y pulse y pulse rie NA E o t 21 15 2 Purge pulse y domain irr atn dec FG channel 1 4 constant 0 5 ms Extension sequences decoupling The defaultis TRUE dante presat The defaultis FALSE tri mode Select Off Presaturation or Homo Decouple T default is Off B Parameters x domain Observation nucleus of the 1 axis The default is Proton X Offset Observation center of the 1 axis The default is 5 ppm X sweep Observation range of the f axis The default is 15 ppm x points Number of points to sample along the t axis The default is 1024 y domain Observation nucleus of the f axis The default is Carbon13 y swee
73. C observation two quantum coherence correlation measurement Directory usr delta global experiments inadequate 27 is abbreviation of Pulsed Field Gradient INADEQUATE is the abbreviation of Incredible Natural Abundance DoublE QUA ntum Transfer Experiment Purpose of measurement To observe the connection between PC and PC Because the sensitivity is very low it is difficult to measure it However if you can acquire data you can analyze a carbon skeleton directly Pulse sequences x pulse x pulsex2 x pulse pulse 90 180 90 120 90 ti relaxation x domain delay 1 4 constant irr atn noe Y noe time Y grad 2 grad 1 FG channel grad 2 amp grad 1 amp Extension sequences noe The default is TRUE decoupling The defaultis TRUE Parameters x domain Observation nucleus The default is Carbon13 x Offset Observation center The default is 100 ppm X sweep Observation range of the 1 axis The default is 250 ppm points Number of points to sample along the t axis The default is 2048 scans Number of scans to accumulate a multiple of 8 The default is 8 scans X_prescans Number of dummy scans The default is four scans 4 54 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES y sweep Observation range of the f axis The defaultis 1 5 x x sweep y points Number of points to sample along the t axis The default is 64 x pulse 90 pulse width of the o
74. CX USM 3 2 53 2 SPECTROMETER CONTROL 2 9 2 Changing an Instrument Parameter 1 Selectthe parameter to change and display the parameter value ata aabe Parameter Tool scc2 nm jeol co jp DELAY RATIO An AUTOSHIM DELAY AUT OSHIM MODE AUT OSHIM TRACK AUT OLOCK LEVEL AUTOSHIM MODE AUTOSHIM OFF d AUTOSHIM TRACK AUTOSHIM OFF 1 2 Input the parameter value into the parameter input box into the right of the parameter name 25 The only parameter that can be changed is the parameter displayed on the parameter display box 25 Parameter related directly to execution of a pulse sequence such as pulse width and pulse waiting time can be changed only in a part f the value of a parameter is changed in this window since value is immediately sent to a spectrometer and the state of a spectrometer will its change cautions are required even if the spectrometer is under measurement 2 54 NM ECA ECX USM 3 2 SPECTROMETER CONTROL omm 2 10 SHAPE VIEWER A tool which a Shaped pulse or a noise source can be viewed is provided by Delta Three kinds of FG Shape RF Shape and Noise can be displayed NM ECA ECX USM 3 5 4 aabe Shape Viewer FG Shapes RF Shapes Noise FreuResponse local 41 093 Square Reference Worksheet 90 Pulse lus Time Power Level dB Attermation GAUSS 2 400 60 0 80 0 abundance 20 0
75. DEOR E REX FIEREHPIS EE 2 17 2 2 6 Selecting the Deuterated 50 2 20 MES usb dl LOCK RR 2 21 Bes AIL DU 2 23 23 EXPERIMENT EDITOR TOOL WINDOW enm 2 2 2 3 1 Measurement File Experiment 1 2 28 Po er epi 2 29 2 33 A47 2 35 UCCNEME cir 2 37 2 4 AUTOMATION TOOL WINDOW emm 2 39 241 Standard M ode in the A utomation 2 39 2 4 2 Advanced ode in the Automation Window eee 2 42 2 5 RUN SAWTOOTH EXPERIMENT WINDOW 2 47 eles 2 48 Lol 2 49 EB mac 2 50 27 NEW INSTANCE OF A SELECTED JOB 2 51 2 52 NM ECA ECX USM 3 gt 29 DISPLAYING AND CHANGE OF AN INSTRUMENT PARAM ETER 2 53 2 9 1 Display of an Instrument 2 53 2 9 2 Changing an Instrument 2 54 EIE ER en eee MEIN 2 55 Zui eu OQ ME DAN CREDERE 2 56 2 10 2 Calculation of Pulse Width and ttenuator V alue
76. ER CONTROL B Setting process list The default process list is described in the measurement file supplied as a standard W hen changing these contents you can change a process list in the following procedure l Click on the Edit button in the Header section of the Experiment Tool window Experiment Tool single pulse exz File Tools View Options Inst i Acquisition Pulse 4 ample 10 active global std proton autophaselist Edit EX Total Collection Time 00 01 03 glabal std _proton_antophasellist Process NDimensianz Process List Fig 2 25 Set Process window 2 30 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 Select the kind of process list Kinds Process Ndimensional Process Local Process Interactive Local Process Global Process Interactive Global Send data to finger Other 3 Selecta process list Explanation The data is sent to 1D Processor or nD Processor after measurement is complete However processing is not performed Data processing is performed using the specified process list in a local directory after a measurement is complete and the result is saved Neither 1D Processor nor nD Processor is displayed Data is sent to 1D Processor nD Processor after measurement is complete Then the specified process list is set in a local direc
77. FUNDAMENTALS OF DELTA 12 DELTA CONSOLE WINDOW W hen you start the Delta program the Delta C onsole window appears lt gt Fig 1 2 Y ou can start all other tools from this window In the Delta Console window you can start each Delta tool using the pull down menu for each item of the menu bar or the tool bar button M ove the mouse pointer to the pull down menu or tool bar item and click on the mouse left button File Processors Viewers Tools Analysis Acquisition Menu bar Tool bar Delta Processing and Control Software View window Copyright 1990 2003 by JEOL USA Inc Version 4 3 Beta 10 16 03 21 55 Linux 1 CFR part 11 technical features are enabled Fig 1 2 Delta Console window 12 1 The menu bar the Delta Console window The list of items is displayed beneath of the title bar of the Delta Console window This is called the menu bar Select any function in this menu bar using the mouse File Processors Viewers Tools Analysis Acquisition Fig 1 3 Menu bar of theDelta Console window Pull down menu Each item of the menu bar has a pull down menu When you select a menu bar item using the mouse left button the pull down menu appears Fig 1 5 select an item from the pull down menu drag the mouse with the left button of the mouse depressed and releasing the left button of the mouse over the item you want to select If you select a pull down menu by mistake after moving th
78. Hz standard 95 Hz 140 to 500 Hz 37 to 1100 Hz e f you set scans to an odd number insert dc balance at the top of the process list of the X axis the 1 axis e tis recommended that you stop spinning the sample tube during measurement NM ECA ECX USM 3 4 49 4 USAGE OF PULSE SEQUENCES 4 3 7 hsqc dec phase pfgzz ex2 Phase sensitive HSQC measurement Directory usr delta global experiments hsqc 25 HSQC is abbreviation of eteronuclear Single Quantum Coherence Purpose To observe correlation signals between H and PC which are directly coupled Since is observed this measurement enhances the S N ratio compared with PC observation heteronuclear shift correlation measurement Selecting single quantum coherence in principle makes the resolution in the f axis better than HM QC measurement Pulse sequences x pulse x pulse 2 x pulse x pulse X 2 x pulse x pulse x 2 90 180 90 180 90 180 relaxation x domain delay y pulse x 240 90 y pulse y pulse 90 90 y pulse x 240 90 Ise y pulse 90 y pulse y pulse 90 90 irr atn dec FG channel o 1 4xj constant 0 5 ms Purge pulse t 21 10 2 y domain Extension sequences decoupling The defaultis TRUE dante presat The defaultis FALSE tri mode Select Off Presaturation or Homo Decouple T he default is Off B Paramet
79. INSTRUCTIONS CONTENTS INDEX JNM ECA Series JNM ECX Series JNM ECS Series Delta V4 3 6 MEASUREMENT USER S MANUAL INMECA ECX USM 3a UG2007 08110237 AUG2007 08110 Printed in Japan Series Series NV ECS Series Delta 3 6 MEASUREMENT USER S MANUAL JNM ECA Series JNM ECX Series JNM ECS Series This manual explains how to adjust the system how to set measurement conditions and other procedures for performing various measurements using the ECA ECX ECS NMR system Please be sure to read this instruction manual carefully and fully understand its contents prior to the operation or maintenance for the proper use of the instrument L NOTICE e This instrument generates uses and can radiate the energy of radio frequency and if not installed and used in accordance with the instruction manual may cause harmful interference to the environment especially radio communications e The following actions must be avoided without prior written permission from JEOL Ltd or its subsidiary company responsible for the subject hereinafter referred to as modifying the instrument attaching products other than those supplied by JEOL repairing the instrument components and parts that have failed such as replacing pipes in cooling water system without consulting your JEOL service office and adjusting the specifie
80. L 2 15 PROBE TUNE This performs tuning on the specified nucleus Although tuning can also be performed at measurement when tuning before measurement tuning is performed by the following procedure 1 Select Config Probe Tune in the menu bar of the Spectrometer Control window The Probe Tune T ool window opens 4 51 aabe Probe Tune Tool Fig 2 54 ProbeTuneT ool window 2 Selectthe coil to tune in Coil 3 Selectthe nucleus to tune in Domain 4 Setan Offset if necessary 5 Click on Force Tune Unless a check mark is placed in Force Tune the tuning of a nucleus which has already been tuned is not performed 6 Click on the Tune Now button Tuning starts 7 Click on the Close button after tuning is complete The Probe Tune T ool window closes 2 66 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 16 PROBE TOOL This displays information on the specified nucleus in the probe file Moreover in Console mode a probe file can be rewritten 2 16 1 Display of Information for a Specified Nucleus 1 Select Config Probe Tool in the menu bar of the Spectrometer Control window The Probe T ool window opens De Soft Power Level dB sas una um 2 Select a coil in Coil 3 Selecta nucleus in Domain A 90 pulse width for the specified nucleus and information on attenuator value are displayed NM ECA ECX USM 3 2 67 2 SPEC
81. LF1 MATCH dial p IU LF1 TUNE dial 6 On completion of tuning click on the GO button After the PC tuning is complete the tuning message appears At this time the probe has already been set to tuning Please tune coil LF1 to Carbonl3 and notify when complete probe tune 0 prohe match 0 7 Perform the H tuning 8 On completion of tuning click on the GO button to start normal PC measurement NM ECA ECX USM 3 2 93 2 SPECTROMETER CONTROL Precise PC tuning l Turn the LF1 MATCH dial to minimize the deflection of LEVEL METER 2 Turn the LF1 TUNE dial to minimize the deflection of LEVEL METER 3 Turn the LF1 MATCH dial by 10 graduations and turn the LF1 TUNE dial to minimize the deflection F1 of LEVEL METER M emorize the deflection F1 of LEVEL METER atthat time 4 Turn the LF1 MATCH dial by 10 graduations and turn the LF1 TUNE dial to minimize the deflection F2 of LEVEL METER Compare the deflection F2 of LEVEL METER at this time with F1 Turn the LF1MATCH dial to minimize the deflection of LEVEL METER and then turn the LF1TUNE dial to minimize the deflection of LEVEL METER 2 94 NM ECA ECX USM 3 2 SPECTROMETER CONTROL a 2 21 2 Array Measurement W hen you perform array measurement there are parameters whose values are changed in some order They are called the array parameters This section describes the methods of se
82. M 3 4 47 4 USAGE OF PULSE SEQUENCES scans X prescans y domain y offset y Sweep y points x pulse x atn y pulse y atn constant relaxation delay repetition time grad selection grad 1 grad 1 amp grad 2 grad 2 amp grad 3 grad 3 amp grad shape grad recover Data processing Number of scans to accumulate The default is 1 scans Number of dummy scans default is four scans Observation nucleus of the f axis The default is Carbon13 Observation center of the f axis The default is 85 ppm Observation range of the f axis The default is 170 ppm Number of points to sample along the t axis The default is 256 90 pulse width of the observation channel H of the f axis The default is x90 in the probe file Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 90 pulse width of the observation channel C of the f axis The default is y90 set in the probe file Attenuator value yatn set in the probe file Every time 6 dB is added the pulse width is halved Value of J The default is 140 Hz W aiting time between repeated pulse sequences T default is 1 5 s relaxation delay x acq time Relative intensity ratio of the to be applied to y domain Pulse width of the first FG pulse PFG1 The default is 1 ms Pulse output of the first FG pulse 1 The default is 60 Pulse width of the second FG pulse PFG2 Th
83. NTROL Shim control button and list box The followings button and list box are used for controlling shims Button Refresh Shims Auto Shims AUTOSHIM OFF Explanation The spectrometer is always monitoring shim value and lock signal intensity has memorized the best shim value at maximum lock signal intensity This best shim value is cleared T he best shim value is called and the value is set to each axis The shim value displayed on the Shim Control part in Sample Tool is updated to the shim value set to the spectrometer now Automatic shim adjustment of the specified axis is performed When performing automatic shim adjustment select the combination of an axes to perform automatic shim adjustment from the list box If selection is complete automatic shim adjustment will start Select AUTOSHIM OFF when you want to stop automatic shim adjustment B Shim control relation parameters Lock signal display T he bar graph in the top of the Shim Control part is called a lock level meter This is used to monitor the lock signal intensity The upper of the bar graph is Coarse and the lower is Fine Moreover the actual lock signal intensity is also displayed numerically 2 26 level meter Lock signal intensity Fig 2 21 Lock level meter NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 3 EXPERIMENT EDITOR TOOL WINDOW If you click on the Expmnt button in the Spectrometer Control windo
84. Nucleus 2H Deuterium is turned ON 2 Specify other measurement conditions Scans Set the number of scans to accumulate 4 multiples X Offset Click on the Once button and turn on Twice and Calculate The resonance position of a signal is searched automatically by Calculate and X Offset sets it to the observation center Once cor rects X Offset only once before performing gradient shimming T wice adjusts it finely after the 1st iteration is terminated Recvr Gain Turn on Calculate Receiver gain is adjusted automatically Relax Delay Setthe waiting time of the repetition pulse 5 85 Iterations Set the number of times of iteration If itis 0 the number of times of iteration is judged automatically Shim Set Turn on Z1 Z2 Z3 and Z4 Specify the combination of the shim that performs gradient shimming 2 74 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Range o W idth Usual measurement does not change When Width is 100 when not specified and When you use the sample whose liquid amounts are different such as micro cell input the effective range which performs gradient shimming lt refer to the subsequent page 3 Turn ON Display Field Map W henever 1 iteration is terminated the magnetic field map is displayed When Display Field M ap is OFF a map is not displayed 4 Turn ON AutoLock A utolock is applied after you finish gradient shimming NM ECA ECX USM 3 2 SPECTROMETER CON
85. ONTROL VT OFF When the temperature hold function is not provided Click on the button in Temperature of the Sample Tool window The temperature controller stops and the state display of a sample changes to the VT OFF state e When the temperature hold function is provided Click on the button in Temperature of the Sample Tool window The temperature controller stops and the sample state changes into the VT OFF state Temperature Hold Click on the button under Temperature in the Sample Tool window In this the temperature hold mode and sample exchange can be performed with the state of VT ON 25 n order to prevent damage by fire from a heater if you cannot terminate sample exchange during a fixed time VT is turned off automatically NM ECA ECX USM 3 2 19 2 SPECTROMETER CONTROL m unum 2 2 6 Selecting the Deuterated Solvent Select a deuterated solvent of a sample from the Solvent list box The following example shows that CHLOROFORM D has been selected If you make mistake in this setting the NMR lock not only cannot be applied but reference setting will not be performed correctly CHLOROFORM D Fig 2 13 Solvent list box 25 When selecting an item from the list box it is convenient to use the skip function If you move the mouse pointer into the list box and enter the first character of an item name from the keyboard it will skip automatically to the positio
86. Parameter window S elect the parameter to add from the Choose Parameter window Click on the Add button Repeat steps 2 3 if necessary Click on the Done button after selecting all the parameters to add The Choose Parameter window is closed and the contents of the parameter list are updated Select the added parameter from the parameter list in the Set Parameters windows The selected parameter is highlighted and the input box to the side displays the value of the present parameter After parameter change is complete click on the Run with Changes button A utomatic measurement starts Change the value of a parameter Repeat steps 6 7 if necessary NM ECA ECX USM 3 2 SPECTROMETER CONTROL 25 RUN SAWTOOTH EXPERIMENT WINDOW If you click on the Sawtooth button in the Spectrometer Control window the Run Sawtooth E xperiment window that displays a swept lock signal opens aabe scc2 nm jeol co jp Lock 42 1 Lock Level 4 180 Lock Phase Sawtooth Range 91 20000 0 19000 0 Cancel Fig 2 38 Run Sawtooth E xperiment window This function is used when verifying a lock signal When automatic locking does not function or composition of the deuterated solvent in a sample differs from the normal example 1096D 20 mixed solvent and other this function is used to verify a lock signal W hen exchanging a sample it is not needed Sawtooth display like other me
87. R sensitivity Detection sensitivity of multinuclear NMR 5 2 The detection sensitivity of NMR signals depends on the nuclear magnetic moment nuclear spin and nuclear spin concentration of the sample The detection sensitivity under a fixed magnetic field is proportional to the following expression 1 1 x N where is the nuclear spin is the resonance frequency and N is the nuclear spin concentration Note that the above expression represents the peak area Therefore a peak with a wide line width will not be as high as expected from the above expression making it difficult to detect Generally a nucleus with 1 gt 1 2 gives rise to a wide line width due to the quadrupole moment resulting in the detection sensitivity the peak height being low The larger the quadrupole moment is and the lower the symmetry of the electric field around the observation nucleus is the wider the line width due to the quadrupole moment becomes The value of and intrinsic to the nucleus and once the measurement nucleus is decided these are determined The value of N depends on the sample concentration and natural abundance Therefore to enhance detection sensitivity you need to increase the sample concentration or use an enriched sample The use of a higher magnetic field SCM 15 especially effective for nuclei of low resonance frequencies NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT B Relative
88. SE SEQUENCES 4 2 7 deptex2 DEPT measurement Directory usr delta global experiments 1d DEPT is the abbreviation of nuclear Distortionless Enhanced by Polarization Transfer Purpose This pulse sequence is used to determine the number of hydrogen nuclei directly coupled to each carbon nucleus This method provides an enhancement of the sensitivity by polarization transfer from a 1H nucleus to a nucleus and by repetition of the pulses after the relaxation time the measurement time can significantly be reduced compared with the off resonance method Spectral additions and subtractions can be performed to edit spectra because the phase shift is less than that in the INEPT method However the signal of quaternary carbon does not appear B Pulse sequence x pulse 5 90 180 relaxation x domain delay puse 5 selection pulse 0 245 90 135 irr domain irr dec 1 1 2 xj constant Extension sequences decoupling The defaultis FALSE B Parameters x domain Observation nucleus The default is Carbon13 x Offset Observation center The default is 100 ppm X sweep Observation range The default is 250 ppm points Number of points to sample The default is 32K scans Number of scans to accumulate a multiple of eight The default is 1000 times prescans Number of dummy scans 4 18 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES e
89. Sample 2 10 Sample temperature 2 17 Sample Tool window 2 10 Saving a value to the probe file 2 68 Saving Sm 2 23 Saving Validation results to a file 2 60 Selecting decoupling 5 14 Selecting 5 11 Selecting the deuterated solvent 2 20 Selection of sample tubes 5 11 Send data to finger 2 31 Sensitivity enhancement by the pulse 5 10 Setting the chemical shift reference 5 12 Shape Viewer 2 55 dis RTT TT 2 23 Shim Control 2 10 Shim control button 2 26 TID Lab reae 2 69 Shim control relation parameters 2 26 SNOW M 2 41 Signal excitation 5 12 signal 5 13 single Z 4 10 single pulse 2 4 11 single pulse shape ex2 4 12 single pulse shape slp ex2 4 13 single pulse wet ex2 4 15 cle 2 40 2 86 2 10 2 40 Spectrometer Configuration 2 78 Spectrometer control tool 1 4 Spectrometer Control win
90. TROL 0 Start and end of a gradient shim 1 Click on the Start button Gradient shimming starts and the job of gradient shimming is performed The Gradient Shim Status window opens and the progress in 96 of the iteration Is displayed aabe Gradient Shim Status Pass 1 Collecting data Experiment 40 5 Complete Ahnrt Saas 1 1 1 L Fig 2 57 Gradient Shim Status window W henever one iteration is terminated the magnetic field map is displayed on the Field Map window When several iterations are performed they are all displayed aabe Map 3 0 2 0 1 0 0 1 0 20 3 0 4 0 11 1 0 kilohertz 21 22 153 932 Hz E 10 Hz 132 82 Hz E1 Hz 22 03 i35 74 83 0 17 57 Hz 201 55 Hz 70 i5 Hz 17 85 Hz 133 45 Hz 72 81 Hz 17 85 Hz 133 45 Hz 72 81 Hz Fig 2 58 Field Map window 2 Click on the Exit button after Gradient Shimming is complete The Gradient Shim T ool window closes Reference e When a good resolution is not obtained increase the number of scans to accumu late W hen the resolution is bad at the start set many iterations e g 3 instead of 0 e Usually try to specify the shim settings for Z1 Z2 Z3 and Z4 Do not change parameter values during an operation If they change the meas urement will be influenced e n the gradient shimming a uniform sample is presu
91. TROMETER CONTROL mmm 2 16 2 Saving a Value to the Probe File l Select Tools Mode Console in the menu bar of the Spectrometer Control window aabe Spectrometer Control Config Queue Machine Options Shape Viewer Status 2 Select Config Probe Tool the menu of Spectrometer Control window The Probe T ool window opens LLLTTESFG iB Coil LOCK 90 Bi FEN Spm 90 Dec spin 3 Selecta coil in Coil 4 Selecta nucleus in Domain The 90 pulse width of the specified nucleus and information on attenuator value are displayed 5 Correct value 6 Click on the Save Probe File button The probe file is updated 2 68 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 17 SHIM ON FID Y ou can adjust the resolution in one window while viewing an actual spectrum Y ou can adjust the resolution while actually verifying situations of the signal such as the shape of the skirt portion of a peak and the line width of a peak as measured 1 Select Config Shim on FID in the menu bar of the Spectrometer Control window The Shim ON FID window opens A aabe Shim On FID 5 2 Processing Current Spin Target XAngle 45 4 XPoints 4096 a u HHA Fig 2 55 Shim ON FID window 2 Click on the Start button A spectrum is displayed A aabe Shim On FID scc2 nm jeol co
92. View machine log old window 2 62 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 13 3 Queue Log Select Tools View Log File View Current Queue Log in the menu bar of the Spectrometer Control window The View queue log window opens to aabe View queue log 5 2003 10 28 46 00 001 aabe atsushi_abe as Atsushi_Abe Deuter 5 DEC 2003 10 29 45 00 002 aabe atsushi abe as Atsushi Abe Deuter Fig 2 51 View queue log window Display of old Queue log Select Tools View Log File View Old Queue Log in the menu bar of the Spectrometer Control window The View queue log old window opens A faabe View queue Ing old File zero length Ausr eclipse queue log old Fig 2 52 View queue log old window Plotting log A log can be printed by clicking on the Print button of the View queue log window the View queue log log window NM ECA ECX USM 3 2 63 2 SPECTROMETER CONTROL 2 14 PRE TUNE When using an autotuning unit it is necessary to set up the dial value of the probe in advance Pre Tune performs these settings Pre Tuning is performed by the following procedure 1 Select Tools Mode Console in the menu bar of the Spectrometer Control window 7 aabe Spectrometer Control Tools Config Queue Machine Options Command Line Upload Manager 90 s Params Shape Viewer Status Validation LN 4 EE atc 2 Select Config PreTune
93. a 10 Find the pulse width whose signal intensity is nearest to zero The pulse width at which the signal intensity of the linearized spectrum is nearest to zero is the 360 pulse width A s the pulse widths become longer the peaks should turn upward Data Slate single_pulse 25 File Options View raiect Slicing Expansion Tools Analysis ej 0 51 0 53 0 55 0 57 0 59 0 61 0 63 0 65 Y microseconds 5 1 5 0 4 9 4 8 4 7 4 6 4 5 4 4 434 52 0 56 0 60 0 64 0 X parts per Million 1H A X microseconds x 90 width 11 Obtain the 90 pulse width by dividing the 360 pulse width by four 25 Take note of the obtained 90 pulse width together with the measurement conditions Measuring pulse widths in the irradiation channel The NMR spectrometer has been adjusted so that the pulse width does not change regardless of whether it is set in the observation channel or in the irradiation channel as long as their frequencies are the same Therefore you need not measure the pulse width in the irradiation channel NM ECA ECX USM 3 3 7 3 ADJUSTMENT PARAMETERS 3 4 CALCULATION OF 90 PULSE WIDTHS AFTER THE ATTENUATOR VALUE IS CHANGED Some measurement modes require a change in the intensity of the RF pulse during the pulse sequence If you change the intensity of the RF pulse you need to measure the pulse width again as it varies However because the RF power in the NMR spectrometer has good
94. al HF1 MATCH dial 5 mm TH Tunable Probe 5 mm TH Auto Tune Probe Fig 5 3 External appearances of major multinuclear probes NM ECA ECX USM 3 5 5 5 MULTINUCLEAR MEASUREMENT gt 5 2 2 Operational Procedure for Multinuclear Measurement l Load the standard sample into the probe Choose a proper standard sample for each nucleus It is recommended that you use the reference substances as explained in the next section 5 2 3 2 Change the observation nucleus Set x domain in Acquisition in the E xperiment window to the observation nucleus 3 Change to a suitable stick Insert a suitable stick referring the table attached the probe Since the sign of the alphabet of 1 character A B C is indicated to a stick select a stick for the observation nucleus lt Refer to the separate manual HANDLING OF HARDWARE 4 Setthe LF1 MATCH and LF1 TUNE dials to suitable values Set MATCH dial to a suitable value which is searched from the graph attached to the probe For typical nuclei such as P PC si H YO and PN adjust the TUNE dial value to that shown in the tuning dial table supplied with the probe For nuclei other than the above set the value of a nucleus whose dial value is known and whose resonant frequency is close 5 Measure the pulse width M easure the pulse width using the standard sample B e sure first to set the peak of the standard sample to the center of the observation frequency and t
95. ally is used If 15 known B can be computed by the following equation 2x yx PW B Principle of measurement of pulse widths The saturation magnetization is a vector parallel to the Z axis If the saturation magnetization is Mo and after the RF pulse with width At and strength B is applied to the saturation magnetization the observed signal intensity is M At TB At Thus the 90 pulse width is the value of At at which the signal intensity becomes a maximum when At is gradually increased However in practice it is much easier to find the position where the signal intensity becomes zero so first find the 180 pulse NM ECA ECX USM 3 3 1 3 ADJUSTMENT PARAMETERS width and then estimate the 90 pulse width as half its duration or first find 360 pulse width and then estimate the 90 pulse width as one fourth of its duration M Fig 3 2 Relationship between the time theRF pulse is applied and the observed signal intensity Effects of inhomogeneity of the RF magnetic field strength B In the previous paragraph it was assumed that the homogeneous RF magnetic field B was applied to the entire sample In practice however depending on the shape of the coil for generating the RF magnetic field and the sample position relative to the coil RF magnetic fields having various strengths are applied to the sample As a result the observed signal intensity is not a simple sinusoidal function o
96. alue is twice the pulse width x90 2 which is set in the probe file obs sel atn Set RF output amplitude of the selective excitation pulse The default Is the attenuator value xatn soft which is set in the probe file obs sel offset Resonance position of the peak to be selectively excited The default is the same as x offset obs sel shape Waveform of the selective excitation pulse The default is GAUSS x spinlock mode Select the mode of the spin lock pulse The default is 18 dB down x spinlock atn Determines RF output for the spin lock pulse The default is x atn minus the value selected in x spinlock mode spinlock strength Indicates the frequency range to be excited by the spin lock pulse mix time M ixing time The default is 250 ms relaxation delay Waiting time between repeated pulses T he default is 7 s repetition time relaxation delay x acq time grad 1 Pulse width of the 1st FG pulse PFG 1 The default is 1 ms grad 1 amp Pulse output of the 1st FG pulse PFG1 The default is 20 grad 2 Pulse width of the 2nd FG pulse PFG2 The default is the same as grad 1 grad 2 amp Pulse output of the 2nd FG pulse PF G2 The default is 30 grad 3 amp Pulse output of the 3rd FG pulse PFG3 The default is 5 grad shape W aveform of the FG pulse Select SQUARE SINE or GAUSS The default 15 SINE grad recover Recovery time after the FG pulse The default is 0 1 ms Data processing The standard process lis
97. and Pulse sections in the Experiment Tool window To tune the probe l Setthe LF COARSE knob of the probe to the PC frequency range 4S For values of tuning and matching dials for the observation nucleus refer to the table provided with the TH 5AT F G2 probe LF COARSE knob NM ECA ECX USM 3 2 91 2 SPECTROMETER CONTROL 2 Click on the force tune check box in the Header section 4 14 Experiment Tool single pulse dec ex2 File Tools View Options force tun save horter 7 Total Collection Time 00 47 27 3 Click on the Submit button The tuning messages are displayed First the tuning message is displayed 4 Setthe sensitivity of tuning If the LEVEL METER on the head amplifier chassis moves too much or too little adjust the sensitivity using the METER GAIN button and knob RF SAMPLE EMPTY CH1 CH2 CH3 CH4 LOAD O LEVEL METER CHECK CECEEECECECCEEECEEEECEEEEEEEEEEEEECECEEE SWR SELECT METER GAIN CH1 CH2 CH3 CH4 METER GAIN button and knob 5 To tune the probe minimize the deflection of LEVEL METER Adjust first the LF1 TUNE dial of the probe and next the LF1 MATCH dial Repeat these operations until no further improvement results 2 92 NM ECA ECX USM 3 2 SPECTROMETER CONTROL
98. asurement performs one signal measurement Therefore the Queue is displayed on the Spectrometer Control window Sometime is required until the first data is acquired after reading a pulse sequence M oreover data is not displayed on the Run Sawtooth Experiment window until the first acquisition is terminated The name Sawtooth arises from the waveform of the sweep of the 70 magnetic field The Z0 shim coil sweeps the magnetic field range specified with a Sawtooth Range A sawtooth signal a signal in the sweep width of sawtooth will be observed if a lock signal lies in this range W hen you cannot observe a lock signal set the L ock L evel to 255 maximum first When you still cannot find a signal set the Sawtooth Range to 8 for the greatest range If a lock signal is found set the mouse pointer to Pick Position in the Pick mode using the cursor tool and click on the lock signal 20 is automatically corrected so that the lock signal may come to the center of the screen NM ECA ECX USM 3 2 47 2 SPECTROMETER CONTROL 2 6 VECTOR VIEWER WINDOW If you click on the View button in the Spectrometer Control window the Vector View window that displays the spectrum during measurement opens aabe Vector View sccz nm jenl co jp Options Processing Ruler 01 0 2 03 0 4 0 5 0 6 07 08 09 10 11 12 13 14 15 16 17 seconds Current Time Expected Finish Delta Time Integral Value 31 OCT 2003 09 17 51 31 OCT 2003 0
99. ber of dummy scans y points Number of points to sample along the t axis The default is 256 x pulse 90 pulse width of the observation channel The default is x90 set in the probe file x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 4 60 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES x spinlock pulse 90 pulse width of the spin lock pulse The value of x90 spin in the probe file is set x spinlock atn Determines the RF output of the spin lock pulse The attenuator value 15 xatn spin set in the probe file trim Pulse width of the trim pulse The default is 1 ms mix time M ixing time The default is 50 ms relaxation delay Waiting time between repeated pulses The default is 1 5 s repetition time relaxation delay x acq time mix time loop Number of times to irradiate of the spin lock pulse total mix time Mixing time to be actually used y pl correction Value to be entered in the first order term P1 of the phase correction of the t axis Data processing The standard process list is 2d homo2d phase autophase list How to interpret the spectrum Both the f axis and the f axis represent chemical shifts The correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross When the mixing time gets longer the correlation signals with further separated nuclei appear althou
100. ber of scans to accumulate a multiple of four The default is 4 scans Number of dummy scans The default is four scans Observation nucleus of the f axis The default is Carbon13 Observation center of the f axis The default is 100 ppm Observation range of the f axis The default is 250 ppm Number of points to sample along the t axis The default is 256 90 pulse width of the observation channel H of the f axis The default is x90 in the probe file Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 90 pulse width of the observation channel of the f axis The default is y90 in the probe file Attenuator value yatn set in the probe file Every time 6 dB is added the pulse width is halved Value of J The default is 140 Hz Value of the long range The default is 8 Hz W aiting time between repeated pulses The default is 1 5 s relaxation delays x acq time Relative intensity ratio of the PFG applied to y domain Pulse width of the first FG pulse PFG1 The default is 1 ms Pulse output of the first FG pulse PFG1 The default is 60 Pulse width of the second FG pulse PFG2 The default is the same as grad 1 Pulse output of the second FG pulse PFG2 The default is the same as grad 1 amp Pulse width of the third FG pulse PFG3 The default is the same as grad 1 Pulse output of the third FG pulse PFG3 The default is computed from g
101. bes refer to the tables supplied with each probe e Stick Insert the specified stick for measurement NO Remove the stick for measurement HF M easure using the irradiation channel independently of a stick LO A n optional low frequency observation probe is required for observation e Relative sensitivity The PC sensitivity reference is taken as 1 00 25 For measurement of PF an optional F observation system is required Table5 4 Sticks used for observed nuclei WBF 3 sii nee sone T dee 300 400 500 600 percent spin sensitivity 20 tms t pe x fx 32 m sanon 00 w c s b c ms 3 220 s no no x soa 32 rsono 3 19 x no ixe 12 im wis 0 ex 2 zaa cnno coc spa se va bo oo ma no wo x we we val no no no wo 100 sz raw awos si 4m 21 cds cocir isome E TI NMECA ECX USM 3 5 19 5 MULTINUCLEAR MEASUREMENT L Reference soven de s percent spin sensitivity i ssc no no no no 10 00 m fto fto r oa
102. bservation channel C The default is x90 in the probe file x_atn Attenuator value xatn set in the probe file Every time 6 dB 15 added the pulse width is halved constant Value of The default is 40 Hz relaxation delay Waiting time between repeated pulses The default is 10 s repetition time relaxation delay x acq time grad 1 Pulse width of the first FG pulse PFG1 The default is 1 ms grad 1 amp Pulse output of the first FG pulse PFG1 The default is 20 grad 2 Pulse width of the second FG pulse PFG2 The default is the same as grad 1 grad 2 amp Pulse output of the second FG pulse PFG2 The default is grad 1 amp x 2 grad shape W aveform of the FG pulse Select SQUARE SINE or GAUSS The defaultis SINE grad recover Recovery time after the FG pulse The default is 0 1 ms Data processing The standard process list is 2d inadequate abs list How to interpret the spectrum The f axis represents the chemical shift The f axis also represents the chemical shift but its frequencies double that of the f axis The symmetrical axis is on the diagonal of the data but the peaks do not appear on the diagonal The correlation signals appear between chemically PC nuclei bonded Pursuing a pair of the correlation signals reveals the connection of the carbon skeleton Supplementary notes e The intensity of correlation signals depends on the value of j constant It is difficult for a sample hav
103. by relaxation time 4 22 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 9 difference 19 2 1D NOE measurement by difference spectroscopy Directory usr delta global experiments 1d noe 4S NOE is abbreviation of Nuclear Overhauser Effect Purpose To observe only the NOE signal of a specific peak by taking the difference between the Same peaks before and after a specific peak is irradiated In this method three dimensional positional relationships among atomic groups can be obtained Pulse sequences x pulse x pulse 90 90 noe buildup noe buildup relaxation _ delay relaxation delay x domain on resonance off resonance Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation Homo Decouple T he default is Off tri mode Select Off Presaturation or Homo Decouple T he default is Off Parameters x domain Observation nucleus default is Proton X Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm x points Number of points to sample The default is 16K scans Number of measurement a multiple of eight The default is 16 scans X_prescans Number of dummy scans X_pulse 90 pulse width of the observation channel The default is x90 set in the probe file x_atn Attenuator value xatn set the probe file Every time 6dB 15 added
104. called the HF High Frequency channel and the other channel the LF Low Frequency channel Do not confuse the HF and LF channels with the observation and irradiation channels The HF or LF channel from which a signal at the frequency of an nucleus being observed is output is called the observation channel The other channel is called the irradiation channel T he signals output from the sequencer are converted to pulses in the DDS After they are modulated they enter into the transmitter At the same time the pulses from the dual FSY enter the transmitter and are mixed there to produce the RF pulses The intensity of the RF pulses can be changed in 1 dB steps by the amplitude control in the DDS and in 0 01 dB steps by the attenuator in the transmitter allowing very fine adjustment W hen you enter a value in the attenuator box the attenuation can automatically be adjusted by the above devices so usually you do not care about them The RF pulses output from the transmitter are entered into either the HF or the LF power amplifier The RF pulses are amplified in the power amplifier and are entered into the corresponding channel in the probe The host computer selects the HF or the LF channel as the observation channel The strong RF pulses are applied to the observation channel through the duplexer A fter the strong RF pulses are switched off the weak observation signals are received by the probe The signal from the probe is amplified in the prea
105. ct the waveform of the selective excitation pulse The default is GAUSS mix time M ixing time The default is 500 ms relaxation delay Waiting time between repeated pulses The default is 7 s repetition time relaxation delay x acq time grad 1 Pulse width of the first FG pulse PFG1 The default is 1 ms grad 1 amp Pulse output of the first FG pulse PFG 1 The default is 20 grad 2 amp Pulse output of the second FG pulse PF G2 The default is 3096 grad 3 Pulse width of the third FG pulse PFG3 The default is 1 ms grad 3 amp Pulse output of the third FG pulse PFG3 The default is 1096 grad shape Select the waveform of the FG pulse from SQUARE SINE and GAUSS The defaultis SINE grad recover Recovery time after the FG pulse The default is 0 1 ms Data processing The standard process list is std proton list How to interpret the spectrum Only the peak changed by NOE due to selective excitation can be observed Thus the spectrum gives information on three dimensional positional relationships among atomic groups in the molecule 4 26 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 11 roesy 19 dpfgse ex2 1D ROESY measurement using shaped pulses Directory usr delta global experiments 1d roesy 25 ROESY is the abbreviation of Rotating frame nuclear Overhauser Effect Spectroscopy ROESY is sometimes called CAM ELSPIN CAMELSPIN is the abbreviation of Cross relaxation A ppropriate f
106. ction of spin coupled peaks while a specific peak is selectively excited This measurement clarifies the spin coupling network including the selective peak Pulse sequence x pulse x pulse x pulse 90 90 4 DIPSI2 x spinlock atn relaxation x domain delay obs sel 180 grad 3 grad 2 Ml WS gf Mp FG channels aw _ grad 1 amp grad 2 amp grad 3 amp Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple default is Off tri mode Select Off Presaturation or Homo Decouple The default is Off B Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm X points Number of points to sample The default is 16K scans Number of scans to accumulate a multiple of 16 The default is 16 scans X prescans Number of dummy scans x pulse 90 pulse width of the observation channel H The default is x90 set in the probe file 4 30 NM ECA ECX USM 3 _ obs sel 180 obs sel atn obs sel offset obs sel shape 4 USAGE OF PULSE SEQUENCES C Determines RF output the attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 180 pulse width of the selective excitation pulse The default is twice the pulse width x90 soft set in the probe file
107. ction of the Experiment T ool 5 3 2 37 2 SPECTROMETER CONTROL B Time chart Display of pulse sequence Y ou can express the time chart of a pulse sequence as the following procedure 1 Click on the Pulse tab in the Experiment Tool window The Pulse section appears 2 Click on the button ta aabe Experiment Tool single pulse ex2 repetition time 7 18383 s dante presat 5 k TRETEN Total Collection Time 00 01 0 Fig 2 33 Pulse Viewer window 2 38 NM ECA ECX USM 3 2 SPECTROMETER CONTROL ro 2 4 AUTOMATION TOOL WINDOW If you click on the Auto button in the Spectrometer C ontrol window the Automation window in which all step from measurement of data to processing and printing of data are automatically performed opens In the Automation window there are the two modes Standard mode and Advanced mode c Refer to the AUTOMATIC MEASUREMENT of separate volume for details on automatic measurement 2 4 1 Standard Mode in the Automation Window In Standard mode measurement is performed according to the measurement conditions of the number of scans to accumulate to repetition time as set as the default in the automatic measurement template aabe Automation scc2 nm jeol co jp amp 8 at 4 25 dC Curr Temp 17 2 d C Temp State TEMP OFF Lock Status CHLOROFORM D TM Notify Carbon and APT Tantam amd f
108. cts the pulse width Therefore the procedure in Section 3 3 cannot be used to measure the 90 pulse width Instead in DEPT 90 measure the 90 pulse width according to the following procedure Measuring 90 pulse width in DEPT90 measurement 1 Prepare a standard sample with as high as possible a concentration of and insert it in the probe Tune the probe Enhance the resolution Set the measurement mode to dept ex2 Setselection angle to 90 deg ou PWN Set irr_pulse for Array measurement 25 The approximate value for carrying out Array measurement is 10 to 15 us when aTH5 probe 1 used Click on the Submit button The pulses are generated starting measurement f the Inform window appears click on the GO button x Carry out the Linearize processing on the obtained data while watching the signal Find the pulse width so that the signal intensity is nearest to zero The pulse width at which the signal intensity of the linearized processed spectrum is nearest to zero is the 90 pulse width A s the pulse widths become longer the peak should turn downward File Options View Project Slicing Expansion Tools Analysis 5 d 10 20 30 4 2 0 1 0 E 2 E 71 I ven qim 67 0 65 0 63 0 5 10 0 12 0 140 160 X parts per Million 13C A X microseconds irr puls Take note of the obtained 90 pulse width together with the measurement con
109. d parts that only field service technicians employed or authorized by JEOL are allowed to adjust such as bolts or regulators which need to be tightened with appropriate torque Doing any of the above might result in instrument failure and or a serious accident If any such modification attachment replacement or adjustment is made all the stipulated warranties and preventative maintenances and or services contracted by JEOL or its affiliated company or authorized representative will be void e Replacement parts for maintenance of the instrument functionality and performance are retained and available for seven years from the date of installation Thereafter some of those parts may be available for a certain period of time and in this case an extra service charge may be applied for servicing with those parts Please contact your JEOL service office for details before the period of retention has passed e n order to ensure safety in the use of this instrument the customer is advised to attend to daily maintenance and inspection In addition JEOL strongly recommends that the customer have the instrument thoroughly checked up by field service technicians employed or authorized by JEOL on the occasion of replacement of expendable parts or at the proper time and interval for preventative maintenance of the instrument Please note that JEOL will not be held responsible for any instrument failure and or serious accident occurred with the instrument inappro
110. ded as a standard and the conditions that can be used the standard gradient shim for every probe 15 set Moreover the function in which the gradient shim can be easily performed only by clicking on an icon is also provided A gradient shim is recommended if it satisfies these two conditions e nucleus of a deuterated solvent can be used as an observed nucleus e Homogeneity spoiling can be applied for all spectrometers and probes Solvent e A Selective Gradient is used for gradient shimming of the solvent containing two or more H signals like methanol d4 or pyridine d5 In a Selective Gradient cali bration is required separate volume ADMINISTRATOR S MANUAL e n the case of a normal water sample since sensitivity of the 0 0 signal is insuffi cient for a lock an observed nucleus uses In a gradient shim calibration is required c amp separate volume ADMINISTRATOR S MANUAL 2 72 NM ECA ECX USM 3 2 SPECTROMETER CONTROL gt 2 18 2 Gradient Shim Operation In the gradient shim operation a method using the Gradient Shim button of the Sample window or a method using the Gradient Shim Tool can be used Usually the Gradient Shim button of the Sample window 15 used Each feature is shown below The Gradient Shim button it Gradient Shim button Gradient Shim and Lock button Click on one of above buttons to perform gradient shimming The Gradient Shim and Lock bu
111. default is 35 Pulse output of the second FG pulse PF G2 The default is 1096 V alue to be entered in the first order term P1 of the phase correction of the t axis The standard process listis 2d inverse phase autophase list How to interpret the spectrum The f axis represents the H chemical shift and the f axis the chemical shift The correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross The correlation signals indicate that corresponding H and PC are directly coupled All correlation peaks appear in the same phase Supplementary note e n principle this measurement method makes the peak separation along f axis and the S N ratio better than the HM QC measurement However the pulse sequences are so complicated that the S N ratio decreases compared with that of HM QC In many cases HM QC is advantageous Therefore use this method only when better peak separation along the f axis is required To utilize the advantage of the HSQC method you must improve the digital resolution along the f axis a great deal using a large value of y points t is recommended that you stop spinning the sample tube during measurement NM ECA ECX USM 3 4 51 4 USAGE OF PULSE SEQUENCES 4 3 8 hsqc tocsy dec phase pfgzz ex2 Phase sensitive PFG HSQC TOCSY measurement Directory usr delta global experiments hsqc tocsy 45 HSQ
112. delay Mix_time obs sel 180 d 2 comp 180 90 240 990 P FG channel pry grad 3 amp grad 1 amp grad 2 amp Extension sequences dante_presat The default is FALSE irr_mode Select Off Presaturation or Homo Decouple The default is Off tri_ mode Select Off Presaturation or Homo Decouple default is Off Parameters x_domain Observation nucleus The default is Proton x_ offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample The default is 16K scans Number of scans to accumulate a multiple of 16 The default is 16 scans X prescans Number of dummy scans x pulse 90 pulse width of the observation channel H The default is x90 set in the probe file x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved NM ECA ECX USM 3 4 25 4 USAGE OF PULSE SEQUENCES C obs sel 180 1809 pulse width of the selective excitation pulse The default is twice the pulse width x90 soft set in the probe file obs sel atn Determines RF output for the selective excitation pulse The default is the attenuator value soft set the probe file Every time 6 dB is added the pulse width is halved obs sel offset Resonance position of selective excitation The default is the same as Offset obs sel shape Sele
113. ditions NM ECA ECX USM 3 3 9 3 ADJUSTMENT OF PARAMETERS 3 6 CALCULATION OF 90 PULSE WIDTH OF SELECTIVE EXCITATION PULSES In the NMR spectrometer the 90 pulse widths of selective excitation pulses can be obtained according to the following calculation To calculate 90 pulse widths of selective excitation pulses The 90 pulse widths of selective excitation pulses can be calculated in the same way as normal pulse widths P Wop 1X 100 2 ATT1 2 P Wap 2 p where 1 90 pulse width when the attenuator value is ATT1 PW 2 90 pulse width when the attenuator value is ATT2 0 Coefficient depending the waveform shown the following table Waveform rectangle 1 gauss 0 41064 sinc 0 587191 sin 0 634135 SEDUCE 0 469984 e burpl 0 067093 e burp2 0 061043 1 0 024613 i burp1 0 149611 i burp2 0 100649 re burp 0 079805 For example when the RF power is half power that is the attenuator value is ATT1 3 dB and the 90 pulse width is PW 12 us the 90 pulse width with the Gaussian waveform for the attenuator value 9 dB is given by 12x 1092x6 3 2 58 3 115 3 041064 Hs 3 10 NM ECA ECX USM 3 3 ADJUSTMENT OF NMR PARAMFTFRS To calculate the attenuator value from the pulse width On the other hand the attenuator value can be determined from the pulse width according to the following equation P Woo 2 2 ATT1 20xlogy
114. djust the sensitivity using the METER GAIN button and knob RF POWER S AMPLE CH2 CH3 CH4 LOAD EMPTY LEVEL METER CEEEEECECEECEEEEEEEEEEEEEEECEEEEEEEEEEEE SWR SELECT METER GAIN CH1 CH2 CH3 CH4 METER GAIN button and knob Fig 2 68 Display panel of the head amplifier chassis NM ECA ECX USM 3 2 89 2 SPECTROMETER CONTROL 4 To tune the probe minimize the deflection of LEVEL METER Adjust first the HF1 TUNE dial of the probe and next the HF1 MATCH dial Finally readjust the HF1 TUNE dial HF1 MATCH dial HF1 TUNE dial Fig 2 69 Automatic tuning 5 mm FG tunable probe 5 On completion of tuning click on the GO button to start normal H measure ment 2 90 NM ECA ECX USM 3 2 SPECTROMETER CONTROL tuning normal measurement C measurement conditions 1 Click on the Expmnt button in the Spectrometer Control window The Open Experiment window appears 2 Click on the Gloval Directory button The contents of the Global Experiment directory are displayed 3 Click on the measurement mode single pulse 2 to highlight it 4 Click on the button The Experiment Tool window appears 5 Set each parameter for normal PC measurement in sequence in the Header Instrument Acquisition
115. dow 2 1 Spectrometer information 2 5 Spectrometer RF system 3 3 2 10 2 16 2 16 Spinning 5 2 16 1 4 Standard 4 2 39 SIUE ed 2 82 Start and end of a gradient shim 2 16 Start of automatic measurement 2 40 Start time of measurement 2 87 Starting Gradient Shim Tool 2 14 Starting measurement Queue 2 1 Starting the Sample T ool window 2 11 BINOS ET 2 1 Starting up l 1 c0 HO 2 82 SHOP BIB NA EM TEE 2 85 Storage area for a measurement file 2 28 t _ 2 4 58 e c 2 40 CRT TOT 2 40 2 10 Temperature 2 19 T he first reference and second i i d NER TR IET TIT 5 7 Time chart Display of pulse 2 38 4 4 30 4 52 _14_4 lt 2 4 30 tocsy mlev1760 phase ex2 4 60 Ot tates 1 4 po o TUNES 4 58 U Using metallic solid sample 5
116. e NM ECA ECX USM 3 5 7 5 MULTINUCLEAR MEASUREMENT gt Reference substances There is general agreement that for H and PC NMR chemical shifts should be given With respect to the tetramethylsilane S reference However for multinuclear NM R there is at present no definite agreement for most nuclei It is recommended that you select a reference compound considering the following conditions e t is readily available e tis commonly used in the literature tisastable compound like TM S signal is a readily detectable single line e The resonance frequency is independent of pH temperature and concentration as much as possible In the case of 1 2 a compound which is ionized in aqueous solution and gives a narrow line is considered as the most suitable reference substance For commonly used reference compounds refer to the table in Section 5 5 1 5 8 NM ECA ECX USM 3 5 MULTINUCLEAR NMR MEASUREMENT 5 2 4 Observation of Nuclei Having a Resonance Frequency Close to that of the 7H Nucleus The measurement techniques explained below apply to the following nuclei 19H g Bp 209p 2H oL 139 Ug 133C 136b 11 and 175 Difficulties with these measurements W hen you observe the H nucleus or nuclei having a resonance frequency close to that of the H nucleus 61 MHz 5 MHz when using the 400 M Hz magnet while operating the deuterium lock c
117. e the electric circuits are the same and the RF power applied to the probes is the same B is inversely proportional to approximately the 1 2 power of the resonance frequency 150 7 is proportional to the resonance frequency therefore the following relation is given 1 0 PW Flip angles of nuclei A B EM Resonance frequencies of nuclei B PW PW Pulse widths of nuclei A If the flip angle is 90 and the corresponding pulse widths are the 90 pulse widths PW90 and PW90 1 PW90 PW90 v Thus the 90 pulse width is inversely proportional to approximately the 1 2 power of the resonance frequency From this equation the lower the resonance frequency of a nucleus the longer the pulse width By using a reference sample whose resonance frequency is close to that of the sample under investigation the pulse width can be calibrated through this equation However apply this equation only to measurements from a nucleus where the stick is the same and the resonance frequency is as close as possible NM ECA ECX USM 3 5 15 5 MULTINUCLEAR MEASUREMENT 5 4 RELAXATION TIMES OF MULTINUCLEI This section explains the tendencies of the multinuclear relaxation time Refer to itfor setting the optimum measurement conditions 5 4 1 General Tendencies of Relaxation Times of Multinuclei The spin lattice relaxation time T and spin spin relaxation time T for
118. e and states of a shim can be verified If you click on the GO button a pause state is canceled and measurement restarts 4 4 aabe Inform scca nm jeoLco jp Sample 57493561 required for 00 039 Fig 2 61 Check message window M easurement that changes into waiting state for an execution with the Queue is as follows Observe displayed on the top line aabe Spectrometer Control WAITING Selected Job UNKNOWN 84493561 single pulse 17 0 2003 13 42 56 Fig 2 62 M easurement Spectrometer C ontrol window for an execution waiting state NM ECA ECX USM 3 2 83 2 SPECTROMETER CONTROL 2 84 mor changes to x n If you click on the GO button the following appears Observe that 4 53 Spectrometer Control 84403561 single pulse l7 DEC 2003 13 42 56 po Me PL DEC 2003 13 44 37 Fig 2 63 Restarting measurement Spectrometer C ontrol window NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 20 4 Cancelling Measurement STOP button The experiment that recorded in a Queue can be canceled using the following procedure 1 Select measurement to cancel Queue State OWNED 00 040 Atsushi_Ahe 000 01 494235 i single_pulse Highlighted by 17 DEC 2003 13 44 03 selecting AE AARAA SOO e 2 Dr Fig 2 64 Selection of a measurement Spectrometer C ontrol window 2 C
119. e by one into the numerical input box aabe Set scans None 7 Check button Numerical value list Numerical value input box 1H mum Numerical value input format 4 To enter the values in a range click on the Listed check button to turn it off 5 Select Array Type from Linear Exponential and Logarithmic The example of x 90 width parameters is shown below NM ECA ECX USM 3 2 97 2 SPECTROMETER CONTROL aabe Experiment Tool single pulse ex2 File Tools View Options Dimension lr i None Listed aed x 90 width 1 us gt 16 us 1 us Sf dB 4 257 relaxation _ repetition time y acq pus E 16 us IAus Set Value Total Collection Time 00 15 02 Selecting L inear If you select Linear enter the values of Start Stop and Step in the input boxes In the above example the parameter varies linearly from 1 us to 16 us with a 1 us interval that is 1 2 3 14 15 and 16 us 16 points in total aabe Experiment Tool single pulse ex2 File Tools View Options relaxation delay repetition time Set Value Total Collection Time 00 02 5 55 Selecting E xponential If you select Exponential enter the values of Start Stop and Points in the input boxes In the above e
120. e correction DC Correct Performs baseline correction aahe Vector View scc2 nm jeal co jp Options Processing f DC Balance ro Hamming _ Hed gt Zexofill x4 SITE yal 6 0 5 0 4 0 3 0 2 0 1 0 0 1 0 m X kilohertz Current Time Expected Finish Delta Time Integral Value 2 50 NM ECA ECX USM 3 2 SPECTROMETER CONTROL R L 2 7 MAKE NEW INSTANCE OF SELECTED J COMMAND Y ou can copy the data in the middle of a measurement and process it data using 1D Processor and nD Processor This function is used when verifying the progress in the middle of an accumulation Click on the Copy button in the Spectrometer Control window The data in the middle of measurement is copied and 1D Processor or nD Proces Sor starts NM ECA ECX USM 3 2 SPECTROMETER CONTROL mom 2 8 90 PULSE WIDTH DISPLAY 90 pulse width for each measurement nucleus and the attenuator value which are described in a probe file can be displayed Select Tools 90 s in the menu bar of the Spectrometer Control window 90 pulse width display window opens 4 aabe 905 for s Probe 2692 i d Gradient Autotune Proton 1H Autotunable Dom Coil 90 hi 90 10 90 spin 90 soft 90 solids atn hi atn lo atn spin atn soft atn solids 206 us 20000 us 9 5 dB 79 dB 79 dB 44 5 dB 79 dB 13 17 us 92 us 28 48 us 10000 us 1 us 6 5 dB 23 dB 12 5 dB 58 6 dB 79 dB 15 us
121. e default is the same as grad 1 Pulse output of the second FG pulse PFG2 The default is the same as grad 1 amp Pulse width of the third FG pulse PFG3 The default is the same as grad 1 Pulse output of the third FG pulse PFG3 The default is computed from grad 1 and the intensity ratio of the PFG to be applied to y domain W aveform of the FG pulse Select SQUARE SINE or GAUSS The defaultis SINE Recovery time after the FG pulse The default is 0 1 ms The standard process list is 2d inverse abs ist 4 48 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES gt How to interpret the spectrum The axis represents the H chemical shift and the f axis is the PC chemical shift The correlation signals between H and PC appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross The correlation signals indicate that the corresponding H and PC are directly coupled Supplementary note e Theratio of the gradient pulse is as follows For the PC nucleus PFG1 PFG2 PFG3 2 2 1 For the N nucleus PFG1 2 PFG3 4 94 4 94 1 For the Si nucleus PFG1 PFG2 2 52 2 52 1 the nucleus PFG1 PFG2 PFG3 1 24 1 24 1 1 1 1 amp PFG2 grad 2x grad 2 amp grad 3 amp e 5 as follows 100 to 250 Hz standard 145 Hz J yy 60 to 140
122. e has been specified and is in the state of Waiting WAITING waiting for an execution 5 3 2 81 2 SPECTROMETER CONTROL 2 20 2 Queue Menu The command for controlling a Queue is provided in the Queue menu of the Spectrometer Control window aahe Spectrometer Control Fig 2 60 Queue pull down menu Menu Detail Start Restarts a Queue stopped If you execute the Stop command after clicking to select a specified Queue all Stop subsequent Queues will be in a pause state _ Since the function of the Stop command differs from the button be careful The measurement that came to a head can be turned to the end of the Queue It R eschedule 15 used when a spectrometer is not ready with a certain reason Delete The whole Queue is canceled except for the currently running measurement Print The recorded Queue is printed 2 82 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 20 3 Restating Measurement GO button Go button B efore performing the first experiment in the Queue a spectrometer compares the name sample id of the last measurement and measurement that it is going to perform from now If the sample id is the same measurement is started immediately When the sample id is not on agreement or is not specified measurement will be in the state of Waiting for execution and a message window will be displayed on a screen Here the states of a sample spinning of a sample tub
123. e mouse pointer away from the pull down menu release the left mouse button The tool bar functions frequently used also appear as icons under the menu bar 1 2 NM ECA ECX USM 3 1 FUNDAMENTALS OF DELTA J aabe Delta View Process File Manager File Search Parameters essinq and Control Software 2903 by JEOL USA Inc Beta 10 16 03 21 55 Linux Fil technical features are enabled Fig 1 4 Pull down menu Accelerator key accelerator key is displayed to the right on the pull down menu If you enter this key from the keyboard you can quickly open a window or select an option Pull down menu of file In displayed an accelerator key the sign indicates the key For example in the case of O this means pressing the O key while pushing the key NM ECA ECX USM 3 Fig 1 5 Accelerator key 1 3 1 FUNDAMENTALS OF DELTA 1 2 2 Tool Bar in the Delta Console Window The icons located under the menu bar form the tool bar A picture of each function is displayed on each button To select a button move the mouse pointer onto a button and click the mouse left button Almost all buttons have the same function as the corresponding menu bar items Fig 1 6 Tool bar in theDelta C onsole window The following table explains the tool bar icon of the Delta Console window Icon Button name E xplain This tool is for data
124. e shim system Is set to it Then the magnetic field map is measured again These measurements and computations are iterated until the field map becomes sufficiently uniform The computer does these tasks so in practice the operation is simply to insert the sample and click on the button A single line of H or H contained in the sample is used to measure the magnetic field map The axial shim terms Z1 to Z6 can be adjusted as the Field gradient of the Z1 axis is used 25 Calibration creating the basic map W hen the gradient shim is used the shim terms Z1 to Z6 are calculated based on the correction magnetic field The correction magnetic field measured using the standard sample is called the basic map and the measurement of the basic map 15 called calibration Calibration varies depending on the probe in use and the measurement nucleus However calibration should be performed once and it is not necessary to do so every time when the actual sample is measured The basic map of Z1 to Z6 is stored in the directory usr people delta delta instrument and is used to correct the magnetic field of the measurement sample NM ECA ECX USM 3 2 71 2 SPECTROMETER CONTROL B Gradient shim In the gradient shim used in the spectrometer there are two methods for homogeneity spoiling homospoil and PFG Pulsed Filled Gradient In this spectrometer the homogeneity spoiling gradient shim whose observed nucleus is H is provi
125. ector View window l Click on the Process button in the Vector View window It changes to the processed data display 2 Click on the Process button again It returns to the FID display Vector View 2 01 0 io Options Processing Ruler 100 0 1900 300 0 300 0 01 0 2 03 04 05 06 07 08 09 10 LI 12 13 14 15 16 17 1412 seconds Current Time Expected Finish Delta Time Integral Value 31 OCT 2003 09 17 51 31 OCT 2003 09 18 24 000 00 33 Vector View sccz nm jeol co jp 0 1 0 20 30 4 0 5 0 6 0 7 0 8 0 90100110 6 0 5 0 m X kilohertz Current Time Expected Finish Delta Time Integral Value 31 OCT 2003 09 18 13 31 OCT 2003 09 18 24 000 00 11 5 3 2 49 2 SPECTROMETER CONTROL gt 2 6 2 Processing Menu The contents of processing can be selected in the Vector View window during processed data display Select the menu displayed in Processing of the menu bar in the Vector View window Processing of the function by which the check mark is placed is them performed Function Explanation DC Balance Corrects the DC component of FID Hamming M ultiplies Hamming window Zero fill x2 Performs 2 times zero filling Zero fill x4 Performs 4 times zero filling FFT Performs FFT Abs Performs an absolute value display Machine Phase Performs automatic phase correction Phase Performs phas
126. ed The default is 5 ppm However in some cases such as when itis the same as offset there is no input box irr noise Decoupling mode The default is WALTS NM ECA ECX USM 3 4 7 4 USAGE OF PULSE SEQUENCES 0 4 1 6 wet suppression This WET sequence is used to reduce a signal that would overwhelm the desired peak such as a water signal in an aqueous solution sample Pulse sequences wet pulse wet pulse wet pulse wet pulse x domain irr domain wet grad PFG2 o 8 e wet grad amp 2 wet g ra d a mp 4 wet grad amp 8 Parameters wet pulse Pulse width of the shaped pulse to be used for WET sequences The default is 10 ms wet attenuator Determines RF output for the shaped pulse to be used for sequences The default is 58 2 dB Every time 6 dB is added the pulse width is halved wet offset Resonance frequency of a peak to be WET irradiated The default is equal to x offset wet shape W aveform of the shaped pulse The default is seduce wet grad Pulse width of the PFG pulse The default is 2 ms wet grad amp Output of the PFG pulse The default is 48 wet grad shape Waveform of the pulse The default is SQUARE wet grad recover Recovery time after the PFG pulse The default is 0 1 ms irr domain Irradiation nucleus The default is C arbon13 irr offset Resonance frequency of the peak to be ir
127. eld Gradient COSY isthe abbreviation of COrrelation SpectroscopY Purpose To observe correlation signals between directly J coupled peaks This measurement gives information on connections of spin spin interaction between the H peaks The use of PFG results in a 2D spectrum with one scan B Pulse sequences laxation del x domain relaxation delay grad 1 grad 2 FG channel Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo decouple T he default is Off tri mode Select Off Presaturation or Homo Decouple T he default is Off B Parameter x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample along the t axis The default is 1024 scans Number of scans to accumulate The default is 1 scan X prescans Number of dummy scans The default is four scans y points Number of points to sample along the t axis The default is 256 x 90 width 90 pulse width set in the probe file 4 36 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES x atn Attenuator value x atn set in the probe file pulse angle 1 Flip angle of the first pulse The default is 90 deg pulse 1 First pulse width It is computed as x 90 width x Pulse_angle_1 90 pulse angle 2 Flip angle of the second pulse The default is 90 deg pulse 2
128. ent shape These fields are added to correct the inhomogeneous magnetic field The basic correction magnetic fields are the axial shim terms Z1 to Z6 used to correct the axial magnetic field of the sample and the radial shim terms such as X1 Y 1 and XZ used to correct the horizontal magnetic field The actual correction magnetic field is a composition of shim terms multiplied by the coefficients In other words the shim adjustment is carried out to adjust the coefficient applied to these shim terms Feature of the gradient shim Conventional shim adjustment searches for the combination of shim values that maximizes the signal intensity while monitoring the lock signal intensity Generally the automatic adjustment function called simplex is used This method requires more time as the number of types of shims used increases M anual shim adjustment requires some experience If the initial shim condition is bad it takes considerable time for even a skilled operator to adjust the shims Using the gradient shim anyone can easily increase the resolution even if the number of the shims increases You can adjust the shims from Z1 to Z6 in afew minutes regardless of the initial shim conditions W hen the gradient shim 15 used the magnetic field distribution the magnetic field map over the sample is measured using the magnetic field gradient The combination of the coefficients of the basic map that makes the field map uniform 15 computed and th
129. epetitions Remaining number Receiver gain of accumulations Liquid helium Level Liquid nitrogen level Fig 2 4 Sample monitor in the Spectrometer C ontrol window NM ECA ECX USM 3 2 9 2 SPECTROMETER CONTROL 2 2 SAMPLE TOOL WINDOW In the Sample Tool window loading a sample spinning NMR lock and shim adjustment can be performed The main information displayed in the Sample T ool window is as follows Items Explanation Field Strength M agnetic field strength T Display only Helium Liquid helium level 96 Display only Nitrogen Liquid nitrogen level 96 Display only Sample State Sample state L oad E ject Spinner Sample Spinning state Spin N o spin and spinning speed Hz Temperature V ariable temperature state ON OFF Solvent D euterated solvent name L ock Control NMR lock condition Gain L ffset Shim Control Lock signal intensity display only and shim conditions 2 10 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 2 1 Starting the Sample Tool Window Click on the Sample button in the Spectrometer Control window 54 aabe Sample scc nm jeol co jp Helium Nitrogen 11 7473579 T 87 95 9255 Sample State Probe ID 2692 SHIM 21 su z2 1 SHIM Z3 l aHa Fig 2 5 Sample T ool window NM ECA ECX USM 3 2 11 2 SPECTROMETER CONTROL gt 2 2 2 Display of SCM Related Information
130. er to Section 5 5 2 W hen you measure nuclei that have a wide chemical shift range you must consider the following three probl ems a Signal fold over b Signal excitation range C Setting of chemical shift reference Item a is explained in Section 5 3 4 Items b and c are explained below B Signal excitation range If the chemical shift range is wide the 90 pulse sometimes cannot excite all peaks sufficiently and the phase shift cannot be corrected by the first order equation As a result you cannot obtain an in phase spectrum for all the observation range In such a case reduce the flip angle and measure the spectrum If you reduce the flip angle shorten relaxation delay to improve the accumulation efficiency B Setting the chemical shift reference Even if the maximum observation range is set on the instrument all peaks may not be measured at once Aso the position of the reference peak for the chemical shift may go out of the observation range Even in such a case the chemical shift scale can be set correctly as the position of the chemical shift reference is recorded as the absolute frequency in the Delta software c For details refer to External reference and internal reference in Section 5 2 3 5 12 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT C 5 3 4 Signal Fold over B Signal fold over There are many cases in multinuclear NMR where the chemical shift goes out of the obser
131. ernal reference and internal 5 7 F 2 50 Field Map 2 76 Field Strength 2 10 File 1 4 RTT 2 40 PREE ice 2 81 EE 2 22 Global 2 28 GO DURON ET 2 83 Gradient Optimization 2 40 Gradient 1 2 12 Gradient 2 22 2 40 Gradient Shim Status window 2 16 Gradient SHIM 2 71 Gradient Shim Tool window 2 14 Gradient Shim amp L ock 2 22 H E18 MENT 2 01 2 50 Header 2 29 HEU 2 10 Bii 1 4 Pre nodi uei 4 40 ji 3 fr 4 40 Hide 2 41 4 44 4 44 ii be PEETA H 4 47 HERE 4 47 1191 2 c eraser 4 30 2 40 Homo 4 5 How to display a 5 2 56 4 50 hsqc dec phase pfgzz ex2 4 50 hsqc tocsy dec phase pfgzz ex2 4 52 I be 4 54 inadequate 2d pfg ex2 4 54 Include Automation File 2 41 Instrument 5
132. ers x domain Observation nucleus of the 1 axis The default is Proton X sweep Observation range of the f axis The default is 15 ppm x Offset Observation center of the 1 axis The default is 5 ppm points Number of points to sample along the t axis The default is 1024 y domain Observation nucleus of the 1 axis The default is Carbon13 y sweep Observation range of the f axis The defaultis 170 ppm y offset Observation center of the f axis The default is 85 ppm y points Number of points to sample along the t axis The defauilt is 256 4 50 NM ECA ECX USM 3 scans X prescans x pulse x atn y pulse y atn constant purge relaxation delay grad 1 amp grad 2 amp y pl correction Data processing 4 USAGE OF PULSE SEQUENCES C Number of scans to accumulate The default is 2 scans Number of dummy scans The default is four scans 90 pulse width of the observation channel The default is x90 set in the probe file Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved 90 pulse width of the irradiation channel of the f axis The default is y90 hi set in the probe file A ttenuator value yatn set in the probe file Value of J The default is 140 Hz Pulse width of the spin lock purge pulse The default is 1 ms W aiting time between repeated pulses T default is 1 5 s Pulse output of the first FG pulse PFG1 The
133. f required 6 Finally click on the Done button The parameter added to the H eader section appears 2 32 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 3 3 Instrument Section In the Instrument section you can set the conditions of an NMR lock receiver and audio filter A O aabe Experiment Tool single pulse exz File Tools View Options mjeoLcejp Total Collection Time 00 01 03 Fig 2 28 Instrument section of the xperiment T ool NM ECA ECX USM 3 2 33 2 SPECTROMETER CONTROL Addition of Instrument parameter Y ou can add a new parameter to the Instrument section using the following methods 1 Click on the Instrument tab in the Experiment Tool window The Instrument section appears 2 Click on the button 4 13 aabe Experiment Tool single pulse ex2 File Tools View Options d Total Collection Time 00 01 03 The Include Parameter window opens Open File Fig 2 29 Include Parameter window 3 Select the parameter to add The selected parameter is highlighted 4 Click on the Add button 5 Repeat steps 3 4 if required 6 Finally click on the Done button The parameter added to the Instrument section appears 2 34 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 3 4 Acquisition Section Y ou can set the parameters related to data acquisition NMR observation frequency observation width and data point in the Acquisition
134. f the duration of the RF pulse Therefore more accurate value can be obtained by finding 360 pulse width and then estimating the 90 pulse width as one fourth of its duration NM ECA ECX USM 3 3 ADJUSTMENT OF NMR SPECTROMETER RF SYSTEM AND FACTORS AFFECTING PULSE WIDTHS In order to adjust the power of the RF pulse to measure the pulse width it is necessary for you not only to learn the procedure for measurement but also to understand the flow of RF pulses in the spectrometer You can understand the meaning of the measurement procedure from understanding the flow of the RF pulses This section describes the flow of the RF pulses in the spectrometer and various factors affecting the pulse widths Outline of the spectrometer RF system In order to help you to understand the operation of the pulse sequence a simplified schematic diagram of the RF system in the spectrometer is shown in Fig 3 3 Receiver Preamplifier lt lt HF power Sequencer Transmitter amplifier Sequencer st LF power Sequencer amplifier Duplexer Probe Dual FSY Fig 3 3 Block diagram of theRF system T he standard probe provided with the spectrometer is a tunable double resonance probe This probe can be tuned to the resonance frequency and the resonance frequencies of nuclei in the range from P to PN The channel into which RF power at the frequency 15 entered is
135. g the t axis The default is 256 scans Number of scans to accumulate a multiple of 4 The default is 4 Scans X prescans Number of dummy scans The default is four scans x pulse 90 pulse width of the observation channel 1H The default is x90 set in the probe file 4 56 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved mix time M ixing time The default is 500 ms relaxation delay Waiting time between repeated pulses The default is 1 5 s repetition time relaxation delay x acq time grad 1 Pulse width of the PFG1 pulse The defaultis 1 ms grad 1 amp Pulse output of the PFG1 pulse The default is 1596 y pl correction Value to be entered in the first order term P1 of the phase correction of the t axis Data processing The standard process list is 2d homo2d phase autophase list How to interpret the spectrum Both the f axis and the f axis represent chemical shifts The correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross The correlation signals due to the J coupling also appear To distinguish them use another method such as the COSY method Supplementary note It may be difficult to observe NOE for samples having medium molecular weights of 1000 to 5000 In this case use the ROESY method or the phase se
136. gh the S N ratio deteriorates NM ECA ECX USM 3 4 61 MULTINUCLEAR MEASUREMENT This chapter presents how to observe NMR signals of nuclei other than the and PC nuclei Such nuclear is called multinuclear Additional functions of the spectrometer and probe are required for multinuclear NM R observation and preparatory knowledge is necessary Please read this chapter before you attempt multinuclear N M R measurement for the first time 5 1 OUTLINE OF MULTINUCLEAR NMR MEASUREMENT ee 5 1 S LI NM R 5 1 5 1 2 Relative Sensitivity of ultinuclear 5 2 5 1 3 Multinuclear NM Observation 5 5 4 5 2 MULTINUCLEAR MEASUREMENT rrr iri rr i Ph tata 5 5 5 2 1 Multinuclear Observation Probes een 5 5 5 2 2 Operational Procedure for M ultinuclear easurement 2 6 5 2 3 Chemical Shifts and Reference 5 7 5 2 4 Observation of Nuclei Having a Resonance Frequency Close to that RA RECETTE 5 9 5 2 5 Sensitivity Enhancement by the Pulse 5 10 5 3 SPECIAL PHENOMENA AND PRECAUTIONS FOR MULTINUCLEAR NMR MEASUREMENT nnm mmn 5 11 5 3 1 Precautions for Sample Preparation
137. h shim value can be saved as a shim file The shim value can be read from the file and used it if necessary In the shim file there are two kinds of shim for a system shim and a user shim One system shim exists per probe M oreover this system shim is saved in the spectrometer anyone can read this shim value However only administrator can rewrite the system shim On the other hand a user can create a user shim for every measurement conditions such as a probe a sample or a solvent A user shim is saved to a user s local directory Saving shim value Saving to the user shim file 1 Click on the button in the Sample Tool 2 Click on the button The Save Shim File window opens aabe Save Shim File Path Ausr people aabe delta instrumen Ja Format JEOL Deta JEOL Delta Fig 2 16 Save Shim File window NM ECA ECX USM 3 2 23 2 SPECTROMETER CONTROL 3 After moving to the directory to save input file name to save to the input box and click on the Ok button The shim value is saved to a user shim file 25 When creating a new directory to save to click the button after speci fying a directory name to the Path input box Create and transfer a directory Then input a saving file name into the file name input box Saving to the system shim file 1 Select Tools Mode Console in the Spectrometer Control window This becomes Console mode JS Work is done by the user w
138. he Sample Tool window Sample State Sample State Slot Changer sample is loaded and the sample state changes into the load state 2 14 NM ECA ECX USM 3 2 SPECTROMETER CONTROL e Ejecting a sample When using the auto sample changer W hen using the auto sample changer a series of work from ejecting to changing the sample can be performed simply setting a slot number Enter the slot number 0 in the Slot in the Sample State of the Sample Tool window Sample State y ole Probe ID Slot The sample is ejected and carried on an auto sample changer The sample state changes to eject state JS n order to prevent the trouble at the time of loading and ejection by the auto sample changer set Spectrometer L oad Eject Disable in the System tab of the Prefer ences T ool window to TRUE The load and eject button of a sample are dimmed by this operation and this can prevent mistake in operation When not using an auto sample changer Click on the button in Sample State of the Sample Tool window No Changer Slot NE Changer A sample is ejected and the sample state changes into the eject state i NM ECA ECX USM 3 2 15 2 SPECTROMETER CONTROL 2 2 4 Sample Spinning B Spinning state oad eject state of the present sample can be verified in the display of a Sample State in the Sample T ool window Spinning ON Spinning OFF P
139. he sample d Power output by the power amplifier The factor a is a characteristic of the probe The factor b varies with the frequency of the RF pulse room temperature and sample temperature and with c susceptibility of the sample W hen the state of the tuning circuit changes it can be corrected to a certain extent by retuning the probe and returned to near the optimum condition However when the sample has a large susceptibility it is impossible to return it completely to the same conditions even if the probe is tuned The factor d varies for many reasons The output of the analog power amplifier may change with time It also depends temperature which influences the transistors in the power amplifier Generally the output increases with a decrease in temperature It is also frequency dependent Signals entered into the power amplifier are most likely influenced by temperature and elapsed time as well B Pulse widths to be adjusted or measured Precise pulse widths have been preset in the spectrometer at the time of installation However they may change due to various conditions When they change adjust or measure the following pulse widths e Pulse width when you use output at half power e Pulse width when you change an attenuator value e Pulse width when you measure DEPT 90 e Pulse width of selective excitation pulse For information on how to measure or calculate these pulse widths refer to the sections tha
140. hen measure the pulse width lt Chapter 3 Furthermore be sure the peak is not folded lt Section 5 3 4 6 Setthe chemical shift reference W hen using the first standard as the standard sample record the absolute frequency of the resonant position of the sample The reference value of the chemical shift becomes zero 7 Measure the desired sample See Section 3 3 5 6 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 5 2 3 Chemical Shifts and Reference Substances B Definition of a chemical shift The chemical shift of a multinuclear NMR sample is given in ppm relative to the reference similarly to and PC NMR The chemical shift is defined in the following equation 00 4 6 Chemical shift z 10 3 1 Resonance frequency of sample Resonance frequency of reference It is noted from this equation that the chemical shift of a peak which appears at a lower frequency a higher magnetic field than the reference is given as a negative value of and that which appears at a higher frequency is given as a positive value of B The first reference and second reference The standard substance used in the above equation is called the first reference substance Tetramethylsilane TM S and other compounds which are widely quoted in the literature are utilized as first reference substances Sometimes a solvent signal or the signal from a substance which is easily
141. if possible For example if you measure O NMR use an oxygen free solvent such as chloroform If you use a solvent which contains oxygen such as water H O or D O methanol acetone or dimethyl sulfoxide the solvent itself gives rise to a large signal making signal detection of a low concentration sample difficult You should always keep this type of problem in mind when you perform multinuclear measurement Using a solid sample The bigger the sample tube diameter the more easily powder and pellet samples are filled and measured Use a sample tube with as big a diameter as possible usually 10 mm when performing solid sample measurement B Using a metallic solid sample Take the following precautions when performing metal or conductive sample measurement An RF pulse applied to a conductive material does not penetrate inside the sample due to the skin effect Instead it penetrates only a few microns in from the surface T herefore if the sample tube is filled with a normally shaped metal a spectrum with a good S N ratio cannot be obtained To improve the S N ratio make a plate sample as thin as possible a rod sample as slender as possible or pulverize block samples as finely as possible so that the surface area of the samples becomes larger 5 3 2 Selection of Sample Tubes Common NMR sample tubes are made of glass which contains compounds of silicon boron and sodium Therefore when Si NMR NMR and NMR
142. ified as the queue priorities file of the spectrometer management computer A user can also change the priority of this measurement However possible change in ranking is only from higher to lower If you have any console privilege you can freely change the priority of all measurements 2 20 1 Queue State T he present state of the Queue is displayed on the Spectrometer Control window aahe Spectrometer Control 7 I State of Queue en 1n 4 QueweState WAITING 2 Selected Job UNKNOWN 00 037 Mtsushi Abe 37 000 01 426403 single pulse 17 DEC 2003 11 51 00 Fig 2 59 State display of Queue 2 80 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Hereafter each state is explained State Display axplanation In the state where the system is connected with the spectrometer using the Connect button a user can occupy a Queue it is owned Though other users record a measurement experiment only the user who connected previously using the Connect button can perform a measurement Occupancy In this state another user is performing measurement Console M easurment privilege is required when changing the Queue In this state the Queue was stopped using the Stop command or Stop HALTED H old flag If the Queue is restarted using the Start command all measurements will restart Free Queue is in a free state M easurement start tim
143. ill be indicated 2 12 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 2 3 Loading and Ejecting a Sample Sample state Load Eject state of the present sample can be confirmed in display of the Sample State in the Sample T ool window Sample State Sample State Loaded state Ejected state Fig 2 9 Sample State display 25 When the greener indicator turns yellow this means changing from eject to load state or eject from load state is shown NM ECA ECX USM 3 2 13 2 SPECTROMETER CONTROL Loading a sample When using the auto sample changer W hen using the auto sample changer a series of steps from changing to loading a sample can be performed simply by automatically setting a slot number Enter the slot number to set a sample on the auto sample changer in a Slot in the Sample State of the Sample Tool window Sample State gt Slot En After carrying the sample in the slot that specified on the auto sample changer on SCM itis loaded and the sample state changes to load state 27 n order to prevent trouble during loading and ejecting a sample by the auto sample changer set Spectrometer oad Eject Disable in the System tab of the Prefer ences T ool window to TRUE Theload and eject button of a sample are dimmed in this way and to prevent mistake in operation When not using the auto sample changer Click on the button in the Sample State of t
144. ing a wide range of J values to display all correlation signals using one constant value In this case you need to perform measurement several times with different constant values e t is very effective for a sample having a long relaxation time to add a relaxation reagent for example to the sample NM ECA ECX USM 3 4 55 4 USAGE OF PULSE SEQUENCES 4 3 10 noesy phase pfgzz ex2 Phase sensitive detection NOESY measurement Directory usr delta global experiments noesy NOESY is abbreviation of Nuclear Overhauser Effect SpectroscopY Purpose of measurement To observe correlation signals due to NOE and chemical exchange The spatially nearby nuclei can be identified by observing NOE This method is useful for three dimensional structural analysis Pulse sequences x pulse x pulse x pulse 90 90 90 Purge pulse mix time relaxation delay presat time x domain FG channel Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple The default is Off tri mode Select Off Presaturation or Homo Decouple default is Off Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm X points Number of points to sample along the t axis The default is 1024 y points Number of points to sample alon
145. ion highlights the name of the selected spectrometer A aabe Spectrometer Control Tools Config Queue Machine Options Selected spectrometer OHNED ECA600 5th BLD FREE ECA500 5th BLD OWNED ECX400 R amp D DEHO scc5 OWNED ECA500 R amp D DEHO scc6 OWNED ECA600 R amp D DEHO scc OWNED ECA600 R amp D Basement Spectrometer list can be communicated aj Prio Slot JobSubmitTime 6 mem Auto Sawth View 2 2 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 Click on the Connect button Connect scc2 nm jenlco j Node name of connection n mode and connection Queue State OWNED Selected Job UNKNOWN place appear Fees 4S f status display of the selected spectrometer is not Free it cannot be connected in the Connect mode It is connected automatically in M onitor mode NM ECA ECX USM 3 2 3 2 SPECTROMETER CONTROL Release of a spectrometer Click on the Unlink button of the Spectrometer Control window Connection with a spectrometer is released and a connectable spectrometer is displayed Tools Config Queue Machine Options AAA 2 4 NM ECA ECX USM 3 2 SPECTROMETER CONTROL e Confirming spectrometer information The information on a spectrometer to connect or on the connected spectrometer can be verified using the following procedures
146. ircuit noise increases due to the interaction of the lock system and the observation system For this reason it is necessary to stop the operation of the lock circuit Since the lock signal cannot be used adjust the resolution using FID If a deuterium solvent can be used adjust the resolution first using this solvent and then stop the lock circuit to measure the sample W hen you measure a peak with a wide line width like that of the H spectrum of a liquid crystal adjust the resolution once using deuterium solvent and then measure without readjusting the resolution Stopping the lock circuit To stop the lock circuit turn the H OSC off according to the following procedure l Select Tools Params in the Spectrometer control window The Parameter Tool window opens 2 Click on LOCK OSC STATE in File to highlight it Fig 5 4 Selecting File the Parameter Tool window 3 Click on the downward arrow button Change display of 2H OSC ON to 2H OSC OFF and turn off H LOCK NM ECA ECX USM 3 5 9 5 MULTINUCLEAR MEASUREMENT 5 2 5 Sensitivity Enhancement by the Pulse Technique The pulse technique is useful for sensitivity enhancement of nuclei with 2 1 2 that is directly coupled to the proton H Two methods INEPT Insensitive Nuclei Enhanced by Polarization Transfer and DEPT Distortionless Enhanced by Polarization Transfer are commonly used These methods use spin population transfer by app
147. ith administrator privilege who user s right to Console mode 2 Click on the button in the Sample Tool 3 Click on the button The Confirm window opens 4 aabe Confirm Are you sure you want to save the system Shims Fig 2 17 Confirm window 4 Click on the Ok button when saving a system shim file The shim value is saved to a system shim file 2 24 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Reading a shim file Reading a system shim file 1 Click on the button in the Sample Tool 2 Click on the button The Confirm window opens aabe Confirm Are you sure you want to Load New System Shims Fig 2 18 Confirm window 3 Click on the Ok button when reading a system shim file A system shim is loaded Reading a user shim file 1 Click on the button in the Sample Tool 2 Click on the button The Open Shim File window opens aabe Open Shim File Path usr people aabe delta instrumen Format Filter IN Fig 2 19 Open Shim File window 3 Select a shim file name to read with the mouse and click on the button T he shim file is read and the shim value is set to each axis Information of the read shim file appears on the Inform window aabe Inform These Shims were saved hy Atsushi For the scc2 nm jeol co jp On 28 OCT 2003 10 51 56 Fig 2 20 Inform window NM ECA ECX USM 3 2 25 2 SPECTROMETER CO
148. l This voltage is proportional to the square root of the power The relationship between the attenuator value and the RF magnetic field strength B is expressed by the following equation as long as the amplification factor is linear 1 1 0 2 2 1 B B 10 where B 1 Magnetic field strength when the attenuator value is ATT1 B Magnetic field strength when the attenuator value is 2 The pulse width is inversely proportional to Thus PW PW 109 2 1 2 where 1 90 pulse width when the attenuator value is ATT1 PW 2 90 pulse width when the attenuator value is ATT2 For example to double the pulse width increase the attenuator value by approximately 6 dB 25 Decibel dB The number of decibels denotes the ratio of the two amounts of energy or amplitudes of waves such as electromagnetic waves and sound waves A decrease in energy by 10 dB for example means that the energy becomes one tenth of its previous value A decrease in amplitude by 20 dB means that the amplitude becomes one tenth of its previous value NM ECA ECX USM 3 3 5 3 ADJUSTMENT PARAMETERS Measuring 90 pulse width in the observation channel As explained in Section 3 1 first obtain the 360 pulse width and then estimate the 90 pulse width as one fourth of its value In practice obtain the 90 pulse width according to the following procedure l Insert a standard sample or a desired
149. l directory Clicking on the button in the O pen Experiment window lists the measurement file in a local directory A local directory is a directory specified to Experiment in the Directory tab of the Preferences T ool window The measurement files which are user created and corrected are stored in this directory Global directory Clicking in the button in Open Experiment window lists the measurement file in a global directory A global directory is a directory specified to Global Experiment in the Directory tab of the Preferences T ool window The measurement file of the standard which J EOL supplies is stored in this directory 2 28 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 3 2 Header Section In the H eader section of the Experiment T ool window parameters such as sample id filename and comment are set The Header section has two important functions in addition to this One is setting a process list It specifies which process list is to be used on the data after acquisition Another 15 a header parameter If you use this function various spectrometer functions and data acquisition conditions can be controlled 4 5 aabe Experiment Tool single pulse exz File Tools View Options wi e tune LJ jeol co n Total Collection Time 00 01 03 active global std proton antophase ist Edit Fig 2 24 Header section of the E xperiment T ool NM ECA ECX USM 3 2 29 2 SPECTROMET
150. lationships Between Nuclear Species and Sticks 5 19 5 5 2 Multinuclear NM Chemical 5 23 INDEX C 4 NM ECA ECX USM 3 FUNDAMENTALS OF DELTA Chapter 1 describes the operation of the fundamental processing tool of the Delta program The Delta program consists of various tools Each tool uses two or more windows Processing analysis and plot out for data are performed using these tools 1 1 SIARTING UP DELTA S iisdem ron HER Ene essi 1 1 1 2 DELTA CONSOLE via ebur E ERE ERES p IHR EYRERO Ea ERR ps 1 2 1 2 1 Themenu bar in the Delta Console window ccnmmH 1 2 1 2 2 Tool Bar in Delta Console W indow eenm n 1 4 NM ECA ECX USM 3 1 FUNDAMENTALS OF DELTA 1 1 STARTING UP DELTA This section assumes that operator is already logged into a workstation c Refer to the manual the login procedure to a workstation B When Delta icon is displayed on the desktop screen Double click on the Delta icon The Delta program starts and the Delta C onsole appears 4 4 Delta File Processors Viewers Tools Analysis Acquisition Delta Processing and Control Software Copyright 1990 2003 by USA Inc Version d 3 Beta 10 16 03 21 55 Linux 21 CFR part 11 technical features are enabled Fig 1 1 Delta Console window NM ECA ECX USM 3 1 1 1
151. le decoupled or non decoupled measurement is shown Parameters The parameters to be set before measurement is carried out their meanings and default values or recommended initial values are shown Some of the initial values are set as defaults stored in a probe file x90 90 pulse width of the observation channel spin lock 90 90 pulse width of the spin locking M LEV 17 sequence attenuator Attenuator value of the observation channel in spin locking y90 hi 90 pulse width of the irradiation channel These values are adjusted for individual probes Data processing The name of the process list which is to be loaded after the measurement is complete is indicated These process lists are located in the global directory usr delta global process list How to interpret the spectrum Briefly describes how to interpret and analyze the spectrum obtained using this measurement method NM ECA ECX USM 3 4 1 4 USAGE OF PULSE SEQUENCES Supplementary notes Brief remarks regarding measurement and parameters to be adjusted 4S Directory tree structure Individual experiment files are stored in the directories The directories and files form a tree structure as shown in the figure below Global directory 2 usr delta global experiments M 10 cosy Basic 1D 2D measurement Relaxation time uus solid state Solid measurement Directory tree structure 4 2 NM ECA ECX USM 3
152. lick on the STOP button Several seconds are required before measurement is canceled by the state of a network and measurement repetition time W hen save aborted of the E xperiment flag was True data is read while having been canceled and it is displayed on the 1D Processor window Data is deleted when it is not True This is True unless the setting is changed NM ECA ECX USM 3 2 85 2 SPECTROMETER CONTROL m unum 2 20 5 Measurement Priority As described above priorities from 0 to 255 exist in a measurement experiment and a measurement priority already recorded in a Queue can be changed in the Spectrometer Control window If you select measurement and input a numerical value in the Priority input box the order of measurement will change according to the priority However change of a common user s priority is only the change to the lower one M easurement priority can be changed freely by a privilege user 4S Change to Queue under measurement cannot be performed now 5 aabe Spectrometer Control Tools Config Queue Machine Options Connect see2 nn n jen 53405215 single pulse 17 DEC 2003 13 45 42 Atsushi 5 495233 single pulse 17 2003 13 45 43 Priority fon oubmit Time Input box aes CEP 7 2003 13 45 43 DEC 2003 13 45 43 ee aes 6 Iter 12 0 2003 13 46 57 He 99 Fig 2
153. lt is 100 ppm X sweep Observation range The default is 250 ppm points Number of points to sample along the t axis The default is 1024 scans Number of scans to accumulate a multiple of eight The default is eight scans X prescans Number of dummy scans The default is four scans y domain Observation nucleus of the f axis The default is Proton y offset O bservation center of the f axis The default is 5 ppm y sweep Observation range of the f axis The defaultis 15 ppm y points Number of points to sample along the t axis The default is 128 4 40 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES x pulse 90 pulse width of the observation channel PC on the f axis The default is x90 in the probe file x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved y pulse 90 pulse width of the observation channel H on the f axis The default is y90 set in the probe file y atn Attenuator value yatn set in the probe file Every time 6 dB is added the pulse width is halved j constant Value of J The default is 140 Hz relaxation delay Waiting time between repeated pulse sequences The default is 1 5 s Data processing The standard process list is 2d hetcor abs list How to interpret the spectrum The correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and 1 axis cross NM ECA ECX USM
154. lying a combination of pulses to the protons that are directly coupled to the observation nuclel and possess big magnetic moments The signal enhancement factor the factor of increase of signal intensity is much greater than that produced by the nuclear Overhauser effect NOE which uses the common proton decoupling method This is shown in the following table For example in the case of the nucleus the enhancement factor of the signal by NOE is about 4 whileitis about 10 when the INEPT or DEPT method is used Table5 1 Signal enhancement factor of observed nuclei resulting from NOE INEPT and DEPT Onserved 11 13 15 20c 57 103 109 119 183 INEPT 25 settings of measurement conditions are the same as those for INEPT or DEPT of NMR but adjust the coupling constant to the H nucleus depending on the observation nucleus For the coupling constants of typical nuclei to refer to the table shown in Section 5 5 1 e The measurement mode for INEPT is hp inept dec ex2 and that for INEPT is hp dept dec ex2 5 10 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT SPECIAL PHENOMENA AND PRECAUTIONS FOR MULTINUCLEAR NMR MEASUREMENT This section explains various precautions and phenomena to keep in mind when you perform multinuclear measurement 5 3 1 Precautions for Sample Preparation B Selecting a solvent It is better to use a solvent which does not contain the observed nucleus
155. mation contained in this manual or the software described in this manual Some countries do not allow the exclusion or limitation of incidental or consequential damages so the above may not apply to you e This manual and the software described in this manual are copyrighted all rights reserved by JEOL and or third party licensors Except as stated herein none of the materials may be copied reproduced distributed republished displayed posted or transmitted in any form or by any means including but not limited to electronic mechanical photocopying recording or otherwise without the prior written permission of JEOL or the respective copyright owner e When this manual or the software described in this manual is furnished under a license agreement it may only be used or copied in accordance with the terms of such license agreement Copyright 2002 2003 2004 2007 JEOL Ltd e n some cases this instrument the software and the instruction manual are controlled under the Foreign Exchange and Foreign Trade Control Law of Japan in compliance with international security export control If you intend to export any of these items please consult JEOL Procedures are required to obtain the export license from Japan s government TRADEMARK e Windows is a trademark of Microsoft Corporation e All other company and product names are trademarks or registered trademarks of their respective companies MANUFACTURER JEOL Ltd 1 2 Musashi
156. middle mouse button The copied position is pasted and the numerical value is entered into the list box 4 Repeatthe copy and paste operation and enter the numerical values into the list box 27 You can perform array measurement only if the array parameter window opens when you click on the item e You cannot use the parameters related to the size of files and the sampling points as the array parameters for example domains sweep widths and points If you want to change these parameters and perform successive measurements use the ordinary queue NM ECA ECX USM 3 2 99 ADJUSTMENT OF NMR PARAMETERS The greatest feature of the pulsed NMR method is that various informations can be derived from spectra which are affected by applying combinations of pulses pulse sequences The nuclear magnetization can be controlled by the pulsed RF excitation To manipulate the magnetization precisely you must set the parameters for controlling the magnetization Chapter 3 explains the procedures for these operations 3 1 PURPOSE OF MEASURING PULSE WIDTHS emm 3 1 32 SPECTROMETER RF SYSTEM AND FACTORS AFFECTING Ep IDE IE 3 3 33 MEASUREMENT OF PULSE WIDTHSWHEN OUTPUT IS Sui RN i EL 3 5 3 4 CALCULATION OF 90 PULSE WIDTHS AFTER THE ATTENUATOR VALUE IS CHANGED mms 3 8 35 MEASUREMENT OF PULSE WIDTHS IN 3 9 36 CALCULATION OF 90
157. mplifier and reaches the receiver The RF pulses are also applied to the irradiation channel through the duplexer NM ECA ECX USM 3 3 3 3 ADJUSTMENT PARAMETERS 1 W hen the RF pulses are output the spectrometer automatically selects the sequencer to use The output power differs a little depending on the selected sequencer but its error is less than 3 96 and is negligible in actual measurement T herefore measure only the pulse width when observation is carried out You do not need to measure the pulse width when irradiation is carried out Also when you change the RF power using the attenuator you can compute a pulse width because of its good linearity Factors affecting the pulse width The pulse width is determined by the strength of the RF magnetic field applied to the sample The strength of the RF magnetic field is determined by the shape of the RF coil and the current running through the coil The shape of the RF coil is a characteristic of the probe However the current running through the RF coil depends on various factors understanding these factors it is possible to consider when the pulse width should be measured and what points attention should be paid to for performing precise measurement The electric current running through the RF coil depends mainly on the following four factors a Design of the probe tuning circuit b State of the tuning circuit c Susceptibility of t
158. multinuclear NM are explained below Definition of multinuclear NMR M ultinuclear NMR is defined as all nuclear NMR except that for the H and nuclei where NMR signals can theoretically be observed Features of multinuclear M ultinuclear NM R has the following features e NMR signals of many nuclei can be easily detected and measured in a shorter time than that for the PC nucleus as commonly used in organic chemistry e The range of chemical shifts is wide as the specific nucleus possesses a large mass number and p electrons and d electrons are present around the atomic nucleus The sample can be measured even if it is not in solution e T here are many nuclei with 1 gt 1 2 when the nuclear spin exceeds 1 2 e The nuclei with 1 gt 1 2 possess a quadrupole moment resulting in short relaxation that gives rise to a wide signal line eA fast repetition pulse rate can be used for measurements of nuclei with short relaxation times to shorten the measurement time To observe multinuclear NMR it is necessary to use experimental conditions different from those for H and PC NMR and to have knowledge about the different measurement conditions and ranges of chemical shifts The various issues you may encounter when measuring multinuclear NM R are explained below NM ECA ECX USM 3 5 1 5 MULTINUCLEAR MEASUREMENT 5 1 2 Relative Sensitivity of Multinuclear NMR This section explains multinuclear NM
159. n of the target item For example if C a capital letter is entered from the keyboard when the mouse pointer is in the Solvent list box it will skip to CHLOROFORM 2 20 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 2 7 Control the NMR Lock The NMR lock is controlled in the Lock Control part of the Sample T ool window Lock HA TD gt Fig 2 14 Lock Control In the NMR lock a system in order to retain the magnetic field stability the magnetic field is locked using NMR signal of H nucleus in the sample If the magnetic field is changed or drifts the magnetic field will be stabilized using the ZO axis shim coil M oreover the lock signal intensity is used for shim adjustment The intensity of a signal becomes strong so that the magnetic field is uniform W hen using the NMR lock system the H nucleus must be contained in the sample Usually the H nucleus exists in the deuterated solvent such as Chloroform d B enzene d6 and A cetone d6 M easurement is performed without applying the NMR lock for the sample in which the H nucleus is not contained M oreover when measuring the H nucleus measurement is performed using the mode without the lock NM ECA ECX USM 3 2 21 2 SPECTROMETER CONTROL B NMR Lock Control Button Click the following button in Lock Control to control the NMR lock Icon Function Explanation l Lock ON Lock OFF A uto Lock e
160. nce data for relaxation times T and measurement conditions of principal nuclei Approx S Relative Coupling Chemical il Mb In 5 GEILE VENE ii Li p xo MN 5N 70 295 19A g Inc 19H g NM ECA ECX USM 3 0 008 20 ppm 2s eet m mm w Lan im om aaron a o mm 3 Lam sm o sow as Lan pam w o Tom Arwen n a ao we n om o ome Lum m o sow Cx m a ox we ow s a o e ow m m o ims 2 me o 1 Lan ws i O ws is Lan ss o wwe 5 17 5 MULTINUCLEAR MEASUREMENT 5 18 Repetition time FID acquisition time x acq time Repetition pulse waiting time relaxation delay Observation range FR Chemical shift range Resonance frequency Example NMR tH resonance frequency of 400 M Hz FR 1 000 ppm 88 676 MHz 88 7 kHz NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT _ L 5 5 CHARTS AND MEASUREMENT MODES FOR MULTINUCLEAR NMR MEASUREMENTS This section contains useful data for multinuclear NM R measurements 5 5 1 Relationships Between Nuclear Species and Sticks Sticks used with the TH5 probe are indicated in the table For sticks used with other pro
161. no 3 chome Akishima Tokyo 196 8558 Japan Telephone 81 42 543 1111 Facsimile 81 42 546 3353 URL http Avww jeol co jp Note For servicing and inquiries please contact your JEOL service office NOTATIONAL CONVENTIONS AND GLOSSARY B General notations CAUTION Points where great care and attention is required when operating the device to avoid damage to the device itself 2 Additional points to be remembered regarding the operation lt reference to another section chapter manual 1 2 3 Numbers indicate a series of operations that achieve a task A diamond indicates a single operation that achieve a task File The names of menus commands or parameters displayed on the screen are denoted with bold letters File Exit A command to be executed from a pulldown menu is denoted by linking the menu name and the command name with a dash For example File E xit means to execute the Exit command by se lecting it from the File menu Keys the keyboard are denoted by enclosing their names in a box Mouse operation M ouse pointer An arrow shaped mark displayed on the screen which moves with the movement of the mouse It is used to specify a menu item command parameter value and other items Its shape changes ac cording to the situation Click To press and release the left mouse button Double click To press and release the left mouse button twice quickly Drag
162. nsitive ROESY method NM ECA ECX USM 3 4 57 4 USAGE OF PULSE SEQUENCES 4 3 11 t roesy phase ex2 Phase sensitive detection ROESY measurement Directory usr delta global experiments roesy 25 T roesy is the abbreviation of Transverse Otating frame nuclear Overhauser Effect Spectroscopy CAUTION Too large an output too small a value of attenuator can damage the instrument Purpose of measurement To observe correlation signals due to ROE NOE in a rotating frame This method is useful for measuring samples having intermediate molecular weights 1000 to 5000 whose NOE is usually difficult to observe Nuclei existing spatially close to each other can be determined in the same way asin the NOESY method Pulse sequences relaxation x domain delay spinlock atn x spinlock 180 x spinlock 180 Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple The default is Off tri mode Select Off Presaturation or Homo Decouple default is Off B Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample along the t axis The default is 1024 4 58 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES y points Number of points to sample along the t axis The default is 256 Scan
163. nuclei with a nuclear spin of 1 2 as represented by the PC nucleus are several seconds to more than 10 seconds The half height width of an observed signal is narrow within several hertz as it is the reciprocal of the T relaxation time On the other hand for nuclei with a nuclear spin greater than 1 2 quadrupolar nuclei is fast milliseconds to sub milliseconds due to quadrupole moment effects The line width of the observed signal is wider than a few hundred hertz Generally the width at half height of the peak of a quadrupolar nuclei in solution is given by the following equation under the condition Wt lt lt l1 where the molecular motion is sufficiently fast 2 Js Nuclear spin 1 1 2143 A symmetry parameter of the electric field gradient around the nucleus under investigation Quadrupolar coupling constant Wo Observation frequency A uto correlation time of the molecule approximately equal to the time required for one rotation of the molecule in solution e Qq h NS From this equation it is seen that the relaxation time of a quadrupolar nucleus depends on and e Qg h Since 7 reflects the magnitude of the electric field gradient around the nucleus 7 is greatly dependent on coordination For example ions have coordination number of four with molecules in aqueous solution Because of this n becomes very small and T increases to about 2 seconds For your refe
164. obtained is used as the chemical shift standard Such substances are called second reference substances When you use a second reference substance you should measure the chemical shift in advance using the first reference substance If this chemical shift is the resonance frequency of the first reference substance is given by the following equation Then the chemical shift is given by equation 3 1 Resonance frequency of the first reference _ resonance frequency of the second reference 3 2 1 0 x10 W hen the chemical shift reference is set to a value other than zero in the data processing program the above calculation is performed B External reference and internal reference If the standard peak of the chemical shift is in the spectrum under investigation the peak 15 called an internal reference peak of a solvent the peak of a reference substance which is dissolved in the sample is used as the internal reference However in the multinuclear NMR the range of the chemical shifts may be too wide to measure the peaks of the sample and reference substance simultaneously Also the peaks of the sample and reference substance may overlap due to a wide line width In this case the absolute frequency of the reference substance peak has been measured in advance and the chemical shift scales can be calibrated with reference to this position This reference substance peak for the chemical shift is called an external referenc
165. ol co jp AE Atsushi Abe aabe gt B DEC 2003 16 39 36 NMR Instrument Control Software Version vl 3 Beta 12 04 03 09 11 AIX Instrument seed nm jecl co jp Model No JNM ECA500 Serial No 1 0360001 Files Passed 197 Files Failed 0 Files Not Found 0 Total Files DS PASSED control 2 12 3 Saving Validation Results to a File l Click on the Save the results button in the Delta Installation Validation window 4 aabe Delta Installation Validation 2 hi Abe aabe B DEC 2003 16 39 36 Instrument Control Software vdl 3 Beta 12 04 03 05 11 AIK 5022 1 2 JNM ECASOO 1 1 No NM10360001 Files Passed E ESN Total Files PASSED control The Save file window opens 2 Input a saving file name into the Name input box after moving to the directory to save and click on the Ok button The Validation result is saved 25 When creating a new saving directory click on the button after specifying a directory name to the Path input box Create and transfer the directory Then the saving file name is entered into the file name input box 2 60 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 13 DISPLAY OF LOG FILE This displays the spectrometer log Three kinds of Log Machine Log and Queue L og are saved as log 2 13 1 Cryogen Log Select Tools
166. only the correlation signals due to the ROE but also those due to HOHAHA appear NM ECA ECX USM 3 4 59 4 USAGE OF PULSE SEQUENCES 4 3 12 tocsy mlev1760 phase ex2 Phase sensitive detection TOCSY measurement using the M LEV 17 sequence Directory usr delta global experiments tocsy 25 TOCSY is the abbreviation of TOtal Correlation SpectroscopY TOCSY is another name for HOHAHA 15 abbreviation of HOmonuclear HA rtmann HA hn spectroscopy B Purpose of measurement To extract a group of peaks a spin network connected with each other couplings Unlike in the relayed shift correlation method correlation signals appear non selectively The phase sensitive detection enhances the separation and the S N ratio of signals B Pulse sequence x pulse 90 mix time MLEV17 relaxation x spinlock atn delay x domain gt trim Extension sequences dante_presat The default is FALSE irr_mode Select Off Presaturation or Homo Decouple T he default is Off tri_mode Select Off Presaturation or Homo Decouple T he default is Off Parameters x_domain Observation nucleus The default is Proton offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample The default is 1024 scans Number of scans to accumulate a multiple of 4 The default is 4 Scans X prescans Num
167. or M inimolecules Emulated by L ocked Spins Purpose To observe only the peaks enhanced by ROE NOE in the rotating frame due to selective excitation of a specific peak This method is effective for samples having medium molecular weights of 1000 to 5000 whose NOE is difficult to observe Pulse sequences obs sel 180 x pulse 90 x pulse 90 relaxation E x domain delay x spinlock atn Mix time grad 3 grad 2 FG channel grad 1 amp grad 3 amp grad 2 amp Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple The default is Off tri mode Select Off Presaturation or Homo Decouple default is Off Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm X points Number of points to sample The default is 16K scans Number of scans to accumulate a multiple of 16 The default is 16 scans 5 3 4 27 4 USAGE OF PULSE SEQUENCES X prescans Number of dummy scans x pulse 90 pulse width of observation channel H The default is x90 set in the probe file x atn The attenuator value is xatn set in the probe file Every time 6 dB is added the pulse width is halved obs sel 180 Set 1809 pulse width of the selective excitation pulse The default v
168. ormation about a peak integration and assignment in table format Parameter viewer A connection tool is to connect the display range of different data set Connection is performed using the reference of an axis You can Connection associate any data sets regardless of the number of data points tool observation width and magnetic field strength If connection is performed and the display range is changed to one data file other related data will be automatically set to the same display range Spectrometer A spectrometer control tool is tool which connects and disconnects the control tool host computer and the spectrometer Help The help button displays an electronic manual using crobat Reader 1 4 NM ECA ECX USM 3 SPECTROMETER CONTROL L SPECTROMETER CONTROL WINDOW aue vani 2 1 2 11 Starting the Spectrometer Control W indow ee 2 1 2 1 2 Connecting and Releasing 6 2 2 2 1 3 Management of the M easurement 2 7 PIS cee 2 9 crnan E 2 10 Jed Storing Sample Tool Mc pH 2 11 2 2 2 Display of SCM Related 2 12 2 2 3 Loading and Ejecting a BOIS ua abor MERE 2 13 Uo NES ur es mm 2 16 2249 Variable Temperature UY
169. ose of measurement To set the 90 shifted laminate pulse width when obs sel atn is used to adjust the RF output Pulse sequences obs sel pulse obs sel atn x domain relaxation delay Shifted laminate pulse Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple T he default is Off tri mode Select Off Presaturation or Homo Decouple T he default is Off Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Sampling points The default is 16K scans Number of scans to accumulate T he default is 16 scans X prescans Number of dummy scans obs sel pulse 90 pulse width of the shaped pulse The default is the pulse width X90 soft set in the probe file obs sel atn Determines RF output for the selective excitation pulse The default 15 the attenuator value xatn soft set in the probe file Every time 6 dB is added the pulse width is halved obs sel shape Waveform of the selective excitation pulse The default is GAUSS NM ECA ECX USM 3 4 13 4 USAGE OF PULSE SEQUENCES number Number of peaks to be irradiated by the laminate pulse up to six The default is 1 offset1 Resonance frequency of the peak to be irradiated by the laminate pulse The default is 5 ppm 91 offset2 51 offset2 slp off
170. p Observation range of the f axis The defaultis 170 ppm y offset Observation center of the f axis The default is 85 ppm y points Number of points to sample along the t axis The default is 256 scans Number of scans to accumulate T he default is 16 scans X prescans Number of dummy scans The default is four scans 4 52 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES Z x_pulse 90 pulse width of the observation channel H The default is x90 set in the probe file x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved y pulse 90 pulse width of the irradiation channel of the f axis The default is y90 hi set in the probe file y atn Attenuator value yatn set in the probe file constant Coupling constant default 15 14 purge Pulse width of the spin lock purge pulse The default is 1 ms x spinlock pulse 90 pulse width of the M LEV 17 sequences spin lock The default is x90 spin set in the probe file x spinlock atn Determines the power of the observation channel during spin lock The attenuator value is xath spin set in the probe file trim Pulse width of the trim pulse The default is 1 ms mix time M ixing time The default is 50 ms relaxation delay Waiting time between repeated pulses Set it to about 1 3 times T of The default is 1 5 grad 1 amp Pulse output of the first FG pulse PFG1 The default is 3596 grad 2 amp P
171. pectrometer The connectable spectrometers are listed in the Spectrometer C ontrol window By connecting with the spectrometer in this list you can perform NM R measurement Connecting to spectrometer T here are three ways to connect to the spectrometer W hen performing out N M R measurement connect in the C onnect mode 25 Connection is restricted by the account logged into Refer to the ADMINISTRATOR S MANUAL for these setting 4S Even if you have the right to connect connection in a specified mode may not be performed according to the state of the spectrometer Mode Explanation Monitors the state and measurement conditions of the spectrometer When other users have already connected with spectrometer only Monitor mode may be Monitor connected NMR measurement cannot be performed However measurement can be reserved M easurement can be started when anyone who has connected in Connect mode releases the spectrometer Connect NMR measurement and spectrometer control are performed in this mode In this mode deleting the jobs records to the Queue from other work stations forced release of spectrometer connection from other work stations change in a job priority and rewriting of system files can be performed However NMR measurement cannot be performed Console l Select the target spectrometer using the mouse from the spectrometer list displayed in the Spectrometer Control window and can be communicated Select
172. pposed If the homogeneity of a sample is bad operation of the gradient shim will be affected Especially when the solvent is water take to remove ant small bubble founded in a sample 2 76 NM ECA ECX USM 3 2 SPECTROMETER CONTROL Lim gt n order to determine the effective range of the magnetic field map set 96 W idth to 1 set Iterations to 10096 and turn ON Display Field M ap then perform gradient shimming The flat portion of the magnetic field map becomes the effective range In order to make a percent display for the horizontal axis of the magnetic field map select Ruler Percent in the menu with the right mouse button NM ECA ECX USM 3 2 77 2 SPECTROMETER CONTROL 2 19 SPECTROMETER CONFIGURATION tool which changes the spectrometer Configuration file is provided CAUTION Configuration files such as machine config file are required for setting spectrometer information When they are not correctly defined not only an instrument does not operate correctly but they also become the cause of instrument trouble Since the configuration file is set up by commonly at the time of in strument delivery do not usually change this file Select Tools Mode onsole in the menu bar of the Spectrometer Control window aabe Spectrometer Control Config Queue Machine Options ode Monitor Command Line Tab Connect Upload Manager U f Console o Z
173. priately controlled or managed for the maintenance e After installation or delivery of the instrument if the instrument is required for the relocation whether it is within the facility transportation resale whether it is involved with the relocation or disposition please be sure to contact your JEOL service office If the instrument is disassembled moved or transported without the supervision of the personnel authorized by JEOL JEOL will not be held responsible for any loss damage accident or problem with the instrument Operating the improperly installed instrument might cause accidents such as water leakage fire and electric shock e The information described in this manual and the specifications and contents of the software described in this manual are subject to change without prior notice due to the ongoing improvements made in the instrument e Every effort has been made to ensure that the contents of this instruction manual provide all necessary information on the basic operation of the instrument and are correct However if you find any missing information or errors on the information described in this manual please advise it to JEOL service office e n no event shall JEOL be liable for any direct indirect special incidental or consequential damages or any other damages of any kind including but not limited to loss of use loss of profits or loss of data arising out of or in any way connected with the use of the infor
174. rad 1 and the intensity ratio of the PFG to be applied to y domain W aveform of the FG pulse SELECT SQUARE SINE or GAUSS The default is SINE Recovery time after the FG pulse The default is 0 1 ms 4 45 4 USAGE OF PULSE SEQUENCES Data processing The standard process list is 2d hmbc abs list How to interpret the spectrum The f axis represents the chemical shift and the f axis is the C chemical shift The correlation signals due to the long range coupling between and PC appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross The correlation signals of the direct coupling between the and H are also observed However these signals can be distinguished as the latter signals are split due to along the f axis Supplementary note The ratios of the gradient pulses are as follows For the PC nucleus PFG1 PFG2 PFG3z2 2 1 For the N nucleus PFG1 2 4 94 4 94 1 For the Si nucleus PFG1 PFG2 2 52 2 52 1 For the nucleus PFG1 PFG2 PFG3 1 24 1 24 1 PFG1 grad 1 grad 1 amp PFG2 grad 2x grad 2 amp PFG3 grad 3x grad 3 amp e The standard value of long range j is 8 2 PC and PN Be careful in that the value of long range j depends on the sample e f you set scans to an odd number insert dc balance at the top of the process list of the X axis the f axis
175. radiated The default is 50 ppm irr pwidth Pulse width irr90 hi of the decoupling pulse that is set in the probe file irr noise D ecoupling mode The default 15 CW irr atn dec Determines RF output for decoupling The default is the attenuator valueirratn hi set in the probe file Every time 3 dB is added the RF output is halved 4 8 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 1 7 raw suppression This RAW RAW SCUBA sequence is used to reduce a signal that would overwhelm the desired peak such as a water signal in an aqueous solution sample B Pulse sequences RAW raw pulse x domain raw grad EM raw interval FG channel raw grad amp x pulse x pulse x pulse x 2 RAWSCU raw_pulse x domain raw grad FG channel raw grad amp raw interval 2 Parameters raw pulse Pulse width of the shaped pulse used for the RAW sequence The default is the pulse width x90 soft set in the probe file raw attenuator Determines RF output for the shaped pulse in the RAW sequence The default is the attenuator value xatn soft set in the probe file E very time is added the pulse width is halved raw shape Select the waveform of the shaped pulse The default is GAUSS raw grad Pulse width of the PFG pulse The default is 1 ms raw grad amp Output of the PFG pulse The default is 38 4 raw grad shape Waveform of pulse The default is SQUARE raw interval Pulse interval
176. rence values of T of several compounds measured in solution or as crystals are shown below Table5 2 Measured values of T Nucleus measured Be 1 3 2 Be 2 1 95 76 Al 0 0 130 CuCl Powder 4 7 ms I 3 2 CuBr Powder 10 ms Cul Powder 21 ms 5 16 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT 5 4 2 Reference Data for Relaxation Times and Measurement Conditions of Principal Nuclei As described above when nuclei with 1 2 are placed in an environment with a large electric field gradient the line widths of the signals become wide due to quadrupole moment effects For such nuclei T is short and the FID free induction decay signals after applying the observation pulse decay rapidly Therefore large observation ranges and rapid signal acquisitions are required Actually with multinuclear NMR measurement it is important to know the approximate T values of the nucleus under investigation beforehand in order to estimate the line width and set the pulse width The following table collects reference data for measurement conditions for principal nuclei Relative sensitivities are based on the standard value of the C nucleus For T and the longest values are shown in the table For coupling to coupling constants can be observed without decoupling for the nuclei marked and cannot be observed without decoupling for the nuclei marked X Table5 3 Refere
177. resent spinning speed Target spinning speed Fig 2 10 Spinner display 25 When the green indicator turns yellow this means changing from the spin off state to the spin on state or the spin off state from the spin on state Spinner on Click on the button in the Spinner of the Sample Tool window Spinner A sample begins a spinning and the sample state changes into the spin on state Spinner off Click on the button in the Spinner of the Sample Tool window A sample 15 ejected and the sample state changes into the eject state 2 16 NM ECA ECX USM 3 2 SPECTROMETER CONTROL m 2 2 5 Variable Temperature VT Sample temperature The temperature control state of the sample can be verified by Temperature display in the Sample Tool window When the Temperature Hold function is not provided VT ON Present sample temperature UCurent 18 5 dC Target sample i orar 1 Target 4130 0 dC lt gt 4 25 0 dC 1 Fig 2 11 Temperature display without the T emperature H old function 25 When the green indicator turns yellow this indicates to change from VT OFF state to VT ON state or VT OFF state from VT ON state is shown e When the Temperature hold function is provided 25 norder to use temperature hold function after changing the value of TEMP HOLD AVAILABLE in the machine config file of the spectrometer into TRUE it is necessary to restart the
178. rvation range The default is 250 ppm x points Number of points to sample The default is 32K Scans Number of scans to accumulate a multiple of 8 The default is eight scans X prescans Number of dummy scans x pulse 90 pulse width of the observation channel C The default is x90 set in the probe file x atn D etermines RF output The default is xatn set in the probe file Every time 6 dB is added the pulse width is halved tau interval Interval between two pulses delay time for the relaxation The default is 10 s 4 34 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES relaxation delay Waiting time between repeated pulse sequences The default is 7 s repetition time relaxation delay x acq time Data processing The standard process list is std carbon list How to interpret the spectrum In the case of single exponential decay the observed magnetization M c at the pulse interval c is expressed by the following equation 2e 1 W hen the magnetization become zero the tau value is called the null point If the null point is indicated by c T is given by the following equation null Tull 1 44 2 null NM ECA ECX USM 3 4 35 4 USAGE PULSE SEQUENCES 4 3 2D MEASUREMENT 4 3 1 cosy pfg ex2 PFG homonuclear shift correlation measurement Directory usr delta global experiments cosy 27 is abbreviation of Pulsed Fi
179. s FALSE tri mode Select Off Presaturation or Homo Decouple default is Off B Parameters x domain Observation nucleus The default is Proton Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm points Number of points to sample The default is 16 scans Number of scans to accumulate The default is 16 scans X prescans Number of dummy scans x pulse 90 pulse width x90 set in the probe file x atn Attenuator value xatn set in the probe file Every time 6 dB is added the pulse width is halved relaxation delay Waiting time between repeated pulses default is 5 s repetition time relaxation delays x acq time Data processing The standard process list is std proton list NM ECA ECX USM 3 4 15 4 USAGE OF PULSE SEQUENCES 4 2 6 aptex2 APT measurement Directory usr delta global experiments 1d 4S APT is the abbreviation of Attached Proton Test Purpose of measurement To determine the number of hydrogen nuclei directly bonded to each carbon nucleus B Pulse sequences relaxation _ delay x domain X ia X_ ib x pulse x 2 lt t 1 j_constant Parameters x_domain x_offset X Sweep x points scans X prescans x angle x 90 width x pulse x pulse 180 x atn j constant Observations nucleus The default is Carbon13 Observation center The default is 100 ppm Observation range
180. s Number of scans to accumulate a multiple of 4 The default is 4 Scans X prescans Number of dummy scans The default is 4 scans x pulse 90 pulse width of the observation channel 1H The default is x90 set in the probe file x atn Attenuator value set in the probe file Every time 6 dB is added the pulse width is halved x spinlock mode Select the mode of the spin lock pulse The default is 18 dB down x spinlock Determines RF output for the spin lock pulse The default is x atn minus the value selected in x spinlock mode spinlock strength Indicates the frequency range to be excited by the spin lock pulse mix time M ixing time The default is 250 ms total mix time X Mixing time to be actually used relaxation delay Waiting time between repeated pulses T default is 1 5 sec repetition time relaxation delay x acq time y pl correction Value to be entered in the first order term P1 of the phase correction of the t axis Data processing The standard process list is 2d homo2d phase autophase list How to interpret the spectrum Both the f axis and the f axis represent H chemical shifts The correlation signals due to ROE appear at the points where the perpendicular lines drawn at the peak positions on the f axis and the f axis cross Supplementary note If the spin lock intensity is too weak the intensity of signals at the end of the observation range decreases If it is too strong not
181. section aabe Experiment Tool single pulse exz File Tools View Options x time 218383 s nn scc Total Collection Time 00 01 03 e Fig 2 30 Acquisition section of the E xperiment T ool NM ECA ECX USM 3 2 35 2 SPECTROMETER CONTROL Addition of the Acquisition parameter Y ou can add a new parameter to the Acquisition section using the following methods 1 Click on the Acquisition tab of the Experiment Tool window TheAcquisition section appears 2 Click on the button ei aabe Experiment Tool single pulse exz File Tools View Options 2 18383 s MM o L xX aco ti G 3 3cc2 nmm jenl Total Collection Time 00 01 03 Fam Fig 2 31 Include Parameter window 3 Selectthe parameter to add T he selected parameter is highlighted 4 Click on the Add button 5 Repeat steps 3 4 if required 6 Finally click on the Done button The parameter added to the A cquisition section appears 2 36 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 2 3 5 Pulse Section Y ou can set parameters such as time and an attenuator that is required for a pulse sequence in the Pulse section 4 aabe Experiment Tool single pulse exz File Tools View Options repetition time presat o u Total Cottection Time 00 01 03 Fig 2 32 Pulse se
182. set3 slp offset4 slp offset5 sip offset6 Resonance frequencies of the peaks two or more peaks to be irradiated by the laminate pulse The default is 0 ppm obs sel shape Waveform of the selective excitation pulse The default is GAUSS obs shape to be irradiated by the laminate pulse The default is 5 ppm relaxation delay Waiting time between repeated pulses The default is 5 s repetition time relaxation delay x acq time Data processing The standard process list is std proton list Supplementary note A shift laminate pulse allows excitation of multiple frequencies by applying rf intensity and phase modulation to the pulse with a specific waveform 4 14 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 5 single pulse wet ex2 Single pulse measurement including the W ET sequence Directory usr delta global experiments 1d Purpose of measurement To reduce a signal that would overwhelm the desired signal such as a water signal in an aqueous solution sample using the WET sequence Pulse sequences wet pulse wet pulse X pulse 4 wet pulse wet pulse X atn relaxation _ delay irr domain atn e s wet grad amp x domain wet grad amp 2 PFG4 Wet grad amp 4 wet grad 8 FG channel Extension sequences wet suppression The default is TRUE dante presat The defaulti
183. signal of a new nucleus or an unknown sample due to the wide chemical shift ranges in multinuclear NMR This is especially true when measuring a new nucleus or an unknown sample However if the chemical shift range for the nucleus or sample under study can be estimated or if the chemical shift value of a similar compound is known the time required to find the signal can be substantially reduced To assist in this estimation reported experimental data for chemical shift ranges of the following nuclei are shown below PC 70 PF Al 951 p 336 977p DAS Se Rh Ag Pt Pb The vertical lines in the figure show the positions of the signals If the signal has two or more lines these are also indicated When you measure a new nucleus or an unknown sample it is recommended that you use these chemical shift figures 60 40 20 0 20 40 60 ppm 22 0 15 2 11 8 55 0 pars B OH 2 CoHs B Hal 16 2 0 7 49 8 5 11 29 6 15 1 14 87 750 Bocanci 12 9 5 18 0 25 8 BIN CoH gan BsH0 C2Hs 47 9 104 0 20 4 556 55 1 BLHsN CHs 16 8 oe dog 22456 3209 61 0 60 40 20 0 20 40 60 Fig 5 6 B chemical shifts NM ECA ECX USM 3
184. spectrometer VT ON VT OFF Holding temperature Current 30 dC _ Target 30 0 Present sample temperature Target temperature Fig 2 12 Temperature display with the Temperature H old functional 25 When the green indicator turns yellow this shows to change from the present VT OFF stateto VT ON state or VT OFF state from VT ON state 27 The temperature in a temperature hold is the temperature of the sample space this means holding this temperature during a sample exchange NM ECA ECX USM 3 2 17 2 SPECTROMETER CONTROL VT ON When the temperature hold function is not provided Click on the button under Temperature in the Sample Tool window The temperature controller begins operation and the state display of a sample changes to the VT ON state 25 When setting the temperature exceeding boiling point and melting point of the selected solvent to Target a warning display appears and the temperature setting is reset e When the temperature hold function is provided Click on the button under Temperature in the Sample Tool window Cox Target 4 25 0 The temperature controller begins operation and the state display of a sample changes into the VT ON state 25 When setting the temperature exceeding boiling point and melting point of the selected solvent to Targe a warning display appears and the temperature setting is reset 2 18 NM ECA ECX USM 3 2 SPECTROMETER C
185. t follow 3 4 NM ECA ECX USM 3 3 ADJUSTMENT OF NMR PARAMFTFRS C MEASUREMENT OF PULSE WIDTHS WHEN OUTPUT IS USED HALF POWER NMR spectrometer contains a power amplifier having sufficient output power The output at full power 15 too strong so usually half power using the attenuator at 3 dB 15 used for measurement This section explains the method of measuring a pulse width at half power supposing you can operate basic and 1D NMR measurement and data processing B Attenuators The maximum output of the power amplifier in the spectrometer is so strong that normally the attenuators are used to reduce the intensity of RF signals The parameters that specify the ratios of attenuation represent attenuator values The parameter of the attenuator in each channel is shown in the following table Channel name Parameter name Observation channel x atn Irradiation channel irr atn T he attenuator values the range from 0 to 120 dB The full power is output at 0 zero dB and the minimum power at 120 dB When the attenuator value increases by 3 dB the input power into the power amplifier decreases by half according to the following equation Pow2 1 1 0 0 2 1 Pow1 Power when the attenuator value is ATT1 Pow2 Power when the attenuator value is ATT2 The magnetic field strength B produced by the RF coil is proportional to the voltage applied to the coi
186. t is std proton list How to interpret the spectrum Only the ROE NOE in the rotating frame signal caused by selectively exciting a specific peak can be observed This method is effective for samples having medium molecular weights of 1000 to 5000 whose NOE is difficult to observe 4 28 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES gt Supplementary Check the accurate value of the selective excitation pulse obs sel 180 using single shaped pulse ex2 e A bout the intensity of spin lock In this measurement method the spin lock intensity is adjusted by the set attenuator value from the output at full power The 90 pulse width during the spin locked period is given by 1 100 53 where a s 90 pulse width at full power b dB Attenuator value which was set from this The spin lock intensity is computed as 1 Spin lock intensity m Set spin lock intensity equal to the observation range t is recommended that you stop spinning of the sample tube before measurement NM ECA ECX USM 3 4 29 4 USAGE OF PULSE SEQUENCES 4 2 12 tocsy 19 dpfgse ex2 DPFG 1D TOCSY measurement using a shaped pulse Directory usr delta global experiments 1d tocsy TOCSY is abbreviation of TOtal Correlation SpectroscopY TOCSY is sometimes called HOHAHA HOHAHA is the abbreviation of HOmo nuclear rtmann HA hn spectroscopy Purpose To observe the conne
187. the pulse width is halved on resonance Position ppm of the peak to be selectively irradiated The default is 0 ppm off resonance Position ppm of the reference spectrum to be irradiated sufficiently apart from that of the sample signal The default is 10 ppm NM ECA ECX USM 3 4 23 4 USAGE OF PULSE SEQUENCES noe buildup Selective irradiation time The default is 5 s attenuator D etermines RF output for the selective irradiation pulse The default is 40 dB Every time 3 dB is added the RF output is halved relaxation delay Waiting time between repeated pulses repetition time relaxation delay x acq time Data processing The standard process list is std proton list B How to interpret the spectrum Only NOE due to selective excitation for a specific peak can be observed Thus the spectrum gives information on three dimensional positional relationships among atomic groups in the molecule 4 24 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES 4 2 10 19 dpfgse ex2 10 NOE measurement using a shaped pulse Directory usr delta global experiments 1d noe Purpose To observe only the NOE signal caused by selectively exciting a specific peak This measurement provides information on three dimensional positional relationships among atomic groups in the molecule Pulse sequences x pulse x pulse 180 pulse 90 90 relaxation x domain
188. time after the FG pulse The default is 0 1 ms The standard process list is std proton list How to interpret the spectrum A specific peak is selectively excited and then spin spin coupling to its excited peak can be observed The spin coupling network including the selectively excited peak can be clarified NM ECA ECX USM 3 4 31 4 USAGE OF PULSE SEQUENCES 4 2 13 double pulse ex2 M easurement using double pulses Directory usr delta global experiments relaxation Purpose To evaluate T the longitudinal relaxation time simply Pulse sequence x pulse x 2 x pulse 180 90 tau interval relaxation x domain delay Extension sequences dante presat The defaultis FALSE irr mode Select Off Presaturation or Homo Decouple default is Off tri mode Select Off Presaturation or Homo Decouple default is Off Parameters x domain Observation nucleus The default is Proton x Offset Observation center The default is 5 ppm X sweep Observation range The default is 15 ppm X points Number of points to sample The default is 16K Scans Number of scans to accumulate a multiple of 8 The default is eight scans prescans Number of dummy scans x pulse Number of preliminary scans before accumulation pulse width of observation channel H The default is x90 set in the probe file x atn Determines RF output the attenuator value set in the probe file Ever
189. tion and the intrinsic line width becomes so sharp that the coupling constant can be observed In VO NMR directly coupled H contributes to the signal line width Of course H 5 14 NM ECA ECX USM 3 5 MULTINUCLEAR MEASUREMENT decoupling is performed for nuclei where 1 2 and the sample contains H When H decoupling is performed the following two problems should be considered a The sample can be heated by the influence of decoupling b The signal can disappear due to the negative N OE effect Problem a occurs when a solvent with a high dielectric constant like an aqueous solution is used Problem b occurs when a nucleus which possess a negative spin like DN Si is measured If the above problems occur use gate decoupling in place of complete decoupling 5 3 7 Calculating the Pulse Width When There Is No Proper Reference Sample If you are unable to obtain a reference sample for measuring or to calibrate the pulse width because it is too expensive or for some reason use the reference sample for a nucleus with a close resonance frequency The pulse width can be calibrated according to the following equations From principles a flip angle 0 at which the magnetization precesses is given by 0 radian y x B4 x PW where B is the magnetic field produced by an RF pulse PW 15 the pulse width and 7 15 the nuclear magnetogyric ratio for the observation nucleus If the sticks are the sam
190. tory Data processing is performed using the specified process list in a global directory after measurement is complete and a result is saved 1D Processor or nD Processor is not displayed Data is sent to 1D Processor or nD Processor after measurement is complete Then the specified process list in a global directory is set The process list of the data displayed on 1D Processor and nD Processor is used The program which performs data processing is performed If you click on the Get Process List button the Select Process L ist window opens Select a process list and click on the button aabe Select Process List Fig 2 26 Select Process L ist window 4 After setting is complete click on the Accept button in the Set Process window The Set Process window is closed and a new process list is set in the process of the H eader section of the Experiment T ool window NM ECA ECX USM 3 2 31 2 SPECTROMETER CONTROL Addition of Header parameter Y ou can add a new parameter to the H eader section using the following methods 1 Click on the Header tab in the Experiment Tool window T he H eader section appears 2 Click on the active global std proton autophase list vi Total Collection Time 00 01 03 Fig 2 27 Include Parameter window 3 Select the parameter to add The selected parameter is highlighted 4 Click on the Add button 5 Repeat steps 3 4 i
191. tting the array parameters in the Experiment Tool window Array measurement can be carried out in the same way as ordinary measurement by clicking on the Submit button There are the two methods of setting the array parameters as described below e Entering anumerical value into the parameter input box directly e Using the array parameter window Array parameter notation M ost of measurement parameters can be used as array parameters using the y_acq command for 1D measurement The character y indicates that the array parameters form the temporary y_domain of 2D data sets The array parameters for 2D measurement are also represented as z_acq and form the temporary z domain of 3D data sets This section describes array measurement in the single pulse ex2 window c For explanation about Array data processing refer to the Processing ser s M anual Preparation before setting array parameters l Select the measurement mode from the Open Experiment window and click on the Ok button The Experiment Tool window opens 2 Enter the parameters such as filename and sample id NM ECA ECX USM 3 2 95 2 SPECTROMETER CONTROL Entering a numerical value into the parameter input box directly The format for input into the parameter input box is y_acq valuel value2 value3 Array parameter values enclosed with braces follow and allow any numerical values or numerical values varying with a constant difference
192. tton turns on the NMR lock after executing gradient shimming Usually sufficient resolution can be obtained by operating these buttons Early shim conditions are read from the system shim file The conditions of the gradient shimming are fixed c Refer to Subsection 2 2 7 IBNMR lock control button for more information on the usage Gradient Shim Tool Gradient shimming 15 performed under specified conditions Change of the resolution can be verified by display of a magnetic field map This gradient shim tool 15 used when good resolution cannot be obtained by the function of the above button and when performing gradient shimming other than on a standard Preparation Preparation before beginning gradient shimming 15 as follows First load a sample into the SCM 1 Open the Sample window and turn ON a spinner 2 Specify a lock solvent from the Solvent list box 3 Turn OFF an NMR lock 5 3 2 73 2 SPECTROMETER CONTROL B Starting Gradient Shim Tool Select Config Gradient Shim in the menu bar of the Spectrometer Control window The Gradient Shim T ool window opens SH aabe Gradient Shim Tool peration NE EM avstem Nucleus 2H ICHLOROFORM D Fig 2 56 Gradient Shim T ool window Setting measurement conditions l Specify the type of the magnetic field gradient and an observation nucleus System H omospoil is turned ON
193. uclear M ultiple Bond Connectivity Purpose To observe long range correlation signals between H and C nuclei The correlation signals between quaternary carbons and H nuclei can also be observed B y observing the H nucleus the S N ratio is enhanced compared with that using the PC observation heteronuclear long range shift correlation coloc ex2 method B Pulse sequences x pulse x pulse x 2 90 180 domain relaxation delay y pulse y pulse y pulse 90 90 90 t 2 y domain grad 1 grad 2 grad 3 FG channel grad 1 amp grad 3 amp grad 2 amp 1 1 2 Xj constant t 1 2Xlong range 1 2Xj constant Extension sequences dante presat The defaultis FALSE tri mode Select Off Presaturation or Homo Decouple T he default is Off Parameters x domain Observation nucleus of the 1 axis The default is Proton x Offset Observation center of the 1 axis The original valueis 5 ppm 4 44 NM ECA ECX USM 3 sweep x points SCans X prescans y domain y offset y Sweep y points x pulse x atn y pulse y atn constant long range j relaxation delay repetition time grad selection grad 1 grad 1 amp grad 2 grad 2 amp grad 3 grad 3 amp grad shape grad recover NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES C Observation range of the 1 axis The defaultis 15 ppm Number of points to sample along the t axis The default is 2048 Num
194. uclear Observation PIODSS 5 5 5 2 2 Operational Procedure for M ultinuclear easurement 5 6 5 2 3 Chemical Shifts and Reference Substances 5 7 5 2 4 Observation of Nuclei Having a Resonance Frequency Close Wmo me A REID e ien ROOMS 5 9 5 2 5 Sensitivity Enhancement the Pulse Technique 5 10 5 3 SPECIAL PHENOMENA AND PRECAUTIONS FOR MULTINUCLEAR NMR 5 11 5 3 1 Precautions for Sample 5 11 Du Selecion of Sampie TUDES KE DAR KU MEA 5 11 NM ECA ECX USM 3 C 3 CONTENTS 5 3 3 Problems Involved with a Wide Chemical Shift Range 5 12 2355 Sona Fo ONET 5 13 5 3 5 Problems with Low Frequency 5 14 2245 5 14 5 3 7 Calculating the Pulse Width When There Is No Proper TET 5 15 5 4 RELAXATION TIMES OF 1 1 5 16 5 4 1 General Tendencies of Relaxation Times of ultinuclei 5 16 5 4 2 Reference Data for Relaxation Times and M easurement Conditions GI PEDCIBALN UCIBI successerit 5 17 5 5 CHARTSANDMEASUREMENT MODES FOR MULTINUCLEAR NMR 5 19 5 5 1 Re
195. ulse output of the second FG pulse PFG2 The default is 1096 y pl correction Value to be entered in the first order term P1 of the phase correction of the t axis Data processing The standard process list is 2d inverse phase autophase list How to interpret the spectrum The f axis represents the H chemical shift and the f axis the chemical shift The correlation signals appear at the points where the perpendicular lines drawn at the peak positions on the f axis and f axis cross The peaks due to CH and CH lt deflect upward and those due to deflect downward The correlation signals between PC nuclei and not only directly coupled H but also H nuclei connected to it appear W hen the mixing time gets longer the correlation signals with further separated nuclei appear although the S N ratio deteriorates Supplementary note e f the spin lock intensity is too weak signals over wide range cannot be spin locked effectively enough The spin lock intensity is obtained by the equation shown below and there is no problem if its value is twice the measurement range or more 1 Spin lock intensity 2 P Lus 4 spinlock pulse e t is recommended that you stop spinning the sample tube during measurement e Too long a spin lock time deteriorates the S N ratio due to the relaxation time NM ECA ECX USM 3 4 53 4 USAGE OF PULSE SEQUENCES 4 3 9 inadequate 2d pfg ex2 PFG P
196. vation range Also the peak position may unexpectedly go out of the observation range In these cases the peaks which have gone out of the observation range are sometimes observed as fold over peaks However if the signal intensity is strong the fold over peaks may not be recognized When a nucleus or sample is measured for the first time verify according to the following steps that the peak positions are within the observation range l Maximize the observation range 2 Change the observation center frequency 3 Change the value of the electrical filter First maximize the observation range for the measurement N ext change the observation center frequency Observation center frequency Real peak or even numbered fold over peak Observation center frequency Odd numbered fold over peak Fig 5 5 Movement of fold over peak while the observation center frequency is being changed Pay attention to the direction of the peak movement If the peak moves in the same direction as the observation center frequency it is an odd numbered fold over peak If the peak moves in the opposite direction it is the real peak or an even numbered fold over In this way an odd numbered fold over can be recognized Next you need to recognize an even numbered fold over Set the observation center to the peak position Set the filter value to 1 4 of the observation range and then to the maximum remove the filter and compare the peak intensit
197. ven when only the solvent without the sample is measured and thus can be distinguished from the real signal It is possible to decrease the acoustic ringing by using the following two methods e M akethe delay time longer Click on the Expmnt button in the Spectrometer Control window The Open Experiment windowopens In the 1d special directory in this window the pulse sequences single pulse manual ex2 and single pulse dec manual ex2 are available for the X nucleus measurement without H irradiation and the X nucleus measurement with tH irradiation respectively The acoustic ringing can be decreased by prolonging the time between applying the observation pulse and starting the FID sampling dead time delay Usually fix dead time to 10 5 and adjust delay to decrease the acoustic ringing If delay is prolonged the acoustic ringing decreases but when delay approaches T of the peak the signal intensity decays rapidly Also if delay is prolonged the first order phase shift becomes large causing the baseline waving This problem can be solved to some extent by phase simulation 5 3 6 Selecting tH Decoupling tH decoupling for nuclei having gt 1 2 is not needed in most cases as the intrinsic line width is larger than the H coupling constant due to the influence of the quadrupole moment However decoupling is needed for measurement of the following two nuclei The nucleus ionized in solution gives a high symmetrical construc
198. w the Open Experiment window that selects a pulse sequence opens Then if you select a pulse sequence and click on the Ok button the Experiment Tool window that sets a measurement parameter will also open 4 11 aabe Open Experiment Path usr delta global experiments Format Fig 2 22 Open Experiment window If you select a pulse sequence in the Open Experiment window and click on the Ok button the Experiment T ool window opens aabe Experiment Tool single pulse ex2 File Tools View Options 3 a e i3 i son z 4 nstrumen ACC ruse 1 x p browse Hefte DuUwse sample ic rey comme EE 3 4 EIE ul auto filter s auto 4 1 af THe 110411 time Collection Time 04183 x d a Fig 2 23 Experiment T ool window In the Experiment Tool window the parameters foe each section H eader Instrument Acquisition and Pulse are set up and measurement is started by the selecting Submit button NM ECA ECX USM 3 2 27 2 SPECTROMETER CONTROL gt 2 3 1 Measurement File Experiment File In this spectrometer the file in which the pulse sequence was stored is called the measurement file Experiment File A measurement file contains the standard value of a measurement parameter in addition to a pulse sequence Storage area for a measurement file Loca
199. xample the parameter varies exponentially from 1105 to 16 us with the three point interval that is 1 4 and 16 us 2 98 NM ECA ECX USM 3 2 SPECTROMETER CONTROL 4 11 aabe Experiment Tool single pulse ex2 File Tools View oes x 90_width 1 us 12 40116 us 16 us 5 4 90019 relaxation delay repetition time Total Collection Time 00 0 Time 00 02 5 ME Selecting L s If you select Logarithmic enter the values of Start Stop and Points in each input box In the above example the parameter varies logarithmically from 1 us to 16 us with the three point interval that is 1 12 40116 and 16 us 6 Click on the Set Value button The following figure shows the setting of the parameter input box in the Experi ment Tool window aeq 4o us 29 us 4105 Reference The method of entering numerical values from the geometry into the array parameters window You can enter the numerical values from the data geometry displayed on the screen into the array parameters window The procedure is explained using the irr offset parameter as an example 1 Select Pick Copy position to buffer from the cursor tool bar 2 Move the mouse pointer onto the spectrum displayed on the screen and Click the left mouse button on the peak setto irr offset The peak position is copied 3 Move the mouse pointer to the numerical value input box in the array parameters window and click on the
200. y If the peak intensity becomes extremely small when the filter value is set to 1 4 of the observation range it is a fold over In this case move the observation center frequency in the direction that makes the peak intensity stronger and put the peak in the observation range NM ECA ECX USM 3 5 13 5 MULTINUCLEAR MEASUREMENT B Fold over of other nuclei Some nuclei for example Na and have close resonance frequencies when multinuclear NMR is measured In this case fold over signal may be mistaken for a real signal especially if the other nucleus has good sensitivity Take care when performing measurements of the samples that contain other nuclei with close resonance frequencies 5 3 5 Problems with Low Frequency Nuclei When the resonance frequency is low such as with NMR and Ge NMR the distorted baseline that appears is like a signal with a wide line width This occurs due to the oscillation of the NMR signal detection coil induced by the observation RF pulse and is called the acoustic ringing This false signal should be distinguished from the real one Distinguish between them using the following two methods e Shift the observation center frequency A real peak moves with the observation center frequency while acoustic ringing does not move e Put only the solvent into the sample tube and measure it The acoustic ringing appears at almost the same position with the same intensity e
201. y meas urement exists further The range for this every measurement is divided by the red line 4 Click on the button whose group name is displayed on the blue line and place a check mark M easurement for the selected group appears 5 Click on the button next to the measurement name displayed on the red line to place a check mark The parameter setting range of the selected measurement appears Since Filename Comment Slot Solvent Temperature Temp State in the displayed parameters is already set up in the Automation window re setting is not necessary 6 Select a parameter to change from the parameter list The selected parameter is highlighted and the input box to the side displays the value of the present parameter 7 Change the parameter value EM Repeat steps 6 7 if necessary 9 After parameter change is complete click on the Run with Changes button A utomatic measurement starts JS f you click the Run with Default button automatic measurement will start after returning measurement parameter to the default value How to change a parameter other than the parameters displayed W hen changing parameters other than the parameters displayed in the list box perform the following procedure l Click on the Initialize button in the Set Parameters window The Choose Parameter window opens NM ECA ECX USM 3 2 45 2 SPECTROMETER CONTROL W N 6 7 8 2 46 Fig 2 37 Choose
202. y time 6 dB is added the pulse width is halved tau interval Interval between two pulses delay time for the relaxation The default is 10 s relaxation delay Waiting time between repeated pulse sequences The default is 7 s repetition time relaxation x acq time 4 32 NM ECA ECX USM 3 4 USAGE OF PULSE SEQUENCES m Data processing The standard process list is std_proton list How to interpret the spectrum In the case of single exponential decay the observed magnetization 7 at the pulse interval 7 is expressed by the following equation zea 1 W hen the magnetization 7 become zero the tau value c is called the null point If the null point is indicated by c T is given by the following equation null T T 1 44 NM ECA ECX USM 3 4 33 4 USAGE OF PULSE SEQUENCES 4 2 14 double pulse dec ex2 M easurement using double pulses with heteronuclear decoupling Directory usr delta global experiments relaxation Purpose To evaluate T the longitudinal relaxation time simply with heteronucleus decoupling Pulse sequences x pulse x 2 x pulse 180 90 tau interval relaxation x domain Delay noe time E Extension sequences noe The defaultis TRUE decoupling The defaultis TRUE B Parameters x domain Observation nucleus The default is Carbon13 x Offset Observation center The default is 100 ppm X sweep Obse

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