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Varian Solid-State NMR User Manual

Manual is about: Solid-State Spectrometer Systems With VNMR 6.1C Software

Summary of Solid-State NMR

  • Page 1

    User guide: solid-state nmr varian nmr spectrometer systems with vnmr 6.1c software pub. No. 01-999162-00, rev. C0402.

  • Page 2: User Guide:

    User guide: solid-state nmr varian nmr spectrometer systems with vnmr 6.1c software pub. No. 01-999162-00, rev. C0402.

  • Page 3

    User guide: solid-state nmr varian nmr spectrometer systems with vnmr 6.1c software pub. No. 01-999162-00, rev. C0402 revision history: a0800 – initial release for vnmr 6.1c software b0301 – mercuryplus updates— cppwr and dblv12 parameters in xpolar1 experiment. C0402 – updated inova cp/mas paramete...

  • Page 4: Table Of Contents

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 4 table of contents safety precautions .................................................................................... 8 introduction ...................................................................................................... 1...

  • Page 5

    Table of contents 5 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 chapter 5. Solid-state nmr accessories ...................................................... 72 5.1 pneumatics/tachometer box ...................................................................................... 72 5.2 ro...

  • Page 6: List of Figures

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 6 list of figures figure 1. Attenuator control graph for inova systems ............................................................ 18 figure 2. Attenuator control graph for mercury systems ........................................................

  • Page 7: List of Tables

    List of figures 7 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 figure 41. 3qmas1 pulse sequence .......................................................................................... 99 figure 42. Pass1 pulse sequence .....................................................................

  • Page 8: Safety Precautions

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 8 safety precautions the following warning and caution notices illustrate the style used in varian manuals for safety precaution notices and explain when each type is used: warning: warnings are used when failure to observe instructions or pre...

  • Page 9: Continued

    Safety precautions 9 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 warning notices ( continued ) refer to the manuals supplied with the magnet for the size of a typical 10-gauss stray field. This gauss level should be checked after the magnet is installed. Warning: only qualified maintena...

  • Page 10: Continued

    Safety precautions 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 10 warning notices ( continued ) warning: support the magnet and prevent it from tipping over. The magnet dewar has a high center of gravity and could tip over in an earthquake or after being struck by a large object, injuri...

  • Page 11: Continued

    Safety precautions 11 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 caution notices ( continued ) caution: check helium and nitrogen gas flowmeters daily. Record the readings to establish the operating level. The readings will vary somewhat because of changes in barometric pressure from w...

  • Page 12: Introduction

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 12 introduction this manual is designed to help you perform solid-state nmr experiments using a varian solid-state nmr module on a varian nmr spectrometer system running vnmr version 6.1c software. The manual contains the following chapters: •...

  • Page 13

    Introduction 13 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 other manuals this manual should be your basic source for information about using the spectrometer hardware and software on a day-to-day basis for solid-state nmr. Other vnmr manuals you should have include: • getting started •...

  • Page 14

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 14 chapter 1. Overview of solid-state nmr sections in this chapter: • 1.1 “line broadening,” this page • 1.2 “spin-lattice relaxation time,” page 15 • 1.3 “solids modules, probes, and accessories,” page 15 before techniques were developed to o...

  • Page 15

    Chapter 1. Overview of solid-state nmr 15 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 1.2 spin-lattice relaxation time an additional characteristic of some nuclei in the solid state, for example 13 c, is a long spin-lattice relaxation time (t 1 ). To overcome this problem, the abundant ...

  • Page 16: Cp/mas Solids Operation

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 16 chapter 2. Cp/mas solids operation sections in this chapter: • 2.1 “cp/mas solids modules,” this page. • 2.2 “rotor characteristics and composition,” page 20. • 2.3 “preparing samples,” page 21 • 2.4 “spinning the sample,” page 22. • 2.5 “a...

  • Page 17

    Chapter 2. Cp/mas solids operation 17 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 full-solids 1 h/ 19 f 1 kw amplifiers unity inova, unityplus, and unity wide bore systems can be equipped with the full bay solids option that includes a 1 kw 1 h/ 19 f amplifier. The amplifier is a class ...

  • Page 18

    2.1 cp/mas solids modules 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 18 • enable high power amplifier operation place the lo band amplifier switch in the hi power position (an orange led will illuminate) and enable high power with the silver button. • disable the high power amplifier o...

  • Page 19

    Chapter 2. Cp/mas solids operation 19 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 unity systems fine attenuator control is provided over a 6 db range in steps from 0 of 4095 on one or both transmitter boards. It is necessary to use both the fine and course attenuators on unity systems t...

  • Page 20

    2.2 rotor characteristics and composition 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 20 2.2 rotor characteristics and composition varian high-speed rotors (with and without vent holes) are composed of zirconia or of silicon nitride (si 3 n 4 ) with pmma, kel-f, or torlon end caps. The ...

  • Page 21

    Chapter 2. Cp/mas solids operation 21 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 rotor and end cap compositions are given in table 2 . 2.3 preparing samples solid samples are normally packed into hollow rotors and sealed with fluted caps. The method of filling the rotors depends somewh...

  • Page 22

    2.4 spinning the sample 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 22 preserved. Chances are good that the sample will spin adequately if the material can be made to fill the rotor homogeneously. Thick sheet or film materials are best handled by cutting or punching many disks, each hav...

  • Page 23

    Chapter 2. Cp/mas solids operation 23 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 introduction the following applies to spinning the sample regardless of the type of pneumatics/ tachometer box in use. After reviewing these general instructions, see the following sections for operating i...

  • Page 24

    2.4 spinning the sample 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 24 spinning rates and adjusting bearing and drive pressures spin rates and the bearing and drive pressures for the varian cp/mas probe at ambient temperature are listed in table 3 for the 7-mm probe and table 4 for the ...

  • Page 25

    Chapter 2. Cp/mas solids operation 25 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 always checking the spinning quality of the empty rotor before packing it with the sample material. Discard damaged rotors. Worn rotor caps can cause imbalance. Changing caps or rotating them between rotor...

  • Page 26

    2.4 spinning the sample 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 26 9. Install the probe into the magnet. 10. Set the bearing pressure to a value appropriate for the rotor speed you will be using, see table 3 and table 4 for 7 mm and 5 mm rotor bearing pressures. 11. Open the drive v...

  • Page 27

    Chapter 2. Cp/mas solids operation 27 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 using air flow to set the spin speed this procedure describes how to set the air flow to spin the rotor. This mode of operation is applicable when operating at the extremes of the temperature range of the ...

  • Page 28

    2.4 spinning the sample 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 28 changing rotors this procedure describes how to change rotors with mas probes. 1. Set either the airflow or the rotor speed to zero and click turn spinner off. Do not lower the drive-pressure regulator on the pneumat...

  • Page 29

    Chapter 2. Cp/mas solids operation 29 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 changing rotors caution: to prevent damage to the rotor or bearing, always smoothly shut off the rotation gas using the rotation pressure regulator before turning off the bearing gas using the bearing pres...

  • Page 30

    2.5 adjusting homogeneity 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 30 6. Attach the lock cable from lock preamp to the observe (obs) connector on the probe. 7. Lock the spectrometer and shim on the lock signal. The principle shims involved in adjusting homogeneity when a magic angle ...

  • Page 31

    Chapter 2. Cp/mas solids operation 31 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 4. Reconnect the observe (obs) port of the probe to the observe channel on the magnet leg. 5. Enter xpol='n' d1=1.0 nt=1 gain=4 ga . 6. Place the cursor near the d 2 o resonance and enter movetof . 7. Ente...

  • Page 32

    2.6 adjusting the magic angle 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 32 g. Make the same large positive change in the z1 shim as in step b. If the d 2 o resonance moves again, note the direction and magnitude of the change. If the change is smaller, continue moving the probe in the...

  • Page 33

    Chapter 2. Cp/mas solids operation 33 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 very close in frequency to 13 c, it is easy to switch between the two nuclei. The magic angle can easily be set or checked as described below. 1. Enter rt(‘/vnmr/parlib/xpolar1’) . 2. Enter tn='br79' to ob...

  • Page 34

    2.6 adjusting the magic angle 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 34 figure 7. Fid display of kbr on angle figure 8. Fid display of kbr 1/2 turn off angle figure 9. Typical hexamethylbenzene (hmb) spectrum 20 0 -20 40 60 80 100 120 140 160 180 200 ppm hmb aromatic carbons hmb me...

  • Page 35

    Chapter 2. Cp/mas solids operation 35 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 2.7 calibrating the cp/mas probe calibrating 13 c nucleus pulse width the following steps cover calibrating the pulse width. 1. Insert a rotor containing liquid-state p-dioxane and spin at 200-300hz. Do no...

  • Page 36

    2.7 calibrating the cp/mas probe 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 36 calibrating decoupler power using the previously determined pw , calibrate decoupler power ( γ b 2 ) as follows. 1. Recall the parameters used in the previous test. 2. Set pw, tpwr, and tpwrm to the values o...

  • Page 37

    Chapter 2. Cp/mas solids operation 37 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 6. Enter crossp=dipolar cntct=2500 at=0.02 d1=1 nt=4 sw=45000 . 7. Set the following parameter values according to the spectrometer used. 8. Enter lb=50 ga . 9. When acquisition is finished, enter dssh to ...

  • Page 38

    2.9 xpolar1—cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 38 the transmitter is placed in the center of the spectrum. 3. Enter ga . 4. Put the cursor on the tall methyl line and type nl rl(17.43p) ga . The reference ( reffrq ) is set only after you use the rl command to...

  • Page 39

    Chapter 2. Cp/mas solids operation 39 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 cross-polarization amplitudes should be controlled using the fine attenuator. The fine attenuator has a range of 60 db for inova and 48 db for mercury systems down from the course attenuator. The coarse at...

  • Page 40

    2.9 xpolar1—cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 40 • tpwrm is the observe linear modulator setting . The parameter tpwrm is linearly proportional to the applied transmitter voltage— doubling tpwrm halves the value of the pulse width. • dpwr is the decoupler po...

  • Page 41

    Chapter 2. Cp/mas solids operation 41 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 2.10 optimizing parameters and special experiments this section provides information on parameters used for specific optimizations, such as contact time and repetition rate. Also included in this section a...

  • Page 42

    2.10 optimizing parameters and special experiments 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 42 toss is less effective at high spinning speeds. Note that if suppression is not complete, check that srate is correct. Toss uses 180 ° pulses based on pwx . It may be necessary to adjust pw...

  • Page 43

    Chapter 2. Cp/mas solids operation 43 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 13 c t 1 ρ experiments measurements of the spin-lattice relaxation time in the rotating frame (t l ρ ) are possible using the standard xpolar1 pulse sequence. Anytime that pcrho is set to a non-zero value,...

  • Page 44

    2.11 useful conversions 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 44 1 h t 1 through 13 c cross-polarization l h t 1 can be measured using the xpolar1 pulse sequence by setting it up to perform a standard inversion-recovery experiment on the protons followed by cross-polarization of t...

  • Page 45

    Chapter 2. Cp/mas solids operation 45 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402.

  • Page 46

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 46 chapter 3. Wideline solids module operation sections in this chapter: • 3.1 “wideline solids module,” this page. • 3.2 “wideline experiments,” page 50. • 3.3 “ssecho pulse sequence,” page 51. • 3.4 “data acquisition,” page 51. • 3.5 “standa...

  • Page 47

    Chapter 3. Wideline solids module operation 47 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 • the older wideline adc board was shipped with unity and vxr-s systems. It acquires data in a fundamentally different manner. Data is temporarily stored in its on- board, 2 x 8 kword buffer (maxi...

  • Page 48

    3.1 wideline solids module 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 48 both amplifiers are linear, with gating provided for noise blanking. Operational details for the high-power amplifiers are included in the manuals provided by the manufacturers of the amplifiers. These should be r...

  • Page 49

    Chapter 3. Wideline solids module operation 49 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 although you should study the ar manual before using the amplifier, an abbreviated set of operating instructions are given here (words in all capital letters refer to controls on the front panel)....

  • Page 50

    3.2 wideline experiments 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 50 • the off button grounds the inputs of both high power amplifiers and routes the transmitters through the standard unity inova, unityplus, and unity electronics appropriate for liquids operation (note that both ampl...

  • Page 51

    Chapter 3. Wideline solids module operation 51 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 normally the breadth of a line comes from two sources, dipolar coupling and chemical shift anisotropy. There are a number of techniques, referred to as line narrowing, or multipulse techniques, to...

  • Page 52

    3.4 data acquisition 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 52 should be placed symmetrically in the coil when in the probe. Remember that the nmr tube has a 29 si, ( l3 na) 27 al and 11 b background signal. Warning: dangerous high voltage exists inside the probe that can cause bur...

  • Page 53

    Chapter 3. Wideline solids module operation 53 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 3.5 standard wideline samples two standard wideline samples are provided with the system, malonic acid-d 4 for 2 h and sodium nitrate for 23 na wideline nmr. These samples are provided as an aid t...

  • Page 54

    3.5 standard wideline samples 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 54 13. Replace the d 2 o sample with the malonic acid–d 4 sample and tune the probe. 14. Enter ssecho to convert the s2pul parameter set to one suitable for the ssecho pulse sequence. Set tau1=20 tau2=15 nt=16 . 1...

  • Page 55

    Chapter 3. Wideline solids module operation 55 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 • remember that for solid samples of quadrupolar nuclei, the 90 ° pulse usually cannot be determined from a pw array. 3.6 data processing most data processing needs of wideline spectra are the sam...

  • Page 56

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 56 chapter 4. Cramps/multipulse module operation sections in this chapter: • 4.1 “introduction to multipulse experiments,” this page • 4.2 “cramps/multipulse module hardware,” page 57 • 4.3 “multipulse experiments and user library,” page 60 • ...

  • Page 57

    Chapter 4. Cramps/multipulse module operation 57 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 4.2 cramps/multipulse module hardware multipulse capability is available with all unity inova and unityplus spectrometers. Unity and vxr-s spectrometers require an additional sync module to impr...

  • Page 58

    4.2 cramps/multipulse module hardware 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 58 c. After tuning at lower power, fine tune at the maximum power that will be used in order to obtain the maximum linearity of the cpi or the cma. D. Record the values for future reference. Overdrive mode...

  • Page 59

    Chapter 4. Cramps/multipulse module operation 59 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 the receiver and the fast adc have a sufficiently short turn-on time for detection between the pulses of br24. Note that the value of sw in br24 is set to 2 mhz to select the fast adc but the tr...

  • Page 60

    4.3 multipulse experiments and user library 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 60 4.3 multipulse experiments and user library the macros for some of the multipulse nmr sequences are located in maclib . The macros for other multipulse nmr sequences are located in the user librar...

  • Page 61

    Chapter 4. Cramps/multipulse module operation 61 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 configure the spectrometer 1. Connect the preamplifier and cable that are used for 1 h detection to the 1 h port of the probe to be used. If this is a tune-up for 1 h decoupling instead of cramp...

  • Page 62

    4.4 multipulse tune-up procedure (flipflop) 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 62 • optionally a. Type phaser=phfid , phfid='n' b. Reacquire the spectrum. This will adjust the pulse phase to place the signal in one of the two adc channels. Otherwise, it usually sufficient to ob...

  • Page 63

    Chapter 4. Cramps/multipulse module operation 63 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 the rf homogeneity can be enhanced by reducing the sample size and by using care to center the sample in the coil. Data similar to figure 18 is suitable for most cramps experiments. Probes with ...

  • Page 64

    4.5 1 h cramps experiment (br24 or mrev8) 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 64 output on the tune-interface or note the frequency of the minimum reflected output with qtune. Return to this value when tuning the sample. Phase transient can also be removed more-or-less permanent...

  • Page 65

    Chapter 4. Cramps/multipulse module operation 65 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 12. Set the spin rate at 13. Set d1=5 for glycine and d1=60 for adipic acid. 14. Type nt=2 ga the result for adipic acid should be similar to figure 21 . 15. Scale the spectrum. A. Place two cur...

  • Page 66

    4.7 quadrature 1h cramps 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 66 the transmitter is typically set upfield ( tof=-2000 to -5000 hz ) from the spectrum of interest and line narrowing is usually best at these frequencies. Mrev8 and br24 spectra also always have a quadrature image an...

  • Page 67

    Chapter 4. Cramps/multipulse module operation 67 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 scan to scan. When set properly, a four scan phase cycle should remove both the image and the pedestal and it should be possible to set the transmitter in the center of the spectrum. There are n...

  • Page 68

    4.9 flipflop - pulse width and phase transient calibration 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 68 4.9 flipflop - pulse width and phase transient calibration the flipflop.C pulse sequence ( figure 22 ) is the standard sequence for multiple-pulse tune up. It is applicable for unit...

  • Page 69

    Chapter 4. Cramps/multipulse module operation 69 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 4.10 br24 and cylbr24 - multiple pulse line narrowing (24-pulse cycle) br24 ( figure 23 ) is the usual sequence used for 1 h cramps. Cylbr24 is a modification that allows quadrature detection wi...

  • Page 70

    4.11 mrev8 and cylmrev - multiple pulse line narrowing (8-pulse cycle) 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 70 4.11 mrev8 and cylmrev - multiple pulse line narrowing (8-pulse cycle) mrev8 ( figure 24 ) is a sequence used for 1 h cramps. Cylmrev is a modification that allows quadr...

  • Page 71

    Chapter 4. Cramps/multipulse module operation 71 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 4.12 wahuha and wahuhahs - mp-assisted high-speed spinning (4-pulse cycle) wahuha ( figure 25 ) is the original 4-pulse multipulse sequence. Wahuhahs is a semi- windowless version of wahuha and ...

  • Page 72: Solid-State Nmr Accessories

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 72 chapter 5. Solid-state nmr accessories sections in this chapter: • 5.2 “rotor synchronization operation,” this page. • 5.3 “rotor speed controller accessory operation,” page 76. • 5.4 “variable temperature operation with solids,” page 78 5....

  • Page 73

    Chapter 5. Solid-state nmr accessories 73 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 • the time between successive edges can be measured (note that the edges are always in the same sense, so that this interval is one rotor period). This has a precision of 50 ns. This is shown as “mode ...

  • Page 74

    5.2 rotor synchronization operation 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 74 for light detection, the tachometer box provides the light source and the detector. The rotor has a blackened sector on its base ( figure 28 ) so that as it rotates, differing amounts of light are reflect...

  • Page 75

    Chapter 5. Solid-state nmr accessories 75 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 using rotor synchronization table 10 lists parameters used with the rotor synchronization accessory. The rotor synchronization accessory can be used in a number of ways, from simple monitoring of spinn...

  • Page 76

    5.3 rotor speed controller accessory operation 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 76 of each acquisition, the initial spinning speed is noted. If, during acquisition, the speed alters by more than 100 hz and the interlock parameter in is set to 'y' , acquisition is halted. The ...

  • Page 77

    Chapter 5. Solid-state nmr accessories 77 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 the dac value can be changed while continuously displaying the rotor speed by pressing the following keys and simultaneous key combinations on the pc keyboard: closed loop mode in closed loop (c) mode,...

  • Page 78

    5.4 variable temperature operation with solids 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 78 the configuration parameters can be saved to a file on the pc (e.G., gain.Set ). Upon initial startup, the parameters in this file are loaded in order to set the configuration. Be sure to make ...

  • Page 79

    Chapter 5. Solid-state nmr accessories 79 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 doty solids vt system the varian solids vt accessory can also be added to the doty cp/mas probe for vt operation. When this accessory is added, connection of the gas supplies to the probe is altered in...

  • Page 80: Solid-State Nmr Experiments

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 80 chapter 6. Solid-state nmr experiments sections in this chapter: • 6.1 “xpolar—cross-polarization, unity,” page 81 • 6.2 “xpolar1—cross-polarization,” page 85 • 6.3 “xpwxcal—observe-pulse calibration with cross-polarization,” page 87 • 6.4 ...

  • Page 81

    Chapter 6. Solid-state nmr experiments 81 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 this chapter describes cp/mas, triple-resonance, wideline, and multipulse pulse sequences for solid-state nmr. To aid in identification, the names of pulse sequences are given in all capital letters. I...

  • Page 82

    6.1 xpolar—cross-polarization, unity 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 82 two processes happen simultaneously, the magnetization buildup from cross-polarization and the magnetization loss from rotating-frame relaxation. A time exists for which an optimum in the magnetization o...

  • Page 83

    Chapter 6. Solid-state nmr experiments 83 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 measurement of 13 c t 1 ρ measurements of the spin-lattice relaxation time in the rotating frame (t 1 ρ ) are possible using the standard xpolar pulse sequence. The parameter p3 is the spinlock time af...

  • Page 84

    6.1 xpolar—cross-polarization, unity 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 84 obtained just as with any other text file. The graphical display of the data can be viewed on screen by using the command exp1 or plotted with the command pexp1 . Measurement of the 1 h t 1 through cross...

  • Page 85

    Chapter 6. Solid-state nmr experiments 85 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 maximum level of 255, or linear, with a maximum of 63. 0 is the minimum power on unity systems and –16 is the minimum on unity inova and unityplus systems. Level1f and level2f are only active for linea...

  • Page 86

    6.2 xpolar1—cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 86 cross-polarization amplitudes should be controlled using the fine attenuator. The fine attenuator has a range of 60 db for inova and 48 db for mercury systems down from the course attenuator. The coarse attenu...

  • Page 87

    Chapter 6. Solid-state nmr experiments 87 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 • tpwrm is the observe linear modulator setting . The parameter tpwrm is linearly proportional to the applied transmitter voltage— doubling tpwrm halves the value of the pulse width. • dpwr is the deco...

  • Page 88

    6.3 xpwxcal—observe-pulse calibration with cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 88 polarization is used for preparation, xpwxcal can be run in less time than xpolar1 with xpol='n' . Figure 35 is a diagram of the sequence. Applicability xpwxcal is available only...

  • Page 89

    Chapter 6. Solid-state nmr experiments 89 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 phase=2 sets the phase of pwx 90 ° to the contact pulse and is necessary for measurement of pwx . Setting phase=1 sets the two phases the same, and all array members of a pwx array have the same intens...

  • Page 90

    6.5 masexch1—phase-sensitive rotor sync sequence for exchange 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 90 cp90 is the 13 c 90 ° pulse, in microseconds. Mix is the mixing time, in seconds. Sync is set to 'y' to run rotor with sync; sync is set to 'n' to run unsynchronized (normal noes...

  • Page 91

    Chapter 6. Solid-state nmr experiments 91 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters masexch1makes use of the unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw and cntct . See page 85 for a description of these parameters. Pwx i...

  • Page 92

    6.6 hetcorcp1—solid-state hetcor 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 92 6.6 hetcorcp1—solid-state hetcor hetcorcp1 is a 1 h – 13 c heteronuclear chemical shift correlation (hetcor) experiment for solid-state materials. Analogous to solution-state hetcor experiments, this sequenc...

  • Page 93

    Chapter 6. Solid-state nmr experiments 93 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 reference bielecki, a.; burum, d. P.; rice, d. M.; karasz, f. E. Macromolecules 1991, 24, 4820. 6.7 wise1—two-dimensional proton wideline separation wise1 correlates the cp/mas spectrum of the observe ...

  • Page 94

    6.8 xpolwfg1—cross-polarization with programmed decoupling 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 94 xpolwfg1 gates the waveform generator on and off with a fastline (no ap bus delay) at the beginning and end of the acquisition period if dm='nny' and dmm='ccp' . If dm='c' the usual...

  • Page 95

    Chapter 6. Solid-state nmr experiments 95 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 fslg2.Dec provides phase continuous frequency switched lee-goldberg decoupling. This pattern decouples protons from themselves, but leaves a residual 13 c– 1 h dipolar interaction. Reference bennett, a...

  • Page 96

    6.9 xpolxmod1—waveform modulated cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 96 for vnmr 5.1 and later crossp scales the proton waveform and tpwrm scales the x waveform. The macros xmodramp and xmodcos create their respective .Dec files. They also serve as a prototype...

  • Page 97

    Chapter 6. Solid-state nmr experiments 97 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 references hediger, s.; meier, b. H.; ernst, r. R. Chem. Phys. Lett. 1993, 213, 627. 6.10 vacp—variable amplitude cross-polarization as typical field strengths and rotor speeds used for cp/mas increase...

  • Page 98

    6.11 xpoledit1—solids spectral editing 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 98 parameters vacp uses the unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , dblvl2 , pw , and cntct . See page 85 for a description of these parameters. Vacp is an array of lin...

  • Page 99

    Chapter 6. Solid-state nmr experiments 99 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters xpoledit1 makes use of the unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw and cntct . See page 85 for a description of these parameters. P3 ...

  • Page 100

    6.12 3qmas1—triple-quantum 2d for quadrupole nuclei 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 100 (dor) and dynamic angle spinning (das). 3qmas1 is a robust experiment that is well worth trying before contemplating the use of dor or das. Macro the macro s3qmas1 converts a parameter se...

  • Page 101

    Chapter 6. Solid-state nmr experiments 101 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 medek, a.; harwood, j. S.; frydman, l. J. Am. Chem. Soc. 1995, 117, 12779–12787. Baltsberger, j. H.; xu, z.; stebbins, j. F.; wang, s. H.; pines, a. J. Am. Chem. Soc. 1996. Massiot, d.; touzo, b.; tru...

  • Page 102

    6.14 cpcs—cross-polarization with proton chemical shift selection 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 102 parameters pass1 makes use of the unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw and cntct . See page 85 for a description ...

  • Page 103

    Chapter 6. Solid-state nmr experiments 103 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters pw is the 1 h 90 ° pulse for cross-polarization, in microseconds. P2 is the contact time, in microseconds. D2 is the evolution time, in seconds. Dm is set to 'nny' for no proton decoupling ...

  • Page 104

    6.16 cpnoesyps—cross-polarization phase-sensitive noesy 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 104 parameters cpcosyps uses unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these paramete...

  • Page 105

    Chapter 6. Solid-state nmr experiments 105 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 for cpnoesy, cross peaks occur between resonances that share mutual through-space dipolar coupling or interact through weak spin diffusion. Coupling can be enhanced with the insertion of rotor synchro...

  • Page 106

    6.17 r2selpuls1—rotation resonance with selective inversion 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 106 parameters cpnoesyps uses unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these par...

  • Page 107

    Chapter 6. Solid-state nmr experiments 107 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 macro the macro r2selpuls1 converts a parameter set, obtained with xpolar or xpolar1, for rotational resonance with selective inversion, r2selpuls1. Power levels and the proton 90 ° pulse width are re...

  • Page 108

    6.18 dipshft1—separated local field spectroscopy 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 108 srate is the actual spinning speed. Rotational resonance requires spinning speed control. Set the spinning rate equal to the frequency difference between the two resonances of interest (firs...

  • Page 109

    Chapter 6. Solid-state nmr experiments 109 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters dipshft1 uses unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these parameters. Pp is the pro...

  • Page 110

    6.19 sedra2—simple excitation of dephasing rotational-echo amplitudes 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 110 sedra is applied after cross-polarization and consists of a train of π pulses synchronized with the middle of each rotor period. Acquisition follows at the next rotor pe...

  • Page 111

    Chapter 6. Solid-state nmr experiments 111 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters sedra2 uses unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these parameters. Pwx is the obse...

  • Page 112

    6.20 redor1—rotational echo double resonance 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 112 applicability redor1 is available only on unity inova and unityplus systems. Macro the macro redor1 converts a parameter set, obtained with xpolar or xpolar1, for the redor experiment with xy8 π...

  • Page 113

    Chapter 6. Solid-state nmr experiments 113 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 cycles is the number of rotor cycles before detection. An array is most often set with cycles=2,4, ... To the number of maximum cycles, typically 64. Be sure the parameter array is in the order 'cycle...

  • Page 114

    6.21 doublecp1—double cross-polarization 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 114 parameters doublecp1 uses the unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these parameters. Dbcpfl...

  • Page 115

    Chapter 6. Solid-state nmr experiments 115 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 array the value of crossp2 . The hartmann-hahn match corresponds to the minimum signal intensity. Cntct2 is the contact time for the dilute-spin cross polarization, in microseconds. References schaefe...

  • Page 116

    6.23 hahncp1—spin 1/2 echo sequence with cp 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 116 reference torchia, d. A. J. Magn. Reson. 1978, 30, 613. 6.23 hahncp1—spin 1/2 echo sequence with cp the hahncp1 pulse sequence provides a 90 - tau - 180 - tau hahn spin echo. If xpol='y' , the in...

  • Page 117

    Chapter 6. Solid-state nmr experiments 117 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 parameters hahncp1 uses unity inova and unityplus parameters tpwr , tpwrm , dpwr , cppwr , dipolr , crossp , dblvl2 , pw , and cntct . See page 85 for a description of these parameters. Xpol is set to...

  • Page 118

    6.24 ssecho1—solid-state echo sequence for wideline solids 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 118 applicability ssecho1 is available only on unity inova and unityplus. It is found in userlib . Macro the macro ssecho1 converts a parameter set for the quadrupole echo pulse sequen...

  • Page 119

    Chapter 6. Solid-state nmr experiments 119 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 with width pw . The delay before acquisition is tau1+tau2+pw . A difference spectrum 'n'–'y' selects a quadrupole echo spectrum in the presence of a large central resonance. Compul set to 'y' implemen...

  • Page 120

    6.25 wlexch1—wideline solids exchange 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 120 macro the macro wlexch1 converts a solids parameter set obtained with ssecho1 to the wlexch1 spin i=1 solids exchange experiment. Power levels and pw are retained. If tpwrm is not present (as in many o...

  • Page 121

    Chapter 6. Solid-state nmr experiments 121 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 blumich, b.; spiess, h. W. Angew. Chem., int. Ed. Engl. 1988, 27, 1655. 6.26 hs90—90-degree° phase shift accuracy at the completion of use of the multiple pulse tune-up sequences flipflip and flipflop...

  • Page 122

    6.27 mrevcs—multiple pulse chemical-shift selective spin diffusion 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 122 reference haubenreisser, u.; schnabel, b. J. Magn. Reson. 1979, 35, 175. 6.27 mrevcs—multiple pulse chemical-shift selective spin diffusion figure 56 shows the diagram of a...

  • Page 123

    Chapter 6. Solid-state nmr experiments 123 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 reference spiess, h..; schmidt-rohr, k.; clauss, j.; blumich, b. Magn. Reson. Chem. 1990, 28, s3. 6.28 mq_solids—multiple-quantum solids a 1 h multiple-quantum spectrum can be obtained in the solid st...

  • Page 124

    6.29 spindiff—spin diffusion in solids 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 124 6.29 spindiff—spin diffusion in solids spindiff is a pulse sequence for 2d exchange spectroscopy in which spin diffusion is occurring in solid dense homonuclear dipolar coupled spin systems. Figure 58...

  • Page 125

    Chapter 6. Solid-state nmr experiments 125 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 the particular example used here is the simultaneous observation of 27 al and 2 h. For this experiment, a triple-resonance probe was used with the coil doubly tuned to 27 al (referred to as the high f...

  • Page 126

    6.31 nutate—solids 2d nutation 01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 126 the 2d spectrum places chemical shift along f 2 and γ b 1 along f 1 . Figure 60 is a diagram of the sequence. Macro the macro nutate converts an s2pul sequence parameter set into a 2d nutation experiment. Par...

  • Page 127

    Chapter 6. Solid-state nmr experiments 127 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402.

  • Page 128: Index

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 128 index index numerics 1 kw 1h/19f amplifier, 17 13c chemical shifts reference materials, 38 1h cramps, 64 , 65 1h/19f 1-kw amplifier, 57 3qmas1 pulse sequence, 99 90× phase shift, 121 a absolute position of cp/mas rotor, 72 absolute-value p...

  • Page 129: Index

    Index 129 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 crossp parameter, 40 , 87 , 96 crossp2 parameter, 114 cross-peaks, 90 cross-polarization contact time, 39 , 86 noesy, 104 samples, 81 spectra, 41 time, 41 cycles parameter, 103 , 111 , 113 , 122 cylbr24, 69 , 70 , 71 cylmrev, 69 , 70...

  • Page 130: Index

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 130 index h hahncp1 macro, 116 hahncp1 pulse sequence, 116 hartmann-hahn condition, 81 , 88 matching, 36 helium contact with body, 9 gas flowmeters caution, 11 hetcor pulse sequence, 92 hetcorcp1 macro, 92 hetcorcp1 pulse sequence, 88 heteronu...

  • Page 131: Index

    Index 131 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 br24, 67 multinuclear fast acquisition, 124 multiple pulse line narrowing (8-pulse cycle), 70 multiple-pulse experiments, 81 selection, 102 multiple-quantum experiment, 123 multipulse capability, 57 experiments, 56 multipulse tune-up...

  • Page 132: Index

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 132 index q quadecho sequence, 54 quadrature detection and 1h cramps, 66 quadrupolar, 117 interaction, 14 nuclei, 51 quadrupole echo, 118 pulse sequence, 118 quasi-elliptical filters, 47 r r2selpuls1 macro, 107 r2selpuls1 pulse sequence, 106 r...

  • Page 133: Index

    Index 133 vnmr 6.1c user guide: solid-state nmr 01-999162-00 c0402 editing, 98 resolution, 41 speed control process, 77 spin diffusion, 124 -echo mode, 55 locking pulse, 81 quantum number, 50 rate adjustment, 28 , 76 rates, 28 spindiff macro, 124 spindiff pulse sequence, 124 spin-lattice relaxation ...

  • Page 134: Index

    01-999162-00 c0402 vnmr 6.1c user guide: solid-state nmr 134 index wim parameter, 92 wim-24 cycles, 92 wise1 macro, 93 wise1 pulse sequence, 93 wlexch1 parameter, 120 wlexch1 pulse sequence, 120 x x-channel modulation, 95 xmodcos macro, 96 xmodramp macro, 96 xnoesysync macro, 89 xnoesysync pulse seq...