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Varian Solid-State NMR User Manual

Solid-state spectrometer systems with vnmr 6.1c software
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User Guide:
Solid-State NMR
Varian NMR Spectrometer Systems
With VNMR 6.1C Software
Pub. No. 01-999162-00, Rev. C0402

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Summary of Contents for Varian 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: Solid-State NMR Varian NMR Spectrometer Systems With VNMR 6.1C Software Pub. No. 01-999162-00, Rev. C0402...
  • Page 3 Specifications and performance characteristics of the software described in this manual may be changed at any time without notice. Varian reserves the right to make changes in any products herein to improve reliability, function, or design. Varian does not assume any liability arising out of the application or use of any product or circuit described herein;...

  • Page 4: Table Of Contents

    Table of Contents SAFETY PRECAUTIONS ..................8 Introduction ...................... 12 Chapter 1. Overview of Solid-State NMR ............14 Line Broadening ......................14 Spin-Lattice Relaxation Time ..................15 Solids Modules, Probes, and Accessories ..............15 Chapter 2. CP/MAS Solids Operation ............16 CP/MAS Solids Modules ....................
  • Page 5 MREVCS—Multiple Pulse Chemical-Shift Selective Spin Diffusion ....122 6.28 MQ_SOLIDS—Multiple-Quantum Solids ............. 123 6.29 SPINDIFF—Spin Diffusion in Solids ..............124 6.30 FASTACQ—Multinuclear Fast Acquisition ............124 6.31 NUTATE—Solids 2D Nutation ................125 Index ........................ 128 VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 6 Pneumatics/Tachometer Box for CP/MAS Probes ............ 73 Figure 27. Different Modes of the Rotor Synchronization Accessory ........73 Figure 28. Base of a Varian High-Speed Spinning Rotor ............74 Figure 29. Doty Double Bearing Rotor ..................74 Figure 30. TOSS Pulse Sequence ....................82 Figure 31.
  • Page 7 Rotor Controller Gain Setting and Typical Ranges ............55 Table 8. Multiacquisition Quadrature Corrections for MREV8 ............ 99 Table 9. Multiacquisition Quadrature Corrections for BR24 ............100 Table 10. Multiacquisition Quadrature Corrections for CORY24 ..........100 VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 8: Safety Precautions

    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 precautions could result in injury or death to humans or animals, or significant property damage.
  • Page 9 Written authorization approved by a Varian, Inc. product manager is required to implement any changes to the hardware of a Varian NMR spectrometer. Maintain safety features by referring system service to a Varian service office.
  • Page 10 Failure to comply with these cautions, or with specific cautions elsewhere in Varian manuals, violates safety standards of design, manufacture, and intended use of the instrument. Varian assumes no liability for customer failure to comply with these precautions.
  • Page 11 It is the operator’s responsibility to maintain the instrument in a condition that does not violate rf emission requirements. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 12: Introduction

    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: • Chapter 1, “Overview of Solid-State NMR,”...
  • Page 13 Introduction 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 • Walkup NMR Using GLIDE •...

  • Page 14: Chapter 1. Overview Of Solid-State Nmr

    (about 10 kHz) and therefore can be narrowed to a single, narrow line by magic angle spinning. The residual (second order) linewidth of the central transition is inversely proportional to the applied magnetic field. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 15: Spin-Lattice Relaxation Time

    1.3 Solids Modules, Probes, and Accessories Varian supplies a complete line of solid-state NMR modules, probes, and accessories. Solids modules include CP/MAS, wideline, CRAMPS/multipulse, and complete solids. CP/MAS, wideline, and CRAMPS/Multipulse hardware and operation are covered in Chapters 2, 3, and 4, respectively, of this manual.

  • Page 16: Chapter 2. Cp/Mas Solids Operation

    The MERCURYplus and MERCURY-Vx system CP/MAS amplifier chassis is housed in an accessories console attached to the standard console. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 17 Current and newer systems incorporate the CMA amplifier manufactured in Fort Collins, Colorado, USA by Varian Inc. These amplifiers offer the option of either class AB or class C operation. CMA amplifiers are tuned manually using calibrated tuning knobs. The amplifier is enabled or disabled using the switches on the front panel of the full solids bay.

  • Page 18: Figure 1. Attenuator Control Graph For Inova Systems

    Output in voltage or field strength is linear and quadratic in power. The attenuator Attenuator Value control in dB is shown in Figure Figure 2. Attenuator Control Graph for Mercury Systems 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 19: Table 1. Background Nuclei Of Rotor Material

    The operation of the Pneumatics and Tachometer Box is described in section 2.4 “Spinning the Sample,” page An older standalone PC may be present to provide rotor speed control for UNITYplus and UNITY. Instructions for this controller are provided in older manuals. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 20: Rotor Characteristics And Composition

    2.2 Rotor Characteristics and Composition 2.2 Rotor Characteristics and Composition Varian high-speed rotors (with and without vent holes) are composed of zirconia or of silicon nitride (Si ) with pMMA, Kel-f, or Torlon end caps. The cap twist-fits into the rotor body and is held with two O-rings.

  • Page 21: Preparing Samples

    Machine samples of solid materials to 0.440 ± 0.005 in. (11.176 mm) in length with a diameter of 0.1960 ± 0.0005 in. (4.979 mm) for Varian 7-mm rotors or 0.137 in. (3.48 mm) for Varian 5-mm rotors and placed inside a rotor.

  • Page 22: Spinning The Sample

    For samples that have densities above 3.0 g/cc, decrease the maximum spin rate by 35%. CAUTION: When removing caps or digging out packed samples, take care not to gouge the rotor. Even small scratches can imbalance the rotor. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 23 The black or white half circle can be reapplied on the rotors with a black marking pen and white enamel paint provided in the startup kit. The diameter marking should be straight. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 24 2.4 Spinning the Sample 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 5-mm probe.

  • Page 25: Figure 3. Spinner Speed Control Window

    Using the Rotor Speed Controller The rotor speed controller for Varian MAS probes can be operated with spinning speed regulation or with a specific airflow setting to control the spinning speed of a sample in a magic angle spinning (MAS) probe.
  • Page 26 In an array of spin, the pre-acquisition delay is applied before each FID. Click next to Allow spin control in an experiment with go to return control to the Spinner Control window after the experiment is complete. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 27: Figure 4. Spinner Speed Control Window

    Reduce the drive pressure until the rotor spinning as a result of the bearing air. Set the slider bars to their maximum position (electro-pneumatic valve is now fully open). Adjust the drive pressure to achieve the desired rotor spin speed. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 28 Varian 7-mm and 5 mm CP/MAS probes at ambient temperature. The spin rates shown are approximate values. The actual spin rate varies depending on the properties of the sample and sample holder.

  • Page 29: Adjusting Homogeneity

    Enter rt(‘/vnmr/stdpar/H2’) dm=’n’ su. Tune the probe to observe H by inserting the proper tuning stick and adjusting the probe tuning controls. See the Getting Started manual for instructions on how to tune a probe. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 30 1 and 5 Hz. Finer adjustment and evaluation of the homogeneity is possible using a sample of solid adamantane (not available from Varian). A linewidth between 2 and 10 Hz is typically attainable, see the sample spectrum in...

  • Page 31: Figure 5. Typical Mas Spectrum Of Adamantane

    Loosen the setscrews on the probe flange. Change the height of the probe by a few millimeters (either up or down may be necessary). Tighten the setscrews and return z1 to the original value. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 32: Adjusting The Magic Angle

    The preferred method of adjusting the magic angle uses the Br spectrum of KBr, which, when spun at the magic angle results in an extensive set of spinning sidebands. As Br is 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 33 Typical values are 67 Hz for a 300 MHz system and 90 Hz for a 400 MHz system. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 34: Figure 7. Fid Display Of Kbr On Angle

    2.6 Adjusting the Magic Angle Figure 7. FID Display of KBr on Angle Figure 8. FID Display of KBr 1/2 Turn Off Angle Methyl Carbons HMB Aromatic Carbons Figure 9. Typical Hexamethylbenzene (HMB) Spectrum 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 35: Calibrating The Cp/Mas Probe

    180 and divide by 2. The 180 is not a good measurement of twice the 90 because of r.f. inhomogeneities of the coil. 13. Continue with “Calibrating Decoupler Power,” this page. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 36 C pw90 in “Calibrating Nucleus Pulse Width,” page Enter dpwr dipolr and dof values determined in “Calibrating Decoupler Power,” page Use the second set of values for the H cross polarization field. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 37: Referencing A Solids Spectrum

    The HMB signal-to-noise sample can be used for this purpose. Obtain a spectrum of HMB using the parameters that gave the best spectrum in “Calibrating the CP/MAS Probe,” page Enter cr=100p movetof. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 38: Xpolar1-Cross-Polarization

    INOVA, UNITYplus, and newer UNITY systems. The parameters that control the attenuators and linear modulators are shown in the diagram of XPOLAR1, see Figure cntct (tpwrm) cntct (dipolr) (crossp) Figure 10. XPOLAR1 Pulse Sequence 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 39 TOSS and dipolar dephasing, pwx is in microseconds. • cntct is the cross-polarization contact time, in microseconds. • tpwr is the observe power setting . Spectrometer Minimum, dB Maximum, dB INOVAcpmas MERCURYcpmas VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 40 • toss set to 'y' implements timed spin echoes to suppress spinning side bands. Timing is determined from the value of srate. Note that for toss='y' or pdp='y', srate must be set correctly because delays are calculated from 1.0/srate. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 41: Optimizing Parameters And Special Experiments

    TOSS (TOtal Sideband Suppression) technique. The TOSS pulse sequence is selected by setting toss='y' in the XPOLAR1 sequence (see Figure 10). Note that the parameter srate should be set to the spinning speed in Hz. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 42: Figure 12. Toss Experiment On Alanine (Spectrum And Sequence)

    (protonated dephasing) equal to 'y', setting srate to the spinning speed, and entering appropriate values for pdpd2 (in µ s), the dephasing time. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 43: Figure 13. Protonated Carbon Suppression Of Alanine (Spectrum And Sequence)

    0. Figure 14 shows the l ρ spin-lattice relaxation measurement pulse sequence. cntct (dipolr) (crossp) xpol='y' cntct pcrho (tpwrm) (tpwrm) Figure 14. Rotating-Frame Spin-Lattice Relaxation Measurements Sequence VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 44: Useful Conversions

    Convert from field strength in gauss to field strength in gauss: H: γ H (kHz) ≈ 4.3 * γ H (gauss) C : γ H (kHz) ≈ γ H (gauss) Convert from rf fields to power levels: P (watts) ∝ (γ H) 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 45 Chapter 2. CP/MAS Solids Operation VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 46: Chapter 3. Wideline Solids Module Operation

    3.1 Wideline Solids Module The wideline module for the Varian spectrometer modifies and extends the basic capability of the system in a number of areas. The main components of the wideline module are the wideband ADC, high-power amplifier, and the solids cabinet.
  • Page 47 5-MHz 12-bit ADCs and 2 MB of onboard memory. High-Power Amplifier The wideline high-power (1 kW) amplifier is intended mainly for use in solid-state NMR studies. The amplifier is housed in a third cabinet, as shown in...

  • Page 48: Figure 16. Solids Cabinet Layout, Open Front View

    The amplifier is fully protected against thermal overload, excessive duty cycle, and excessive pulse width. Status lights on the front panel and switches for this unit are visible by opening the front door of the third cabinet. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 49 • 100 W CP/MAS decoupler—operation of this is the same as for CP/MAS. • 1 kW decoupler amplifier. Status Panel The high power amplifiers are controlled by a status panel. The HI POWER ENABLE subpanel contains two switches: VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 50: Wideline Experiments

    The most interesting parameters are relaxation rates such as T , and T measurements the relevant part is the first few microseconds of the FID. The FID may not even be transformed. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 51: Ssecho Pulse Sequence

    The most convenient sample carrier is a 15 mm length of 5 mm outside diameter NMR tube, which can be sealed with Parafilm or some other background-free material. For best results, the sample should be kept small in comparison with the length of the coil and VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 52 0.025 µ s. Adjustment of the power with the parameter tpwr will alter the 90 ° pulse width parameter pw90. In addition, the parameter tpwrm can be UNITY used with INOVA and UNITYplus systems. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 53: Standard Wideline Samples

    Autogain) and acquire the data. Determine the 90 ° pulse width to 25 ns resolution. 12. Set pw and pw90 to the 90 ° pulse width value. This completes the calibration procedure. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 54 Finally, recalibrate the 90 ° pulse with a solution sample, then retune the probe to the same reflected power level. • T can be very long in solids. It may be necessary to set d1 to values of the order of 100 seconds in some cases. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 55: Data Processing

    In addition, spectral symmetry can be forced by software that sets the imaginary channel of the FID to zero. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 56: Chapter 4. Cramps/Multipulse Module Operation

    This chapter describes the procedures used to adjust the pulsewidth and phase transient for CRAMPS and other multiple-pulse cycle experiments. The tune-up sequences described in section 4.4 “Multipulse Tune-Up Procedure (FLIPFLOP),” page 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 57: Cramps/Multipulse Module Hardware

    Set a single repeating pulse of pw = 300 µ s with a d1=30 µ s for either F. Tune the input tuning pot(s) for maximum power or voltage. Iteratively adjust the output tuning (tune and "load" or "match") for maximum power or voltage. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 58 CH A and WB CH B (J246 and J247) with a pair of BNC cables. These ports provide the real and imaginary FID signals and bypass the analog filters. The unfiltered FID signal from 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 59 Consult the probe specification to determine the available 90 pulse. Varian provides a 5 mm narrow-body single-tuned CRAMPS probe for 300 MHz and 400 MHz magnets, which can be tuned from F to H.

  • Page 60: Multipulse Experiments And User Library

    NMR sequences are located in the user library userlib. User Library—Terms and Conditions Material submitted to the user library is distributed by Varian as a service to its users. All rights to the material submitted are retained by the submitter, unless explicitly surrendered in the accompanying README document.
  • Page 61 Acquire a FID and enter df to display both the real and imaginary points. Obtain the imaginary trace with the imaginary menu button. Adjust the phase to minimize the imaginary channel. If this is not possible, check to be sure the FID is on resonance. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 62: Figure 17. Real Channel Fid Pattern

    The ideal signal pattern (1.0,0.0,-1.0,0.0)N results from a 90 pulse. The bulge among the first few zero-points and the decay are due to RF inhomogeneity. A distribution of pw90 values interferes to cause the pattern of Figure 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 63: Figure 19. Flipflop "Tram Tracks

    Phase transient can be removed or balanced by adjusting tuning of the duplex circuit containing probe, amplifier, quarter-wave cable and preamplifier. A small adjustment of the probe tuning capacitor is often quite effective. In this case record the value of the reflected VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 64: Cramps Experiment (Br24 Or Mrev8)

    10. Record the tuning values for Qtune or the tune interface for future use in tuning the probe with the sample. 11. Insert a sample of solid adipic acid or glycine and retune to the previous values. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 65: How To Obtain Good Cramps Spectra

    Typical spinning speeds for H CRAMPS are less than 2 kHz, and at these speeds the multiple-pulse cycle does all the narrowing of H dipolar interactions. ppm (sc) Figure 21. Adipic Acid Spectrum VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 66: Quadrature 1H Cramps

    90 positions in the plane of precession. Table 8 Table 9 show these phases and flip angles. In these sequences the flip angle and small-angle phase are varied 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 67: Fast Mas Assisted With A Multiple-Pulse Cycle (Wahuhahs)

    The result is often an improvement over high-speed spinning alone or slow spinning 1H CRAMPS. WaHuHaHS requires the same multiple-pulse set-up procedure described above for MREV8 and BR24. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 68: Flipflop - Pulse Width And Phase Transient Calibration

    8.0 ms. these two times are controlled by hardware adjustment in the magnet leg. Set rof2=0.2 µ s for a High-Power preamp. Set rof2=0.5 µ s for a Solids F preamp. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 69: Br24 And Cylbr24 - Multiple Pulse Line Narrowing (24-Pulse Cycle)

    S is the multiple-pulse scale factor for Br24 (0.385 for ideal pulses). rof1 and rof2 (see 4.9 “FLIPFLOP - Pulse Width and Phase Transient Calibration,” page VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 70: Mrev8 And Cylmrev - Multiple Pulse Line Narrowing (8-Pulse Cycle)

    S is the multiple-pulse scale factor for MREV8 (0.471 for ideal pulses). rof1 and rof2 (see 4.9 “FLIPFLOP - Pulse Width and Phase Transient Calibration,” page 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 71: Wahuha And Wahuhahs - Mp-Assisted High-Speed Spinning (4-Pulse Cycle)

    S is the multiple-pulse scale factor for WaHuHa (0.707 for ideal pulses). rof1 and rof2 (see 4.9 “FLIPFLOP - Pulse Width and Phase Transient Calibration,” page VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 72: Chapter 5. Solid-State Nmr Accessories

    • 5.4 “Variable Temperature Operation with Solids,” page 78 5.1 Pneumatics/Tachometer Box The variable temperature (VT) Pneumatics/Tachometer Box is used with Varian VT CP/ MAS probes. The Pneumatics/Tachometer Box handles all air/gas supply distribution to the probe. The supply line is permanently connected to the wall supply, which must be clean, dry air.

  • Page 73: Figure 26. Pneumatics/Tachometer Box For Cp/Mas Probes

    A potential source of error exists in determining the point of the light transition on which to trigger the digital circuitry. This is a factor determined by two variables: the light detection circuitry and the markings on the rotor. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 74: Figure 28. Base Of A Varian High-Speed Spinning Rotor

    –50 ° C to +100 ° C, provided that the tachometer amplifier gain is correctly adjusted to give a signal of no less than 1 Vpp into the tachometer box. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 75 “Spinning the Sample,” page 22, and the spinning speed may be read on the tachometer box LCD display. Note that for Varian probes, the optical fibers should be plugged into the tachometer box, and for Doty probes the probe should be connected to the...

  • Page 76: Rotor Speed Controller Accessory Operation

    5.3 Rotor Speed Controller Accessory Operation The Varian rotor speed controller accessory provides computer control of the spin rate of a CP/MAS sample. By using the controller in a closed loop mode, the sample spinning rate can be held constant to a few hertz or better over a long acquisition time (days or weeks).
  • Page 77 Table 11. Rotor Controller Gain Setting and Typical Ranges Gain Setting Typical Ranges 4 to 5 1 to 2 VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 78: Variable Temperature Operation With Solids

    The Varian solids variable temperature accessory (Part No. 00-958994-00) can be added to a Varian VT CP/MAS probe for VT operation. When this accessory is added, connection of the gas supplies to the probe is altered in the following ways.
  • Page 79 Chapter 5. Solid-State NMR Accessories 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 the following ways: •...

  • Page 80: Chapter 6. Solid-State Nmr Experiments

    • 6.27 “MREVCS—Multiple Pulse Chemical-Shift Selective Spin Diffusion,” page 122 • 6.28 “MQ_SOLIDS—Multiple-Quantum Solids,” page 123 • 6.29 “SPINDIFF—Spin Diffusion in Solids,” page 124 • 6.30 “FASTACQ—Multinuclear Fast Acquisition,” page 124 • 6.31 “NUTATE—Solids 2D Nutation,” page 125 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 81: Xpolar-Cross-Polarization, Unity

    None of these sequences are available on and GEMINI 2000 systems. ERCURY The macros for some of the solid-state NMR sequences are located in maclib. The macros for other solid-state NMR sequences are located in the user library userlib. User Library—Terms and Conditions Material submitted to the user library is distributed by Varian as a service to its users.

  • Page 82: Figure 30. Toss Pulse Sequence

    The experiment is run by setting pdp='y', setting srate to the spinning speed and entering appropriate values for the dephasing time d2 (in seconds). Figure 31 shows the pulse sequence diagram for cross-polarization with interrupted decoupling. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 83: Figure 31. Protonated Carbon Suppression Sequence

    T list, results in the construction of the file analyze.list, where the summary of the data analysis and calculations are stored in the current experiment. A hard copy can be VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 84: Figure 33. Pulse Sequence For Measuring H T

    Hartmann-Hahn matching. The decoupler is set with the config display and can be either class C, with a 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 85: Xpolar1-Cross-Polarization

    INOVA, UNITYplus, and newer UNITY systems. The parameters that control the attenuators and linear modulators are shown in the diagram of XPOLAR1, see Figure cntct (tpwrm) cntct (dipolr) (crossp) Figure 34. XPOLAR1 Pulse Sequence VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 86 TOSS and dipolar dephasing, pwx is in microseconds. • cntct is the cross-polarization contact time, in microseconds. • tpwr is the observe power setting . Spectrometer Minimum, dB Maximum, dB INOVAcpmas MERCURYcpmas 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 87: Xpwxcal-Observe-Pulse Calibration With Cross-Polarization

    6.3 XPWXCAL—Observe-Pulse Calibration with Cross-Polarization The pulse sequence XPWXCAL, derived from XPOLAR1, is used to calibrate the observe 90 ° pulse if observe pulses are to be used explicitly in pulse sequences. Because cross- VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 88: Figure 35. Xpwxcal Pulse Sequence

    For HETCORCP1, pwx must be set to pw (by adjusting tpwrm), and pw is used for both observe and proton pulses. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 89: Xnoesysync-Rotor Sync Solids Sequence For Exchange

    0 for P type, phase is 1 for N type, or phase is 1,2 for phase sensitive. The Veeman experiment requires phase=0. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 90: Masexch1-Phase-Sensitive Rotor Sync Sequence For Exchange

    The macro masexch1 converts a parameter set obtained with XPOLAR or XPOLAR1 for the MASEXCH1 experiment. Power levels and pulse widths are retained. The default is phase=1,2,3,4 and the data are transformed with wft2d(1,0,0,1,1,0,0,- 1,0,-1,1,0,0,1,1,0). 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 91: Figure 37. Masexch1 Pulse Sequence

    (normal) NOESY. nt is a minimum of 16. Reference Luz, Z.; Spiess, H. W.; Titman, J. J. Israel J. of Chem. 1992, 32, 145. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 92: Hetcorcp1-Solid-State Hetcor

    . In this case, set dipoff for the center of the H shift region for best decoupling. dipof2 is set to 'n' to use dof during the evolution period and decoupling. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 93: Wise1-Two-Dimensional Proton Wideline Separation

    “liquids” patterns, waltz, xy32, etc., are not necessarily useful for solids. Several useful patterns are described below and are included in the shapelib directory of SolidsLib, version 2.1. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 94 .DEC file for best decoupling at a particular field strength and spinning speed. blew 48.DEC provides decoupling with BLEW-48 according to Burum et. al. BLEW-48 decouples protons from themselves but leaves a scaled C– H dipolar interaction. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 95: Xpolxmod1-Waveform Modulated Cross-Polarization

    One waveform generator is required, and it can be placed on channel 1 or channel 2 as needed. Macros The macros xpolxmod1 and xpolhmod1 convert a parameter set obtained with XPOLAR or XPOLAR1 for these experiments Power levels and pulse widths are retained. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 96 0 to 2 π radians. For a ramp, the slope is negative (1-4t/per) for t=0 to per/2 and positive (1+4t/per) for t=per/2 to per. Set per relative to cntct to obtain a specific shape or ramp during the contact time. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 97: Vacp-Variable Amplitude Cross-Polarization

    Units are the same as crossp. vacp[0]=crossp, vacp[n]–vacp[n–1]=500, and n=11. Syntax is as follows: vacp<(<<<vacp[n]–vacp[n–1],vacp[0]>,n>)>. The vacplist macro lists VACP levels and resets array='' (two single quotes). VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 98: Xpoledit1-Solids Spectral Editing

    XPOLEDIT1 is available on UNITY INOVA and UNITYplus and present in userlib. Macro The macro xpoledit1 converts a parameter set obtained with XPOLAR or XPOLAR1 for XPOLEDIT1. Power levels and pulse widths are retained. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 99: 3Qmas1-Triple-Quantum 2D For Quadrupole Nuclei

    The processing parameter daslp is present in VNMR 5.2 and later. The 3QMAS1 experiment requires only MAS hardware and in many circumstances this method can replace the need to do the more complicated experiments, double rotation VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 100: Table 10. Multiacquisition Quadrature Corrections For Cory24

    I=5/2. daslp is available for VNMR version 5.2 and later (refer to the VNMR Command and Parameter Reference). phase=1,2 are the sine and cosine components of hypercomplex Fourier transform, wft2da. References Frydman, L.; Harwood, J. S. J. Am. Chem. Soc. 1995, 117, 5367. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 101: Pass1-2D Sideband Separation For Cp/Mas

    INOVA and UNITYplus and present in userlib. Macro The macro pass1 converts a parameter set obtained with XPOLAR or XPOLAR1 for the 2D PASS experiment. Power levels and pulse widths are retained. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 102: Cpcs-Cross-Polarization With Proton Chemical Shift Selection

    C CP/MAS detection. cntct (tpwrm) cntct (dipolr) (crossp) dtau 'cycles' times tau+dtau Figure 43. CPCS Pulse Sequence Macro The cpcs macro sets up parameters for the CPCS pulse sequence. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 103: Cpcosyps-Cross-Polarization Phase-Sensitive Cosy

    The macro cpcosyps converts a parameter set, obtained with XPOLAR or XPOLAR1, for the solids homonuclear correlation experiment CPCOSYPS. Power levels and the 90° ° pulse width are retained. Default parameters set up for a phase-sensitive hypercomplex acquisition with sw1=sw and xpol='y'. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 104: Cpnoesyps-Cross-Polarization Phase-Sensitive Noesy

    NOESY experiment. CPNOESYPS can be run as a direct polarization experiment or the first 90 ° pulse can be substituted with a cross-polarization pulse element. Figure 45 is a diagram of this sequence. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 105: Figure 45. Cpnoesyps Pulse Sequence

    2D exchange correlation experiment CPNOESYPS. Power levels and the proton 90 ° pulse width are retained. Default parameters set up for a phase-sensitive hypercomplex acquisition with rfdr set to 'y'. Also, sw1 is set equal to sw and xpol='y'. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 106: R2Selpuls1-Rotation Resonance With Selective Inversion

    Rotational resonance is often used for the determination of the structure of biomolecular materials such as membrane proteins. CPNOESY with rfdr='y' provides similar information. Applicability R2SELPULS1, found in userlib, is available only on UNITY INOVA and UNITYplus. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 107: Figure 46. R2Selpuls1 Pulse Sequence

    Set tof2 in r2selpuls1 equal to the this tof. mix is the mixing period in milliseconds. Use caution, because setting dm='y' during the mix period may lead to an unacceptable duty cycle. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 108: Dipshft1-Separated Local Field Spectroscopy

    DIPSHFT1. Power levels and the proton 90 ° pulse width are retained. The value of pp is estimated from pw, dipolr, and crossp. Further calibration of pp may be necessary. Parameters refocus and setup are both set to 'n'. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 109: Sedra2-Simple Excitation Of Dephasing Rotational-Echo Amplitudes

    Therefore, special methods are needed to obtain the connectivity information. SEDRA, Simple Excitation of Dephasing of Rotational-Echo Amplitudes, is one of the new experiments created for this purpose. Figure 48 is a diagram of SEDRA. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 110: Figure 48. Sedra2 Pulse Sequence

    The macro sedra2 converts a parameter set, obtained with XPOLAR or XPOLAR1, for the transverse SEDRA experiment of Guillion and Vega. Power levels and the proton 90 ° pulse width are retained. The value of pwx must be calibrated (use XPWXCAL). 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 111: Redor1-Rotational Echo Double Resonance

    N pulses serves as a control experiment. The typical plot is (So-S)/S, where S is the spectral intensity the and N pulses and So is the intensity without. The carbon-nitrogen bond distance is determined by simulation of the curve. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 112: Figure 49. Redor1 Pulse Sequence

    REDOR modulation of the peak intensity. rdflag is set to 'n' to apply π pulses only to the observe channel and thus obtain observe peak intensity without REDOR modulation. Typically, the array rdflag='n','y' is used. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 113: Doublecp1-Double Cross-Polarization

    Observe and decoupler power levels and the proton 90 ° pulse width are retained. Third-channel power levels and the dilute-spin Hartmann-Hahn match must be calibrated (see crossp2 below). VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 114: Figure 50. Doublecp1 Pulse Sequence

    (0 to 4095). The parameters crossp and crossp2 determine the Hartmann-Hahn match for the dilute-spin cross- polarization. The dilute-spin Hartman-Hahn match is determined with DOUBLECP1. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 115: T1Cp1-T

    See page 85 for a description of these parameters. pwx is the observe 90 ° pulse, in microseconds. d2 is the delay of the T inversion recovery, in seconds. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 116: Hahncp1-Spin 1/2 Echo Sequence With Cp

    Observe and decoupler power levels and the 90 ° pulse width are retained, as well as the value of xpol. By default, pwx=pw. Fine calibration of pwx is recommended, tau1=tau2=10 (in microseconds). 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 117: Ssecho1-Solid-State Echo Sequence For Wideline Solids

    (I>3/2), because different types of line shape information may be sought, a number of different echo sequences may be used, depending on the quantum transitions in interest. Figure 53 is a diagram of the SSECHO1 pulse sequence. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 118: Figure 53. Ssecho1 Pulse Sequence

    Other Parameters echo set to 'y' implements either a quadrupole echo or a composite echo (see compul below). echo set to 'n' implements a single pulse (the first pulse of the quadrupole echo) 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 119: Wlexch1-Wideline Solids Exchange

    At a given mixing time, one ellipse for each of these reorientation angles can be measured. Applicability WLEXCH1 is available only on UNITY INOVA and UNITYplus. It is found in userlib. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 120: Figure 54. Wlexch1 Pulse Sequence

    WLEXCH1. Adjust tau2 or use lsfid to set the beginning point of the Fourier transform. References Schmidt, C.; Blumich, B.; Spiess, H. W. J. Magn, Reson. 1988, 79, 269. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 121: Hs90-90-Degree° Phase Shift Accuracy

    'y', and the signal of the 500 kHz clock plugged into the external trigger input located on the Pulse Sequence Controller board. np is usually set to 128 points. tau is 20 microseconds. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 122: Mrevcs-Multiple Pulse Chemical-Shift Selective Spin Diffusion

    12*tau. mix is the mixing time, in microseconds, for H spin diffusion. cycles is the number of times through the multiple pulse cycle. cycles and tof, in combination, determine the chemical shift. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 123: Mq_Solids-Multiple-Quantum Solids

    The units of this parameter have not been fully checked. Use the display command to confirm units. Reference Baum, J.; Munowitz, M.; Garroway, A. N.; Pines, A. J. Chem. Phys. 1985, 83, 2015. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 124: Spindiff-Spin Diffusion In Solids

    (X,Y) the fastest possible acquisition of sequential spectra of two nuclei—for example, pulse – acquire (27Al) – pulse acquire (2H) – pulse – acquire (27Al)—storing FIDs in separate buffers. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

  • Page 125: Nutate-Solids 2D Nutation

    Portions of the data can be displayed with the standard arguments of the command dssh. 6.31 NUTATE—Solids 2D Nutation NUTATE is a two-dimensional solids nutation experiment patterned after that of Lippmaa and coworkers. The experiment illustrates the effect of pulse width on the spectra obtained. VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 126: Figure 60. Nutate Pulse Sequence

    1/sw1, in an analogous way to all standard 2D experiments. Processing The data is processed by the command wft2d(0,0,0,1). Reference Samoson, A.; Lippmaa, E. J. Magn. Reson. 1988, 79, 255. 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 127 Chapter 6. Solid-State NMR Experiments VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...

  • Page 128: Index

    CPNOESY experiment, booster power supply for VT controller, cpnoesyps macro, BR24, 64, 69, 70, CPNOESYPS pulse sequence, Multacquisition Quardrature Correction, CRAMPS, 56, pulse sequence, CRAMPS/multipulse, CRAMPS/Multipulse Module, CRAMPS/multipulse module hardware, credit cards caution, 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 129 (xpol=’n’), Doty gating input to linear amplifier, CP/MAS probe, generic power parameters, rotors, granular materials in a rotor, Double Cross experiment, doublecp1 macro, double-resonance experiments, dps command, 92, 109, VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 130 MQ_SOLIDS pulse sequence, MREV8, 64, 69, 70, cycles, Multacquisition Quardrature Correction, 1/2 Turn Off Angle, proton decoupling, On Angle, mrevcs macro, MREVCS pulse sequence, Multacquisition Quardrature Correction MREV8, Multiacquisition Quardrature Correction 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 131 FLIPFLIP, parameter, pwx parameter, 88, 104, 106, 107, 111, 113, 115, p1 parameter, 69, 84, 107, 113, p180 parameter, 40, 87, p2 parameter, 81, 84, 89, p3 parameter, 83, pacemaker warning, VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 132 TOSS, spinner command, 25, Array of Contact Times, rotor synchronization, Hexamethylbenzene, rotors changing, off angle, rotors for solids, on angle, rotorsync option, referencing, rotor-synchronization accessory, spectral rotor-synchronized CP/MAS exchange sequence, 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...
  • Page 133 (ADC) board, timed spin echoes, 40, experiments, tof parameter, module hardware, tof2 parameter, NMR experiments, Torlon end caps, 20, patterns, toss parameter, 40, 41, 82, 84, Wideline Receiver and Filter board, VNMR 6.1C User Guide: Solid-State NMR 01-999162-00 C0402...
  • Page 134 XPOLAR1 pulse sequence, 38, 39, 85, xpoledit1 macro, XPOLEDIT1 pulse sequence, xpolhmod1 macro, XPOLHMOD1 pulse sequence, xpolwfg1 macro, XPOLWFG1 pulse sequence, xpolxmod1 macro, XPOLXMOD1 pulse sequence, xpwxcal macro, 88, XPWXCAL pulse sequence, zirconia rotors, 28, 01-999162-00 C0402 VNMR 6.1C User Guide: Solid-State NMR...

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