Solid-state NMR pulse programs

This web page provides solid-state NMR pulse programs, most of which were introduced or improved by our group. It is our goal to make these NMR methods (which were developed with support by tax-payers' money) more widely available.

Users of Bruker DSX/DRX/Avance spectrometers should be able to run the programs with minor modifications, and may find the parameter files (click after the "Requires" category where possible) useful. For users of other platforms, the pulse timings, phase sequences, and comments given should still be useful.

Compatibility

With small modifications, the programs should work with Bruker XWINNMR 2.6 to 3.5. The most likely required change involves the detection commands and the frequency switches.

Order and Complexity

Within each category, the programs are listed roughly chronologically by publication date. A new program will usually be added at the end of the appropriate category.

In the "Requires" line, the simplest experiments are marked by a single !, the most difficult by !!!!!!.

WARNING and Disclaimers

The pulse programs provided here are intended only as guides. We cannot guarantee that they will work on your spectrometer. Incorrect parameter values, incompatible or malfunctioning pulse programmers, etc., could result in long pulses that may destroy your sample, probehead, preamplifier, and/or transmitter (high-power amp). You need to check the programs yourself, e.g. using a dummy load and oscilloscope, and adjust all parameters carefully for your system before use. We cannot be held responsible for any loss or damage caused by the use of the pulse programs and/or information provided here.

Some comments in the pulse programs may refer to older program versions and may not be accurate. Some phase lists may not be required in the current program version.

For background on the techniques listed, please refer first to the references provided. We will try to address specific questions, and certainly appreciate warnings, comments, and suggestions. However, for general questions of how to make pulse programs work on your spectrometer, please contact an application scientist of your spectrometer manufacturer.

  1. Quantitative NMR
  2. This material is based upon work supported by the National Science Foundation under grants No. 0138117 and EEC-0813570.

    1. DP/MAS with Hahn echo at 2 tr
    2. Difficulty
      !
      Description
      Quantitative 13C spectra (after long recycle delay), without baseline distortion.
      Requires
      high spinning frequency (e.g. 14 kHz)
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Accurate Quantification of Aromaticity and Nonprotonated Aromatic Carbon Fraction in Natural Organic Matter by 13C Solid State Nuclear Magnetic Resonance" Environ. Sci. Technol. 38: 2680-2684 (2004).
      • Jingdong Mao , Wei-Guo Hu , Klaus Schmidt-Rohr , G. Davies , E. A. Ghabbour and B. Xing "Quantitative Characterization of Humic Acids by Solid-State 13C NMR" Soil Sci. Soc. of Am. J. 64: 873-884 (2000).

    3. MultiCP (with Hahn echo at 2 tr)
    4. Difficulty
      ! !
      Description
      Essentially quantitative cross-polarization 13C spectra, without baseline distortion.
      Requires
      Usually high spinning frequency (e.g. 14 kHz)
      References
      • Robert L. Johnson and Klaus Schmidt-Rohr "Quantitative Solid-State 13C NMR Spectra with Signal Enhancement by Multiple Cross-Polarization" J. Magn. Reson. 239: 44-49 (2014).

    5. ComPmultiCP (with Hahn echo at 2 tr)
    6. Difficulty
      ! !
      Description
      MultiCP with composite flip-store pulse, providing better tolerance to flip-angle error and/or B1 inhomogeneity, and wider Hartmann-Hahn matching condition.
      Requires
      Usually high spinning frequency (e.g. 14 kHz)
      References
      • Pu Duan and Klaus Schmidt-Rohr # "Composite-pulse and partially dipolar dephased multiCP for improved quantitative solid-state 13C solid-state NMR" Journal of Magnetic Resonance 285: 68 - 78 (2017).

  3. SPECTRAL EDITING etc.
  4. This material is based upon work supported by the National Science Foundation under grant No. 0138117. Any opinions, findings, and conclusions or recommendations expressed in this material are those of author(s) and do not necessarily reflect the views of the National Science Foundation.

    1. Dipolar DEPT for CH-only spectra
    2. Difficulty
      ! ! ! !
      Description
      Selects CH (methyne) signals
      Requires
      Higher power during 2.16 tr = 540 us; 4kHz MAS
      References
      • Jingdong Mao , L. S. Hundal , M. L. Thompson and Klaus Schmidt-Rohr "Nuclear Magnetic Resonance and Diffuse-Reflectance Infrared Fourier-Transform Spectroscopy of Sludge-Derived Biocolloidal Organic Matter" Environ. Sci. Technol. 37: 1751-1757 (2003).
      • Klaus Schmidt-Rohr and Jingdong Mao "Efficient CH-Group Selection and Identification in 13C Solid-State NMR by Dipolar DEPT and 1H Chemical-Shift Filtering" J. Am. Chem. Soc. 124: 13938-13948 (2002).

    3. CP/T1/TOSS
    4. Difficulty
      !
      Description
      Use to determine recycle delay for DP/MAS
      Requires
      high sensitivity and therefore moderate spinning frequency (6.5 kHz)
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Accurate Quantification of Aromaticity and Nonprotonated Aromatic Carbon Fraction in Natural Organic Matter by 13C Solid State Nuclear Magnetic Resonance" Environ. Sci. Technol. 38: 2680-2684 (2004).
      • Jingdong Mao , Wei-Guo Hu , Klaus Schmidt-Rohr , G. Davies , E. A. Ghabbour and B. Xing "Quantitative Characterization of Humic Acids by Solid-State 13C NMR" Soil Sci. Soc. of Am. J. 64: 873-884 (2000).

    5. Recoupled long-range dipolar dephasing reference sequence
    6. Difficulty
      !
      Description
      Selects nonprotonated aromatic carbons far from protons (e.g. charcoal)
      Requires
      DP/TOSS or CP/TOSS at ca. 7 kHz MAS
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Recoupled Long-Range C-H Dipolar Dephasing in Solid-State NMR, and Its Use for Spectral Selection of Fused Aromatic Rings" J. Magn. Reson. 162: 217-227 (2003).

    7. SPIDER (Saturation-Pulse-Induced Dipolar Exchange with Recoupling)
    8. Difficulty
      ! ! ! !
      Description
      Selects C bonded to N
      Requires
      1H-14N-13C triple-resonance equipment, 5 kHz MAS
      References
      • Klaus Schmidt-Rohr , Jingdong Mao and D. C. Olk "Nitrogen-Bonded Aromatics in Soil Organic Matter and Their Implications for a Yield Decline in Intensive Rice Cropping" Proc. Natl. Acad. Sci. USA 101: 6351-6354 (2004).
      • Klaus Schmidt-Rohr and Jingdong Mao "Selective Observation of Nitrogen-Bonded Carbons in Solid State NMR by Saturation-Pulse Induced Dipolar Exchange with Recoupling" Chem. Phys. Lett. 359: 403-411 (2002).

    9. CSA filter: 3-pulse version
    10. Difficulty
      !
      Description
      Selects alkyl (i.e. sp3-hybridized) C, e.g. O-C-O (which overlap with aromatic C) by three- pulse CSA dephasing
      Requires
      ca. 5 kHz MAS; short CP for O-CH-O selection; long CP & gated decoupling for O-Cq-O selection
      Notes
      compare SUPER sequence (5.3) for measurement of all three CSA principal values
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Separation of Aromatic-Carbon 13C NMR Signals from Di-Oxygenated Alkyl Bands by a Chemical-Shift-Anisotropy Filter" Solid State NMR 26: 36-45 (2004).

    11. CH2 spectral editing by selection of three-spin coherence
    12. Difficulty
      ! ! ! !
      Description
      Selects CH2 (methylene) signals
      Requires
      Higher power during tr = 140 us; 5.8 kHz MAS
      Notes
      ca. 6% efficiency; Mao & KSR, unpublished

    13. CSA filter: 5-pulse version
    14. Difficulty
      !
      Description
      Selects alkyl (i.e. sp3-hybridized) C, e.g. O-C-O (which overlap with aromatic C) by five-pulse CSA dephasing
      Requires
      ca. 5 kHz MAS; short CP for O-CH-O selection; long CP & gated decoupling for O-Cq-O selection
      Notes
      compare SUPER sequence (5.3) for measurement of all three CSA principal values
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Separation of Aromatic-Carbon 13C NMR Signals from Di-Oxygenated Alkyl Bands by a Chemical-Shift-Anisotropy Filter" Solid State NMR 26: 36-45 (2004).

    15. RIDER (Relaxation-Induced Dipolar Exchange with Recoupling)
    16. Difficulty
      ! !
      Description
      Selects C bonded to N (and slowly rotating segments)
      Requires
      Same pulse sequence as CODEX; in contrast to SPIDER, only 1H-13C double-res. equipment is needed; but slow dynamics will produce artifacts.
      References
      • Kay Saalwächter and Klaus Schmidt-Rohr "Relaxation-Induced Dipolar Exchange with Recoupling: A MAS NMR Method for Determining Heteronuclear Distances without Irradiating the Second Spin" J. Magn. Reson. 145: 161-172 (2000).

    17. CSA filter: 5-pulse version(2)
    18. Difficulty
      !
      Description
      Selects alkyl (i.e. sp3-hybridized) C, e.g. O-C-O (which overlap with aromatic C) by five-pulse CSA dephasing
      Requires
      ca. 5 kHz MAS; short CP for O-CH-O selection; long CP & gated decoupling for O-Cq-O selection
      Notes
      compare SUPER sequence (5.3) for measurement of all three CSA principal values
      References
      • Jingdong Mao and Klaus Schmidt-Rohr "Separation of Aromatic-Carbon 13C NMR Signals from Di-Oxygenated Alkyl Bands by a Chemical-Shift-Anisotropy Filter" Solid State NMR 26: 36-45 (2004).

  5. 2D HETCOR FOR SITE IDENTIFICATION
  6. The FSLG as programmed in the following HETCOR experiments probably works only in the specified XWINNMR version. You may need to replace it with your own version of FSLG.

    1. HETCOR after 1H CSA filter
    2. Difficulty
      ! ! ! ! !
      Description
      Suppresses NH/OH signals in HETCOR spectra (overlap with aromatic H)
      References
      • Klaus Schmidt-Rohr and Jingdong Mao "Selective Dephasing of OH and NH Proton Magnetization Based on 1H Chemical-Shift Anisotropy Recoupling" J. Magn. Reson. 157: 210-217 (2002).

    3. 1H-13C HETCOR
    4. Difficulty
      ! ! !
      Description
      1H-13C HETCOR with FSLG decoupling and LGCP transfer
      Requires
      higher power for good 1H resolution; 6 – 12 kHz MAS
      Notes
      HETCOR has been used and improved by various groups, after the pioneering work of Caravatti et al.Chem. Phys. Lett., 100, 305 (1983). Also compare HETCOR with fast MAS at high field (Spiess ***)

  7. 1H SPIN DIFFUSION with 13C detection (HETCOR, CHHC)
    1. CHHC with MAD (Multiple Alternating Depolarization)
    2. Difficulty
      ! !
      Description
      2D 13C-13C NMR with cross peaks due to 1H spin diffusion
      Notes
      long measuring times at long mixing times (2% effic.)
      References
      • S-S. Hou , Qiang Chen and Klaus Schmidt-Rohr "Two-Dimensional 13C NMR with 1H Spin Diffusion for Characterizing Domain Sizes in Unlabeled Polymers" Macromolecules 37: 1999-2001 (2004).

    3. HETCOR after on-resonance 1H chemical-shift filter
    4. Difficulty
      ! ! !
      Description
      Suppression of dominant signals in HETCOR to reveal small bands
      Notes
      KSR & Mao, unpublished

  8. 1H NMR
    1. 1H background suppression
    2. Difficulty
      !
      Description
      Probehead background suppression in 1H one-pulse spectra
      Requires
      static or MAS spectra
      References
      • Qiang Chen , S-S. Hou and Klaus Schmidt-Rohr "A Simple Scheme for Probehead Background Suppression in One-Pulse 1H NMR" Solid State NMR 26: 11-15 (2004).

    3. 1H CRAMPS after 1H CSA filter
    4. Difficulty
      ! ! ! !
      Description
      Suppression of NH/OH signals in 1H CRAMPS spectra
      Requires
      relatively slow MAS
      References
      • Klaus Schmidt-Rohr and Jingdong Mao "Selective Dephasing of OH and NH Proton Magnetization Based on 1H Chemical-Shift Anisotropy Recoupling" J. Magn. Reson. 157: 210-217 (2002).

    5. PRIDE (PRoton Inverse-detected DEuteron) NMR by HMQC and pulsed 1H spin-lock
    6. Description
      Sensitivity-enhanced deuteron NMR of partially deuterated systems by 1H detection
      Requires
      static 2D experiment
      References
      • Klaus Schmidt-Rohr , K. Saalw&uuml , chter. chter , S. -F. Liu and Mei Hong "High-Sensitivity 2H-NMR in Solids by 1H Detection" J. Am. Chem. Soc. 123: 7168-7169 (2001).

  9. DYNAMICS
    1. CODEX (Centerband-Only Detection of Exchange)
    2. Difficulty
      ! !
      Description
      Detection of slow (1-ms to 10-s) exchange dynamics under MAS of any spinning frequency
      Requires
      rotation-synchronized mixing time (MAS trigger)
      References
      • D. Reichert , T. J. Bonagamba and Klaus Schmidt-Rohr "Slow-Down of 13C Spin Diffusion in Organic Solids by Fast MAS: A CODEX NMR Study" J. Magn. Reson. 151: 129-135 (2001).
      • E. R. deAzevedo , Wei-Guo Hu , T. J. Bonagamba and Klaus Schmidt-Rohr "Principles of Centerband-Only Detection of Exchange, and Extension to Four-Time CODEX" J. Chem. Phys. 112: 8988-9001 (2000).
      • E. R. deAzevedo , Wei-Guo Hu , T. J. Bonagamba and Klaus Schmidt-Rohr "Centerband-Only Detection of Exchange: Efficient Analysis of Dynamics in Solids by NMR" J. Am. Chem. Soc. 121: 8411-8412 (1999).

    3. WISE (2D 1H WIdeline SEparation by 13C chemical shifts) with LGCP
    4. Difficulty
      ! !
      Description
      Detect fast rotational dynamics by 1H line narrowing with 13C site resolution
      References
      • Klaus Schmidt-Rohr and Jingdong Mao "Efficient CH-Group Selection and Identification in 13C Solid-State NMR by Dipolar DEPT and 1H Chemical-Shift Filtering" J. Am. Chem. Soc. 124: 13938-13948 (2002).

    5. SUPER (Separation of Undistorted Powderpatterns by Effortless Recoupling)
    6. Difficulty
      ! ! !
      Description
      Separation of regular chemical-shift anisotropy powder patterns of dilute spins (13C, 29Si) with 0.155 scaling factor
      Requires
      2.5 – 4 kHz MAS, 13C w1 = 12.12 wr, 1H w1 = 30 wr.
      References
      • S. -F. Liu , Jingdong Mao and Klaus Schmidt-Rohr "A Robust Technique for Two-Dimensional Separation of Undistorted Chemical-Shift Powder Patterns in Magic-Angle Spinning NMR" J. Magn. Reson. 155: 15-28 (2002).

  10. Fluoropolymers
  11. This work has been authored at Iowa State University of Science and Technology under Contract No. W-7405-ENG-82 with U.S. Department of Energy. Any opinions, findings, and conclusions or recommendations expressed in this material are those of author(s) and do not necessarily reflect the views of the National Science Foundation.

    1. 2D 19F exchange NMR with fast MAS (>25 kHz)
    2. Difficulty
      ! !
      Description
      Determine proximity of various 19F sites
      References
      • Qiang Chen and Klaus Schmidt-Rohr "19F and 13C NMR Signal Assignment and Analysis in a Perfluorinated Ionomer (Nafion) by Two-dimensional Solid-State NMR" Macromolecules 37: 5995-6003 (2004).

    3. 13C CP NMR with fast MAS (>25 kHz) and pulsed 19F decoupling
    4. Difficulty
      ! ! ! !
      Description
      High-resolution 13C spectra of fluoropolymers
      Requires
      fast spinning (>14 kHz); demanding set-up due to narrow CP condition and small signal of small sample.
      References
      • S. -F. Liu and Klaus Schmidt-Rohr "High-Resolution Solid-State 13C NMR of Fluoropolymers" Macromolecules 34: 8416-8418 (2001).

    5. 19F-13C HETCOR
    6. Difficulty
      ! ! ! !
      Description
      One-bond correlations of 19F and 13C peak positions in fluoropolymers
      Requires
      little difficulty after 13C CP NMR with fast MAS (>25 kHz) and pulsed 19F decoupling
      References
      • Qiang Chen and Klaus Schmidt-Rohr "19F and 13C NMR Signal Assignment and Analysis in a Perfluorinated Ionomer (Nafion) by Two-dimensional Solid-State NMR" Macromolecules 37: 5995-6003 (2004).