NMR Pulse Program Library Website of the Schmidt-Rohr Group

Dept. of Chemistry, Iowa State University, Ames, IA 50011

(Click here for Dr. Mei Hong¡¯s NMR web site)

 

This website 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. 

- In experiments with regular detection, you may need to copy the detection command from you CP/MAS program to replace the  ¡°go=2     ph31¡± command

 

- In multiple-pulse experiments with detection between pulses, please copy the detection commands from your MREV-8 or BR-24 programs to replace the ones used in our programs.

 

- For experiments with refocused or multiple-echo detection, we show the more traditional XWINNMR 2.6 as well as the more unusual XWINNMR 3.5 versions.

 

- Frequency switches are shown mostly with the syntax ¡°fq=cnst4: f2¡±, which works well in XWINNMR 3.5 and is convenient.  In XWINNMR 2.6 and 3.1, we always used pointers ¡°fq4: f2¡± to frequency lists found in the ¡°f1¡± subdirectory and accessed through ¡°ased¡±.

 

Order and Complexity

Within each category, the programs are listed roughly chronologically by publication date. A new program will 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 list, 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)      SPECTRAL EDITING etc.

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 necessary reflect the views of the National Science Foundation.

 

1.1) Program:

DP/MAS with Hahn echo at 2 tr

Description:

Quantitative 13C spectra, without baseline distortion

Requires:

!; high spinning frequency (e.g. 14 kHz)

Reference(s):

Mao et al., Soil Sci. Soc. of Am. J. 64, 873-884  (2000), Mao & Klaus Schmidt-Rohr (KSR), Environ. Sci. Technol. 38, 2680-2684 (2004).

 

 

1.2) Program:

DP/MAS with dipolar dephasing at high spinning speed

Description:

Quantitative 13C spectra of unprotonated C

Requires:

!; high spinning frequency (e.g. 14 kHz)

Reference(s):

Mao & KSR, Environ. Sci. Technol. 38, 2680-2684 (2004).

 

 

1.3) Program:

CP/T1/TOSS

Description:

Use to determine recycle delay for DP/MAS

Requires:

!; high sensitivity and therefore moderate spinning frequency (6.5 kHz)

Reference(s):

Mao et al., Soil Sci. Soc. of Am. J. 64, 873-884  (2000), Mao & KSR, Environ. Sci. Technol. 38, 2680-2684 (2004).

 

 

1.4) Program:

Dipolar DEPT for CH-only spectra

Description:

Selects CH (methyne) signals

Requires:

!!!! first set-up; !! run routinely (ca. 15% effic.).  Higher power during 2.16 tr = 540 us; 4 kHz MAS

Reference(s):

KSR & Mao, J. Am. Chem. Soc. 124, 13938-13948 (2002).

Applied in:

Mao et al., Environ. Sci. Technol. 37, 1751-1757 (2003).

 

 

1.5) Program:

Recoupled long-range dipolar dephasing  Reference Sequence

Description:

Selects nonprotonated aromatic carbons far from protons (e.g. charcoal)

Requires:

!; DP/TOSS or CP/TOSS at ca. 7 kHz MAS

Reference(s):

Mao & KSR, J. Magn. Reson. 162, 217-227 (2003).

 

 

1.6) Program:

SPIDER (Saturation-Pulse-Induced Dipolar Exchange with Recoupling)

Description:

Selects C bonded to N

Requires:

!!!!; 1H-14N-13C triple-resonance equipment,  5 kHz MAS

Reference(s):

KSR & Mao, Chem. Phys. Lett. 359, 403-411 (2002), KSR, Mao, Olk, Proc. Nat. Acad. Sci. 101, 6351-6354 (2004).

 

 

1.7) Program:

RIDER (Relaxation-Induced Dipolar Exchange with Recoupling)

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.

Reference(s):

Saalwächter & KSR, J. Magn. Reson. 145, 161-172 (2000).

 

 

1.8) Program:

CSA filter:  3-pulse version,  5-pulse version , 5-pulse version 2

Description:

Selects alkyl (i.e. sp3-hybridized) C, e.g. O-C-O (which overlap with aromatic C) by three- or 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

Reference(s):

Mao & KSR, Solid State NMR 26, 36-45 (2004); compare SUPER sequence (5.3) for measurement of all three CSA principal values

 

 

1.9) Program:

CH2 spectral editing by selection of three-spin coherence

Description:

Selects CH2 (methylene) signals

Requires:

!!!! first set-up; !!! run routinely (ca. 6% effic.).  Higher power during tr = 140 us; 5.8 kHz MAS

Reference(s):

Mao & KSR, unpublished

 

 

           

 

2) 2D HETCOR FOR SITE IDENTIFICATION

 

NOTE: The FSLG as programmed in the following HETCOR experiments probably works only in the specified XWINNMR version.  You may need to replace it by your own version of FSLG.

 

2.1) Program:

1H- 13C HETCOR

Description:

1H-13C HETCOR with FSLG decoupling and LGCP transfer

Requires:

!!!; higher power for good 1H resolution; 6 ¨C 12 kHz MAS

Reference(s):

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 ***)

 

 

 

2.2) Program:

MELODI (MEdium and LOng DIstance) HETCOR

Description:

Suppresses mostly trivial one-bond 1H-13C peaks in HETCOR

Requires:

!!!!; 

Reference(s):

Yao, KSR, Hong, J. Magn. Reson. 149, 139-143 (2001).

 

 

2.3) Program:

HETCOR after 1H CSA filter

Description:

Suppresses NH/OH signals in HETCOR spectra (overlap with aromatic H)

Requires:

!!!!!; 

Reference(s):

KSR & Mao, J. Magn. Reson. 157, 210-217 (2002).

 

 

3) 1H SPIN DIFFUSION with 13C detection (HETCOR, CHHC)

 

3.1) Program:

1H-13C HETCOR with 1H spin diffusion

Description:

1H-13C HETCOR with MREV-8 decoupling and LGCP transfer

Requires:

!!!;  slow spinning (4-kHz)

 

Reference(s):

Mao, Xing, & KSR, Environ. Sci. & Tech. 35, 1928-1934 (2001). Another version of HETCOR with spin diffusion was used widely by P. Mirau, J. White, et al.

 

 

3.2) Program:

1H-13C HETCOR with 1H spin diffusion

Description:

1H-13C HETCOR with FSLG decoupling and LGCP transfer

Requires:

!!!;  faster spinning (6 ¨C 12 kHz)

Reference(s):

Another version of HETCOR with spin diffusion was used widely by P. Mirau, J. White, et al.

 

 

3.3) Program:

1H-29Si HETCOR with refocused detection and 1H spin diffusion. (XWINNMR 2.6 and XWINNMR 3.5)

Description:

Sensitivity-enhanced detection of organic segments near silicate surfaces in composites of organic materials with nanosize silicates

Requires:

!!!;  set 29Si signal on resonance

Reference(s):

Hou et al. Solid State NMR 22, 110-127 (2002), and Macromolecules 36, 2769-2776 (2003).

 

 

3.4) Program:

HETCOR after on-resonance 1H chemical-shift filter

Description:

Suppression of dominant signals in HETCOR to reveal small bands

Requires:

!!!;

Reference(s):

KSR & Mao, unpublished

 

 

3.5) Program:

CHHC with MAD (Multiple Alternating Depolarization)

Description:

2D 13C-13C NMR with cross peaks due to 1H spin diffusion

Requires:

!!; long measuring times at long mixing times (2% effic.)

Reference(s):

Hou, Chen, & KSR, Macromolecules 37, 1999-2001 (2004).

 

 

4) 1H NMR

 

4.1) Program:

1H background suppression

Description:

Probehead background suppression in 1H one-pulse spectra

Requires:

!;  static or MAS spectra

Reference(s):

Chen & KSR, Solid State NMR 26, 11-15 (2004)

 

 

4.2) Program:

1H CRAMPS after 1H CSA filter

Description:

Suppression of NH/OH signals in 1H CRAMPS spectra

Requires:

!!!!;  relatively slow MAS

Reference(s):

KSR & Mao, J. Magn. Reson. 157, 210-217 (2002).

 

 

4.3) Program:

PRIDE (PRoton Inverse-detected DEuteron) NMR by HMQC and pulsed 1H spin-lock

Description:

Sensitivity-enhanced deuteron NMR of partially deuterated systems by 1H detection

Requires:

!!!!;  static 2D experiment

Reference(s):

KSR et al., J. Am. Chem. Soc. 123, 7168-7169 (2001).

                       

 

5) DYNAMICS

 

5.1) Program:

CODEX (Centerband-Only Detection of Exchange)

Description:

Detection of slow (1-ms to 10-s) exchange dynamics under MAS of any spinning frequency

Requires:

!!;  rotation-synchronized mixing time (MAS trigger)

Reference(s):

de Azevedo et al., J. Am. Chem. Soc. 121, 8411-8412 (1999) and J. Chem. Phys. 112, 8988-9001  (2000); Reichert, Bonagamba, KSR, J. Magn. Reson. 151, 129-135 (2001).

 

 

5.2) Program:

PUREX (PURE-EXchange) NMR

Description:

2D exchange experiment with suppression of the diagonal signal (ridge) and its artifacts

Requires:

!!;

Reference(s):

de Azevedo, Bonagamba, KSR J. Magn. Reson. 142, 86-96 (2000).  A somewhat more sensitive version was recently introduced by N. Nielsen.

 

 

5.3) Program:

SUPER (Separation of Undistorted Powderpatterns by Effortless Recoupling)

Description:

Separation of regular chemical-shift anisotropy powder patterns of dilute spins (13C, 29Si) with 0.155 scaling factor

Requires:

!!!; 2.5 ¨C 4 kHz MAS, 13C w1 = 12.12 wr, 1H w1 = 30 wr.

Reference(s):

Liu, Mao, & KSR, J. Magn. Reson. 155, 15-28 (2002).

 

 

5.4) Program:

WISE (2D 1H WIdeline SEparation by 13C chemical shifts) with LGCP

Description:

Detect fast rotational dynamics by 1H line narrowing with 13C site resolution

Requires:

!!;

Reference(s):

KSR, Clauss, Spiess, Macromolecules 25, 3273-3277 (1992).  This program also includes 13C decoupling during t1 introduced by Tekely et al., 

Recent application of this specific pulse sequence: KSR & Mao, J. Am. Chem. Soc. 124, 13938-13948 (2002).

                       

6) FLUOROPOLYMERS

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 necessary reflect the views of the National Science Foundation.

 

6.1) Program:

13C CP NMR with fast MAS (>25 kHz) and pulsed 19F decoupling

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.

Reference(s):

Liu & KSR, Macromolecules 34, 8416-8418 (2001).

 

 

6.2) Program:

19F-13C HETCOR

Description:

One-bond correlations of 19F and 13C peak positions in fluoropolymers

Requires:

!!!!;  little difficulty after 6.1)

Reference(s):

Chen & KSR, Macromolecules 2004

 

 

6.3) Program:

2D 19F exchange NMR with fast MAS (>25 kHz)

Description:

Determine proximity of various 19F sites

Requires:

!!;

Reference(s):

Chen & KSR, Macromolecules 2004

 

 

 

Prof. Klaus Schmidt-Rohr

Tel : 515-294-6105
Email : srohr@iastate.edu

http://www.chem.iastate.edu/faculty/Klaus_Schmidt-Rohr/
Comments/ Suggestions/ Queries: rawal@iastate.edu