2D only HETCOR pulse program for topSpin2.1 operating system

No homonuclear H-H decoupling during t1 period; inf1 = in0.

FSLG homonuclear H-H decoupling during t1 period.

DUMBO homonuclear H-H decoupling during t1 period.

;hxhetcor (TOPSPIN 2.0)

; heteronuclear correlation between protons and X nuclei
; with or without homonuclear decoupling during t1
; possible decoupling schemes are FSLG, PMLG, and DUMBO
; see e.g.: B.-J. van Rossum, H. Foerster, and H.J.M. deGroot, J. Magn. Reson. 124 (2003) 516-519
; create dumbo pulse using AU program dumbo
; create pmlg pulse using AU program pmlg_shape

; written by Stefan Steuernagel (031201)

;Avance II+ version
;parameters:
;ns : 2, n*4
;d1 : recycle delay
;pl1 : power level for X contact
;sp0 : proton power level during contact
;pl2 : =120dB, not used
;spnam0 : e.g. ramp.100 
;spnam1 : lgs-1, lgs-4 or pmlg-36, or dumbo1, set p10 to appropriate multiple of LG period
;pl12: for decoupling and excitation 1H
;sp1: for homonuclear decoupling DUMBO, PMLG
;pl13: for homonuclear decoupling FSLG
;p3 : 1H 90 degree pulse
;p10 : duration of phase modulated shape pulse
;p15 : contact time, short: 50 - 200 us
;pcpd2 : pulse length in decoupling sequence
;phcor3 : phase correction for optimal FSLG peformance: minimize zero frequency glitch in F1
;cpdprg2 : cw, tppm15, spinal64
;cnst20 : LG-RF field as adjusted, in Hz used to calculate cnst22 and cnst23 +and - LG frequency
;cnst21 : additional LG offset, usually =0
;cnst22 : +ve LG offset
;cnst23 : -ve LG offset
;cnst24 : offset for proton evolution under LG, usually 0 - -2000
;l0 : =0, increment for t1
;l3 : 1, 2, or 4 for dwell in t1
;zgoptns : -Dfslg, -Ddumbo, -Dpmlg, -Dnodec
;FnMode : States-TPPI, States, or TPPI for zgoptns -Dnodec
;         undefined for all other zgoptns
;mc2 : States-TPPI, if FnMode undefined, in case of States the statement "1m rp0" must be activated
;      by removing semicolon at the beginning of the corresponding line
;d0 : =3u
;in_010 : =1/swh {f1}, calculated in program
;nd_010 : 1

;$COMMENT=HETCOR (CP based), with or w/o homonuclear decoupling during t1, various schemes possible
;$CLASS=Solids
;$DIM=2D
;$TYPE=cross polarisation
;$SUBTYPE=heteronuclear correlation
;$OWNER=Bruker

define loopcounter nfid
"nfid=td1/2"

;cnst11 : to adjust t=0 for acquisition, if digmod = baseopt
"acqt0=1u*cnst11"

define pulse pma                        ;54.7° = magic angle
"pma=(p3*547)/900"

#ifdef fslg
#include <lgcalc.incl>
;in0 : =(0.578*l3*4*p5)             1/sqrt(3) = 0.578, the scaling factor
"in0=(0.578*l3*4*p5)"
#endif /* fslg */

#ifdef dumbo
;in0 : =0.578*l3*p10
"in0=(0.578*l3*p10)"
#endif /* dumbo */

#ifdef pmlg
;in0 : =0.578*l3*p10
"in0=(0.578*l3*p10)"
#endif /* pmlg */

1 ze
2 10m do:f2
  d1                                    ;recycle delay
  1u fq=cnst21:f2
  (p3 pl12 ph0):f2                      ;proton 90° pulse

#ifdef nodec                            ;no homonuclear H-H decoupling during t1 period
;d0 : =0
;inf1 : =1/swh(f1), increment for t1
"in0 = inf1"
  d0
#endif /* nodec */

#ifdef dumbo
  (pma ph1):f2
  1u fq=cnst24:f2
3 (p10:sp1 ph3):f2
  lo to 3 times l0
  (pma ph7 pl12 fq=cnst21):f2
#endif /* dumbo */

#ifdef pmlg
  (pma ph1):f2
  1u fq=cnst24:f2
3 (p10:sp1 ph3:r):f2
  lo to 3 times l0
  (pma ph7 pl12 fq=cnst21):f2           ;magnetization back to the xy plane for spin-locking
#endif /* pmlg */

#ifdef fslg
  (pma ph1):f2                          ;magnetization in the plane perpendicular to the 
                                        ;effective magnetic field
  1u fq=cnst24:f2
3 (p5 fq=cnst22 pl13 ph3):f2
  (p5 fq=cnst23 ph4):f2
  (p5 fq=cnst22 ph3):f2
  (p5 fq=cnst23 ph4):f2
  lo to 3 times l0
  (pma ph7 pl12 fq=cnst21):f2           ;magnetization back to the xy plane for spin-locking
#endif /* fslg */

  (p15 pl1 ph2):f1 (p15:sp0 ph10):f2    ;CP contact time
  1u cpds2:f2
  go=2  ph31
  1m do:f2
#ifdef nodec
  10m mc #0 to 2 F1PH(ip0,id0)
#else
  10m wr #0 if #0 zd
  1m ip0          ;increment all phases of ph0 by 90° 
                  ;for quadrature detection in F1 dimension
  lo to 2 times 2
4 1m iu0          ;increment counter l0 by 1
  lo to 4 times l3
; 1m rp0          ;in case of States remove semicolon at beginning of line
  lo to 2 times nfid
#endif /* nodec */
exit

ph0=1 3
ph1=1
ph2=0 0 2 2 1 1 3 3
ph3=0 
ph4=2
ph7=3
ph10=0
ph31=0 2 2 0 1 3 3 1
  

Example1: ¹H -> ³¹P in NH₄H₂PO₄ with AV500

¹H 90° pulse duration of NH₄H₂PO₄ in a 4-mm diameter rotor spinning at 14 kHz.

Pulseprogram parameters:

1. Collin M. Kowalchuk, Harald Rösner, Dieter Fenske, Yining Huang, and John F. Corrigan
   Copper tellurolate clusters in trimethylsilylated MCM-41 — Preparation and condensation,
   Can. J. Chem. 84, 196-204 (2006).
   Abstract
2. Robert W. Schurko, Roderick E. Wasylishen, Scott J. Moore, Luigi G. Marzilli, and John H. Nelson
   Solid-state phosphorus-31 NMR study of phosphine- and phosphite-substituted cobaloximes,
   Can. J. Chem. 77, 1973-1983 (1999).
   Abstract
3. K. D. Behringer and J. Blümel
   Immobilization of carbonylnickel complexes: A solid-state NMR study,
   Inorg. Chem. 35, 1814-1819 (1996).
   Abstract
4. Klaus Eichele and Roderick E. Wasylishen
   ³¹P NMR study of powder and single-crystal samples of ammonium dihydrogen phosphate: Effect of Homonuclear Dipolar Coupling,
   J. Phys. Chem. 98, 3108-3113 (1994).
   Abstract

Example2: ¹H -> ³¹P in NaH₂PO₄ with AV500

¹H MAS spectrum of NaH₂PO₄ in a 4-mm diameter, 50 µLitre HRMAS rotor spinning at 10 kHz.

Pulseprogram parameters:

¹H windowed DUMBO spectrum of NaH₂PO₄ in a 4-mm diameter, 50 µLitre HRMAS rotor spinning at 10 kHz.

Pulseprogram parameters for dumbod2:

1. Olivier Lafon, Qiang Wang, Bingwen Hu, Julien Trébosc, Feng Deng, and Jean-Paul Amoureux
   Proton-proton homonuclear dipolar decoupling in solid-state NMR using rotor-synchronized z-rotation pulse sequences,
   J. Chem. Phys. 130, 014504/1-014504/13 (2009).
   Abstract

³¹P{¹H} hetcor spectrum of NaH₂PO₄ in a 4-mm diameter rotor spinning at 14 kHz, no homonuclear H-H decoupling during t1 period.

Pulseprogram parameters:

Acquisition parameters:

References

1. Kanmi Mao and Marek Pruski
   Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS,
   J. Magn. Reson. 201, 165-174 (2009).
   Abstract
2. Kanmi Mao, Jerzy W. Wiench, Victor S.-Y. Lin, and Marek Pruski
   Indirectly detected through-bond chemical shift correlation NMR spectroscopy in solids under fast MAS: Studies of organic-inorganic hybrid materials,
   J. Magn. Reson. 196, 92-95 (2009).
   Abstract
3. Xianyu Xue and Masami Kanzaki
   Proton distributions and hydrogen bonding in crystalline and glassy hydrous silicates and related inorganic materials: Insights from high-resolution solid-state nuclear magnetic resonance spectroscopy,
   J. Am. Ceram. Soc. 92, 2803-2830 (2009).
   Abstract
4. Harris E. Mason, Andrew Kozlowski, and Brian L. Phillips
   Solid-state NMR study of the role of H and Na in AB-type carbonate hydroxylapatite,
   Chem. Mater. 20, 294-302 (2008).
   Abstract
5. Yao-Hung Tseng, Yi-Ling Tsai, Tim W. T. Tsai, Chun-Pin Lin, Shih-Hao Huang, Chung-Yuan Mou, and Jerry C. C. Chan
   Double-quantum filtered heteronuclear correlation spectroscopy under magic angle spinning,
   Solid State Nucl. Magn. Reson. 31, 55-61 (2007).
   Abstract
6. Gregory P. Holland and Todd M. Alam
   Multi-dimensional ¹H-¹³C HETCOR and FSLG-HETCOR NMR study of sphingomyelin bilayers containing cholesterol in the gel and liquid crystalline states,
   J. Magn. Reson. 181, 316-326 (2006).
   Abstract
7. Kinsei Anzai, Hiroyuki Kono, Jun-ichi Mizoguchi, Toshiharu Yanagi, Fumitoshi Hirayama, Hidetoshi Arima, and Kaneto Uekama
   Two-dimensional ¹³C-¹H heteronuclear correlation NMR spectroscopic studies for the inclusion complex of cyclomaltoheptaose (β-cyclodextrin) with a new Helicobacter pylori eradicating agent (TG44) in the amorphous state,
   Carbohydr. Res. 341, 499-506 (2006).
   Abstract
8. Piero Sozzani, Angiolina Comotti, Silvia Bracco, and Roberto Simonutti
   Cooperation of multiple CH…π interactions to stabilize polymers in aromatic nanochannels as indicated by 2D solid state NMR,
   Chem. Commun., 768-769 (2004).
   Abstract
9. Piero Sozzani, Silvia Bracco, Angiolina Comotti, Roberto Simonutti, and Isabella Camurati
   Stoichiometric compounds of magnesium dichloride with ethanol for the supported Ziegler-Natta catalysis: First recognition and multidimensional MAS NMR study,
   J. Am. Chem. Soc. 125, 12881-12893 (2003).
   Abstract
10. Dominique Massiot, Bruno Alonso, Franck Fayon, Florence Fredoueil, and Bruno Bujoli
    New NMR developments for structural investigation of proton-bearing materials at different length scales,
    Solid State Sci. 3, 11-16 (2001).
    Abstract
11. B.-J. van Rossum, H. Förster, and H. J. M. de Groot
    High-field and high-speed CP-MAS ¹³C NMR heteronuclear dipolar-correlation spectroscopy of solids with frequency-switched Lee-Goldburg homonuclear decoupling,
    J. Magn. Reson. 124, 516-519 (1997).
    Abstract

Solid-state NMR bibliography for: