SPC52dbigsw: 2D big double-quantum F1 spectral width SPC5 pulse program for TopSpin2.1




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Double-quantum excitation with SPC5 pulse sequence

Since non-phase cycling is applied to the SPC5 excitation pulse, four-phase cycling is applied to the detection pulse P1 for selecting the 0Q -> -1Q coherence order jump, and four-phase cycling is applied to the SPC5 reconversion pulse for filtering DQ coherences.

parameters for DQ pulse sequences

Andreas Brinkmann thesis, "Dipolar Recoupling in Magic-Angle-Spinning Nuclear Magnetic Resonance", Division of Physical Chemistry, Arrhenius Laboratory, Stockholm University, 2001.


*** Outline ***


Code for Avance III spectrometers with topSpin2.1 operating system

;spc52dbigsw  (TopSpin 2.1)
;modified for AVIII by HF, May 14, 07

;2D SQ-DQ correlation experiment with SPC5 sequence
;for the original C7 sequence see: Lee et al. Chem Phys Lett 242, 304-309, 1995
;see Hohwy, Rienstra, Jaroniec and Griffin, JCP 110, 7983, 1999

;Avance III version
;parameters:
;d1 : recycle delay
;d0 : incremented delay (2D) [1 usec]

;p1 : f1 presaturation pulses and detection pulse at pl1
;p9 : used as t1 increment for d0

;pl2  : =120dB, not used
;pl11 : for SPC5 recoupling sequence B1=5*cnst31 in Hz

;cnst31 : spinning speed
;l0  : number of composite SPC5 cycles multiple of 5 in DQ excitation
;l2  : number of composite SPC5 cycles multiple of 5 in DQ reconversion
;l20 : # of pulses in saturation pulse train
;ns : 16*n
;FnMode : undefined
;mc2 : STATES-TPPI
;nd0 : 1
;WDW : F1 QSINE 3,  F2 QSINE 2 or EM
;use "xau xfshear rotate" to shift spectrum suitably along f1
;zgoptns :-Dpresat or blank

;$COMMENT=SQ-DQ experiment with SPC5 sequence
;$CLASS=Solids
;$DIM=2D
;$TYPE=direct excitation
;$SUBTYPE=homonuclear correlation
;$OWNER=Bruker

define pulse pul360
  "pul360=(1s/cnst31)/5"    ;360° pulse
define pulse pul90
  "pul90=(0.25s/cnst31)/5"  ; 90° pulse
define pulse pul270
  "pul270=(0.75s/cnst31)/5" ;270° pulse

define loopcounter count    ;for STATES-TPPI procedure
  "count=td1/2"             ;and STATES cos/sin procedure

  "d31=(1s/cnst31)"

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

#include <rot_prot.incl>
                            ;protect for too slow rotation

  ze                        ;acquire into a cleared memory

  "d0=0.1u"                 ;make sure a short d0 is used initially

1 d31

#ifdef presat               ;set with -Dpresat
pres, d20                   ;delay between saturation pulses
  (p1 pl1 ph1):f1           ;saturation loop if required
  lo to pres times l20
#endif /* presat */

2 d1                        ;recycle delay

  "cnst1=180*cnst31*d0"     ;phase correction for SPC5 reconversion pulse,
                            ;due to t1 DQ evolution period,
                            ;defined by the phase-time relationships

  1m rpp11                  ;reset the phase ph11 pointer to the first element
  1m rpp12                  ;reset the phase ph12 pointer to the first element
  1m rpp13                  ;reset the phase ph13 pointer to the first element
  1m rpp14                  ;reset the phase ph14 pointer to the first element
  1u pl11:f1                ;switch to SPC5 RF condition

3 pul90  ph11 ipp13 ipp14   ;SPC5 DQ excitation
                            ;increment reconversion phase ph13 and ph14 pointers
  pul360 ph12 ipp12         ;increment phase ph12 pointer
  pul270 ph11 ipp11         ;increment phase ph11 pointer
  lo to 3 times l0          ;l0 = multiple of 5

4 d0                        ;double-quantum evolution period

5 pul90  ph13+cnst1         ;SPC5 DQ reconversion
                            ;increase ph13 by cnst1 due to evolution period
  pul360 ph14+cnst1 ipp14   ;increase ph14 by cnst1 due to evolution period,
                            ;increment phase ph14 pointer
  pul270 ph13+cnst1 ipp13   ;increase ph13 by cnst1 due to evolution period,
                            ;increment phase ph13 pointer
  lo to 5 times l2          ;l2 = multiple of 5

  (p1 pl1 ph5):f1           ;detection pulse, flip into the xy plane
  2u
  gosc ph31                 ;gosc does not loop to 1
                            ;start ADC with ph31 signal routing

                            ;DQ filtering (four phase cycling):
  40u ip13*16384            ;increments all phases of ph13 by 90°
  40u ip14*16384            ;increments all phases of ph14 by 90°
  lo to 1 times ns          ;next scan

  100m wr #0 if #0 zd       ;delay for disk I/O, store signal,
                            ;increase FID number
                            ;delete memory data
                            ;do not perform dummy scans
                            ;with next acquisition

  1m ip11*8192              ;increments all phases of ph11 by 45°, 
                            ;90° phase for DQ coherence
  1m ip12*8192              ;increments all phases of ph12 by 45°,
                            ;90° phase for DQ coherence
  lo to 1 times 2           ;t1 quadrature detection

  "d0=d0+p9"                ;set p9=increment for F1 (to make it usec!)

  ;1m rp11                  ;reset all phases of ph11, ph12, ph13, and ph14 
  ;1m rp12                  ;to their original values, i.e. to the values they 
  ;1m rp13                  ;had before the first ip11, ip12, ip13, and ip14
  ;1m rp14                  ;in case of STATES remove semicolon at beginning of the 4 lines

  lo to 1 times count       ;count = td1/2

HaltAcqu, 1m
exit

ph1=  0                     ;for saturation pulse

ph11= (65536)     0 13107 26214 39322 52429 32768 45875 58982  6554 19661
ph12= (65536) 32768 45875 58982  6554 19661     0 13107 26214 39322 52429
ph13= (65536) 16384 29491 42598 55706  3277 49152 62259  9830 22937 36044
ph14= (65536) 49152 62259  9830 22937 36044 16384 29491 42598 55706  3277

ph5=   0 0 0 0 2 2 2 2 1 1 1 1 3 3 3 3
ph31 = 0 2 0 2 2 0 2 0 1 3 1 3 3 1 3 1    ;ph31 = ph5 + 2*ph13
  

Example: 31P in VPI-5 zeolite with AV700

31P 2D spectrum acquired with SPC52dbigsw pulse sequence

31P 180°-phase shift supercycled POST-C5 (SPC5) DQ-SQ spectrum of VPI-5 zeolite with big DQ F1 spectral width; 3.2 mm-diameter rotor spinning speed: 10 kHz; high frequency Trigamma probehead, P-Al setting.


Pulseprogram parameters for spc52dbigsw.ppm:

General  
PULPROG spc52dbigsw.ppm
TD 2048
NS 32
DS 0
SWH [Hz] 100000.00
AQ [s] 0.0102900
RG 256
DW [µs] 5.000
DE [µs] 5.00
CNST11 0.0000000
CNST31 10000.0000000
D0 [s] 0.00000100
D1 [s] 10.00000000
D20 [s] 0.00800000
d31 [s] 0.00010000
L0 50
L2 50
L20 20
P9 [µs] 50.00
ZGOPTNS -Dpresat
count 100
Channel f1  
CNST1 1.0000000
NUC1 31P
P1 [µs] 4.30
PL1 [dB] -1.50
PL1W [dB] 156.82751465
PL11 [dB] 0.00
PL11W [dB] 111.02538300
pul270 [µs] 15.00
pul360 [µs] 20.00
pul90 [µs] 5.00
SFO1 [MHz] 283.4113792

Acquisition parameters:

  F2 F1
Experiment    
PULPROG spc52dbigsw.ppm  
AQ_mod DQD  
FnMODE   undefined
TD 2048 200
NS 32  
DS 0  
TD0 1  
Width    
SW [ppm] 352.8440 70.5688
SWH [Hz] 100000.000 20000.000
IN_F [µs]   50.00
AQ [s] 0.0102900 0.0050000
Nucleus1    
NUC1 31P 31P
O1 [Hz] -6439.85 -6439.85
O1P [ppm] -22.722 -22.722
SFO1 [MHz] 283.4113792 283.4113792
BF1 [MHz] 283.4178190 283.4178190


References

  1. Robert Schneider, Karsten Seidel, Manuel Etzkorn, Adam Lange, Stefan Becker, and Marc Baldus
    Probing molecular motion by double-quantum (13C,13C) solid-state NMR spectroscopy: Application to ubiquitin,
    J. Am. Chem. Soc. 132, 223-233 (2010).
    Abstract
     
  2. Mei Hong, Tatiana V. Mishanina, and Sarah D. Cady
    Accurate measurement of methyl 13C chemical shifts by solid-state NMR for the determination of protein side chain conformation: The influenza A M2 transmembrane peptide as an example,
    J. Am. Chem. Soc. 131, 7806-7816 (2009).
    Abstract
     
  3. G. P. Drobny, J. R. Long, T. Karlsson, W. Shaw, J. Popham, N. Oyler, P. Bower, J. Stringer, D. Gregory, M. Mehta, and P. S. Stayton
    Structural studies of biomateriaux using double-quantum solid-state NMR spectroscopy,
    Annu. Rev. Phys. Chem. 54, 531-571 (2003).
    Abstract
     
  4. T. Karlsson, A. Brinkmann, P. J. E. Verdegem, J. Lugtenburg, and M. H. Levitt
    Multiple-quantum relaxation in the magic-angle-spinning NMR of 13C spin pairs,
    Solid State Nucl. Magn. Reson. 14, 43-58 (1999).
    Abstract
     
  5. Mei Hong
    Solid-state dipolar INADEQUATE NMR spectroscopy with a large double-quantum spectral width,
    J. Magn. Reson. 136, 86–91 (1999).
    Abstract
     
  6. M. Hohwy, C. M. Rienstra, C. P. Jaroniec, and R. G. Griffin
    Fivefold symmetric homonuclear dipolar recoupling in rotating solids: Application to double quantum spectroscopy,
    J. Chem. Phys. 110, 7983-7992 (1999).
    Abstract
    SPC5 pulse sequence

    Definition of SPC5 excitation pulse.

     
  7. M. Hohwy, H. J. Jakobsen, M. Edén, M. H. Levitt, and N. C. Nielsen
    Broadband dipolar recoupling in the nuclear magnetic resonance of rotating solids: A compensated C7 pulse sequence,
    J. Chem. Phys. 108, 2686-2694 (1998).
    Abstract
     
  8. Y. K. Lee, N. D. Kurur, M. Helmle, O. G. Johannessen, N. C. Nielsen, and M. H. Levitt
    Efficient dipolar recoupling in the NMR of rotating solids. A sevenfold symmetric radiofrequency pulse sequence,
    Chem. Phys. Lett. 242, 304-309 (1995).
    Abstract
     

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Solid-state NMR bibliography for
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Arsenic-75
Barium-135/137
Beryllium-9
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Calcium-43
Cesium-133
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Gold-197
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Iodine-127
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Lithium-7
Magnesium-25
Manganese-55
Mercury-201
Molybdenum-95/97
Neon-21
Nickel-61
Niobium-93
Nitrogen-14
Osmium-189
Oxygen-17
Palladium-105
Potassium-39/41
Rhenium-185/187
Rubidium-85/87
Ruthenium-99/101
Scandium-45
Sodium-23
Strontium-87
Sulfur-33
Tantalum-181
Titanium-47/49
Vanadium-51
Xenon-131
Zinc-67
Zirconium-91



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