DUMBOdqR1445sqbsw: 2D big F1 spectral width R14_4^5 2Q/1Q correlation with DUMBO decoupling pulse program (TopSpin2.1)




Home and Applets > Pulse Program > 2Q/1Q and DUMBO > 2D Big F1 Spectral Width DUMBOdqR1445sqbsw Decoupling
Double quantum / single quantum pulse sequence with DUMBO

Since non-phase cycling is applied to the R1445 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 R1445 reconversion pulse for filtering DQ coherences.


*** Outline ***


Code for Avance III spectrometers with topSpin2.1 operating system

;DUMBOdqR1445sqbsw
;2D DQ-SQ proton-proton shift correlation
;with R14_4^5 DQ excitation/reconversion
;with homonuclear DUMBO decoupling DQ evolution without prepulses during t1
;and windowed DUMBO acquisition
;S. P. Brown, A. Lesage, B. Elena and L. Emsley, J. Am. Chem. Soc. 126, 13230-13231 (2004).
;modified after Leskes, Madhu and Vega, Chem. Phys. Lett. to remove center artefact
;using STATES-TPPI
;This pulse program was written according to the corresponding DUMBO-sequence from
;the ENS-Lyon Pulse Program Library

;p9 2.4-4.5 usec, depending on probe deadtime, usually:
;for 200 and 300 MHz, CRAMPS probe required or use 4.5 usec,
;acqu or p9 must be as short as possible, avoiding dipolar coupling effects between DUMBO sequences,
;l11 or d9 must be as large as possible to improve S/N ratio, but keeping acqu positive and small,

;p1 : 90 degree 1H detection pulse
;p2 : presaturation 90 degree pulse
;p9 : acquisition window, 1.7-4.5 usec, depending on probe deadtime
;p10: dumbo-1   pulse for t2
;p20: dumber-22 pulse for t1
;p25: = inf1, for t1 increment

;d1 : recycle delay
;d5 : z filter delay, 0.1 μs or multiple of 1/cnst31, otherwise no signal
;d10: parameter for t1 value
;d20: delay between saturation pulses

;l0 : 0 as initial t1
;l1 : number R14_4^5 basic cycle elements, for protons 2-4 in real solids
;l3 : t1-increment multiplier, usually 2-4, to reduce required number of rows
;l11: number of oversampled data points to be averaged into one dwell point
;l20: # of pulses in saturation pulse train, 0 if undesired

;pl1 : 1H presaturation power
;pl7 : 1H power for R14_4^5 recoupling sequence, B1=(N/2n)*cnst31=1.75*cnst31 in Hz
;pl12: 1H power for pulses P1
;pl13: dumbo power
;sp1 : 1H power for windowed dumbo-1 (t2)
;sp2 : 1H power for dumber-22 (t1) (usually somewhat less power than sp1 since 
;      there is no window); first set to pl13 as in setup experiments

;cnst1 : phase for R14_4^5 reconversion pulse due to t1 evolution period
;cnst31: spinning frequency
;FnMode: undefined
;MC2   : STATES-TPPI
;NS    : 16*n
;WDW   : F1 QSINE 3, F2 QSINE 2 or EM
;zgoptns :-Dpresat or blank

;$COMMENT=homonuclear decoupling with w-DUMBO
;$CLASS=Solids
;$DIM=2D
;$TYPE=homonuclear decoupling
;$SUBTYPE=explicit acquisition
;$OWNER=hf

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


dwellmode auto

#include <Avancesolids.incl>
#include <Delayssolids.incl>

  "d3=p9"                      ;p9 sets the window to make sure it is in microseconds
  "d9=0.1u*(l11)"              ;set the sampling window, defined in Avancesolids.incl
  "blktr2 = 0.6u"              ;this opens the transmitter gate 0.6 usec before the
                               ;pulse, so the transmitter noise is not sampled
  "l0=0"                       ;reset F1 dwell counter
  "inf1=(l3*(2*d3+p20))*2"     ;t1 increment
  "sp1=pl13"
  "sp2=pl13"

define delay dead
  "dead=1.2u"
define delay acqu              ;small window, defined by d3, 2.5-4.5 usec depending
  "acqu=2*p9-1.2u-d9-.1u"      ;on probe deadtime
                               ;acqu or p9 must be as short as possible, avoiding dipolar coupling effects
                               ;l11 or d9 must be as large as possible but keeping acqu positive
define delay cycle
  "cycle=4*p9+2*p10+.2u"
define loopcounter count
  "count=aq/cycle"             ;make sure td datapoints are sampled
define delay rest              ;make sure sampling proceeds throughout the sequence
  "rest=aq-(count*cycle)"

define loopcounter count1      ;for STATES-TPPI procedure
  "count1=td1/2"               ;and STATES cos/sin procedure

define pulse pul180
  "pul180=(2.0s/cnst31)/7"     ;180° pulse

  "d31=1.0s/cnst31"
  "p25=inf1"

1 ze                           ;acquire into a cleared memory
  "d10=0.1u"                   ;make sure a short d10 is used initially

2 d31

#ifdef presat                  ;set with -Dpresat
pres, d20                      ;delay between saturation pulses
  (p2 pl1 ph4):f1              ;saturation loop if required
  lo to pres times l20
#endif /* presat */

  d1                           ;recycle delay

  "cnst1=-180*cnst31*d10"      ;phase correction for R14_4^5 reconversion pulse,
                               ;due to t1 DQ evolution period,
                               ;defined by the phase-time relationships

  10u reset1:f1                ;synchronise pulse and detection RF
  1m rpp10                     ;reset phase list pointer
  1m rpp20                     ;reset phase list pointer
  1m rpp11                     ;reset the phase ph11 pointer to the first element
  1m rpp13                     ;reset the phase ph13 pointer to the first element
  10u pl7:f1
                               ;R14_4^5 DQ excitation:
3 (pul180  ph11 ipp11):f1      ;increment phase ph11 pointer
  (pul180  ph11 ipp11):f1      ;increment phase ph11 pointer
  lo to 3 times l1

5 d3                           ;DQ evolution:
  d3
  (p20:sp2 ph20^):f1           ;dumber22
  d3
  d3
  (p20:sp2 ph20^):f1           ;dumber22
  lo to 5 times l0

                               ;R14_4^5 DQ reconversion:
6 (pul180  ph13+cnst1 ipp13 pl7):f1  ;increase ph13 by cnst1 due to evolution period
                               ;increment phase ph13 pointer
  (pul180  ph13+cnst1 ipp13):f1      ;increase ph13 by cnst1 due to evolution period
                               ;increment phase ph13 pointer
  lo to 6 times l1

  d5 pl12:f1                   ;z filter delay
  STARTADC                     ;prepare adc for sampling, set reference frequency, 
                               ;defined in Avancesolids.incl
  RESETPHASE                   ;reset reference phase

  (p1 ph1):f1                  ;90° detection pulse at pl12
  .1u DWL_CLK_ON
7 dead
  acqu
  d9 RG_ON
  .1u RG_OFF                   ;take l11 complex data points
  (p10:sp1  ph10^):f1          ;w-dumbo, use 24 usec at 600 MHz  or higher
  dead
  acqu
  d9 RG_ON
  .1u RG_OFF
  (p10:sp1  ph10^):f1
  lo to 7 times count          ;make sure td points are sampled

  rest
  1u  DWL_CLK_OFF
  1m                           ;DQ filtering (four phase cycling):
  1m ip13*16384                ;increments all phases of ph13 by 90°
  rcyc=2                       ;next scan
  100m wr #0 if #0 zd          ;save data

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

8 1m iu0                       ;increment counter l0 by 1
  lo to 8 times l3             ;for multiple t1 increment

  "d10=d10+p25"                ;p25=inf1=increment for F1 (to make it usec!)
                               ;d10 is the t1 evolution period

  ;1m rp11                      ;reset all phases of ph11 and ph13
  ;1m rp13                      ;had before the first ip11 and ip13

  lo to 2 times count1         ;count1 = td1/2
  exit                         ;finished


ph1=  1 1 1 1 2 2 2 2 3 3 3 3 0 0 0 0
ph10= 0 2                      ;windowed dumbo phase during t2

ph11=(65536) 11704 53832       ; 64.29°  295.71°  or  64.29°   -64.29°
ph13=(65536) 28088  4680       ;154.29°   25.71°  or  ph11 + 90°

                               ;an overall constant phase shift of π/2 is applied 
                               ;to the reconversion pulse phases ph13 and ph14 for time reversal

ph4= 0                         ;for presaturation pulse
ph20=0 2                       ;dumber22 phase during t1
ph30=0                         ;needed for acquisition, involved in RESETPHASE
ph31=0 2 0 2 1 3 1 3 2 0 2 0 3 1 3 1                   ;involved in STARTADC
                               ;ph31 = ph1 + 2*ph13 + 1
  

References

  1. Renée Siegel, Luís Mafra, and João Rocha
    Improving the 1H indirect dimension resolution of 2D CRAMPS NMR spectra: A simulation and experimental investigation,
    Solid State Nucl. Magn. Reson. 39, 81-87 (2011).
    Abstract
     
  2. Vadim Zorin and David Rice
    Direct-drive waveform programming for solid-state NMR with the DD2 MR system,
    PDF file
     
  3. Andreas Brinkmann, Suresh Kumar Vasa, Hans Janssen, and Arno P. M. Kentgens
    Proton micro-magic-angle-spinning NMR spectroscopy of nanoliter samples,
    Chem. Phys. Lett. 485, 275-280 (2010).
    Abstract
     
  4. Luis Mafra, Renée Siegel, Christian Fernandez, Denis Schneider, Fabien Aussenac, and João Rocha
    High-resolution 1H homonuclear dipolar recoupling NMR spectra of biological solids at MAS rates up to 67 kHz,
    J. Magn. Reson. 199, 111-114 (2009).
    Abstract
    DQ-DUMBO-RN pulse sequence

    RN-DQ/SQ-DUMBO excitation pulse sequence.

     
  5. Luís Mafra, José R. B. Gomes, Julien Trébosc, João Rocha, and Jean-Paul Amoureux
    1H-1H double-quantum CRAMPS NMR at very-fast MAS (νR = 35 kHz): A resolution enhancement method to probe 1H-1H proximities in solids,
    J. Magn. Reson. 196, 88-91 (2009).
    Abstract
    DQ-SAM-BABA pulse sequence

    BABA-DQ/SQ-SAM excitation pulse sequence.

     
  6. Elodie Salager, Robin S. Stein, Chris J. Pickard, Bénédicte Elena, and Lyndon Emsley
    Powder NMR crystallography of thymol,
    Phys. Chem. Chem. Phys. 11, 2610-2621 (2009).
    Abstract
     
  7. Michal Leskes, P. K. Madhu, and Shimon Vega
    Proton line narrowing in solid-state nuclear magnetic resonance: New insights from windowed phase-modulated Lee-Goldburg sequence,
    J. Chem. Phys. 125, 124506/1-124506/18 (2006).
    Abstract
     
  8. Steven P. Brown, Anne Lesage, Bénédicte Elena, and Lyndon Emsley
    Probing proton-proton proximities in the solid state: High-resolution two-dimensional 1H-1H double-quantum CRAMPS NMR spectroscopy,
    J. Am. Chem. Soc. 126, 13230-13231 (2004).
    Abstract
    DQ-DUMBO-PC7 pulse sequence

    DQ-DUMBO excitation pulse sequence.

     
  9. P. K. Madhu, Elena Vinogradov, and Shimon Vega
    Multiple-pulse and magic-angle spinning aided double-quantum proton solid-state NMR spectroscopy,
    Chem. Phys Lett. 394, 423-428 (2004).
    Abstract
     
  10. 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
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    Annu. Rev. Phys. Chem. 54, 531-571 (2003).
    Abstract
     
  11. T. Karlsson, A. Brinkmann, P. J. E. Verdegem, J. Lugtenburg, and M. H. Levitt
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    Solid State Nucl. Magn. Reson. 14, 43-58 (1999).
    Abstract
     
  12. 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
     
  13. 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
     
  14. W. A. Dollase, M. Feike, H. Förster, T. Schaller, I. Schnell, A. Sebald, and S. Steuernagel
    A 2D 31P MAS NMR study of polycrystalline Cd3(PO4)2,
    J. Am. Chem. Soc. 119, 3807-3810 (1997).
    Abstract
     
  15. 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).
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  16. A. Wokaun and R. R. Ernst
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    Chem. Phys. Lett. 52, 407-412 (1977).
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