DUMBOdqPC7sqbsw: 2D big F1 spectral width 2Q - 1Q PC7 correlation with DUMBO decoupling pulse program (TopSpin2.1)

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DQ/SQ pulse sequence with DUMBO

Since non-phase cycling is applied to the PC7 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 PC7 reconversion pulse for filtering DQ coherences.

*** Outline ***

Code for Avance III spectrometers with topSpin2.1 operating system

;2D DQ-SQ proton-proton shift correlation with POST C7 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
;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 post-c7 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 POST C7, B1=7*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), set to pl13 as in setup experiments

;cnst1 : phase for PC7 reconversion pulse due to t1 evolution period
;cnst31: spinning frequency (usually not more than 15 kHz possible)
;FnMode: undefined
;NS    : = 16*n
;zgoptns :-Dpresat or blank

;$COMMENT=homonuclear decoupling with w-DUMBO
;$TYPE=homonuclear decoupling
;$SUBTYPE=explicit acquisition

;cnst11 : to adjust t=0 for acquisition, if digmod = baseopt

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

define delay dead
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
define loopcounter count
  "count=aq/cycle"             ;make sure td datapoints are sampled
define delay rest              ;make sure sampling proceeds throughout the sequence

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

define pulse tau1
  "tau1=((0.25s/cnst31)/7)"    ; 90° pulse
define pulse tau4
  "tau4=((1s/cnst31)/7)"       ;360° pulse
define pulse tau3
  "tau3=((0.75s/cnst31)/7)"    ;270° pulse


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 PC7 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
  1m rpp12
  1m rpp13
  1m rpp14
  10u pl7:f1
                               ;PC7 excitation:
3 tau1:f1 ph11 ipp13 ipp14     ;increment reconversion phase ph13 and ph14 pointers
  tau4:f1 ph12 ipp12           ;increment phase ph12 pointer
  tau3:f1 ph11 ipp11           ;increment phase ph11 pointer
  lo to 3 times l1

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

6 tau1:f1 ph13+cnst1 pl7:f1    ;PC7 reconversion:
                               ;increase ph13 by cnst1 due to evolution period
  tau4:f1 ph14+cnst1 ipp14     ;iincrease ph14 by cnst1 due to evolution period
                               ;increment phase ph14 pointer
  tau3:f1 ph13+cnst1 ipp13     ;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
  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
  d9 RG_ON
  .1u RG_OFF
  (p10:sp1  ph10^):f1
  lo to 7 times count          ;make sure td points are sampled

  1m                           ;DQ filtering (four phase cycling):
  1m ip13                      ;increments all phases of ph13 by 90°
  1m ip14                      ;increments all phases of ph14 by 90°
  ;1m ip13*16384                ;increments all phases of ph13 by 90°
  ;1m ip14*16384                ;increments all phases of ph14 by 90°
  100m wr #0 if #0 zd

  1m ip11                      ;increments all phases of ph11 by 45°, 
                               ;90° phase for DQ coherence
  1m ip12                      ;increments all phases of ph12 by 45°, 
                               ;90° phase for DQ coherence
  ;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 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, 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 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 = (float,45.0)   0.00  51.43 102.86 154.29 205.71 257.14 308.57 
ph12 = (float,45.0) 180.00 231.43 282.86 334.29 385.71 437.14 488.57 
ph13 = (float,90.0)  90.00 141.43 192.86 244.29 295.71 347.14 398.57 
ph14 = (float,90.0) 270.00 321.43 372.86 424.29 475.71 527.14 578.57 

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

;ph11=(65536)     0  9362 18725 28087 37449 46811 56174 
;ph12=(65536) 32768 42130 51493 60855  4681 14043 23406
;ph13=(65536) 16384 25746 35109 44471 53833 63195  7022
;ph14=(65536) 49152 58514  2341 11703 21065 30427 39790

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


  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).
  2. Vadim Zorin and David Rice
    Direct-drive waveform programming for solid-state NMR with the DD2 MR system,
    PDF file
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    Proton micro-magic-angle-spinning NMR spectroscopy of nanoliter samples,
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    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).
    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).
    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).
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    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).
    DQ-DUMBO-PC7 pulse sequence

    DQ-DUMBO excitation pulse sequence.

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    Multiple-pulse and magic-angle spinning aided double-quantum proton solid-state NMR spectroscopy,
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    Annu. Rev. Phys. Chem. 54, 531-571 (2003).
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Solid-state NMR bibliography for:

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