DUMBOdqR1445sq: 2D R14_4^5 2Q/1Q correlation with DUMBO decoupling pulse program (TopSpin2.1)




Home and Applets > Pulse Program > 2Q/1Q and DUMBO > 2D Non Big F1 Spectral Width DUMBOdqR1445sq 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

;DUMBOdqR1445sq
;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

;d1 : recycle delay
;d5 : z filter delay, 0.1 μs or multiple of 1/cnst31, otherwise no signal
;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

;cnst3 : scaling factor for d3
;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=cnst3*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
  "inf1=(l3*(2*d3+p20))*2"     ;t1 increment
  "sp1=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"

1 ze                           ;acquire into a cleared memory

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
  10u reset1:f1                ;synchronise pulse and detection RF
  1m rpp10                     ;reset phase list pointer
  1m rpp20                     ;reset phase list pointer
  1m rpp11
  1m rpp13
  10u pl7:f1
                               ;R14_4^5 DQ excitation:
3 pul180:f1 ph11 ipp11         ;increment phase ph11 pointer
  pul180:f1 ph11 ipp11         ;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
                               ;phase correction, due to t1 evolution period,
                               ;is not applied to R14_4^5 DQ reconversion pulse. 
                               ;As a result, the 2D spectrum is shifted from F1=0.

                               ;R14_4^5 DQ reconversion:
6 pul180:f1 ph13 ipp13 pl7:f1  ;increment phase ph13 pointer
  pul180:f1 ph13 ipp13         ;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

  ;1m rp11                     ;reset all phases of ph11 and ph13 
                               ;to their original values, i.e. to the values they 
  ;1m rp13                     ;had before the first ip11 and ip13
                               ;in case of STATES remove semicolon at beginning of the 2 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=(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 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
  

Example: 1H in L-Tyrosine.HCl with AV700

1H L-Tyrosine.HCl spectrum, acquired with DUMBO-R14_4^5 DQ/SQ sequence

1H DQ/SQ spectrum of L-Tyrosine.HCl in a 2.5-mm diameter rotor spinning at 31.056 kHz and recorded with Bruker Avance III, 700 MHz SB US magnet; P9 = d3 = 1.80 µsec; 6*(2/cnst31)/7 = (2*d3 + P20)*2.


Pulseprogram parameters for DUMBOdqR1445sq.ppm:

General  
PULPROG DUMBOdqR1445sq.ppm
TD 700
NS 64
DS 0
SWH [Hz] 20000.00
AQ [s] 0.0175500
RG 16
DW [µs] 25.000
DE [µs] 1.10
CNST3 1.0000000
CNST11 1.0000000
CNST31 31056.0000000
D1 [s] 5.00000000
d3 [s] 0.00000180
D5 [s] 0.000000100
d9 [s] 0.00000200
d31 [s] 0.00003220
inf1 [µs] 55.20
L0 0
L1 4
L3 1
L11 20
P9 [µs] 1.80
PL13 [dB] -1.50
ZGOPTNS  
acqu [s] 0.00000030
count 316
count1 128
cycle [s] 0.00005540
de [µs] 0.00
dead [s] 0.00000120
rest [s] 0.00004360
Channel f1  
NUC1 1H
P1 [µs] 2.30
P10 [µs] 24.00
P20 [µs] 24.00
PL1 [dB] 2.00
PL1W [W] 55.62974930
PL7 [dB] 6.00
PL7W [W] 22.14660263
PL12 [dB] 2.00
PL12W [W] 55.62974930
pul180 [µs] 9.20
SFO1 [MHz] 700.1312952
SP1 [dB] -1.50
SP2 [dB] -1.50
SPNAM1 dumbo_1+0
SPNAM2 dumbo_1+0
SPOAL1 0.500
SPOAL2 0.500
SPOFFS1 [Hz] 0.00
SPOFFS2 [Hz] 0.00

Acquisition parameters:

  F2 F1
Experiment    
PULPROG DUMBOdqR1445sq.ppm  
AQ_mod DQD  
FnMODE   undefined
TD 700 256
NS 64  
DS 0  
TD0 1  
Width    
SW [ppm] 28.5661 25.8751
SWH [Hz] 20000.00 18115.941
IN_F [µs]   55.20
AQ [s] 0.0175500 0.0070656
Nucleus1    
NUC1 1H 1H
O1 [Hz] 1295.24 1295.24
O1P [ppm] 1.850 1.850
SFO1 [MHz] 700.1312952 700.1312952
BF1 [MHz] 700.1300000 700.1300000


1H L-Tyrosine.HCl spectrum, acquired with DUMBO-R14_4^5 DQ/SQ sequence

1H DQ/SQ spectrum of L-Tyrosine.HCl in a 2.5-mm diameter rotor spinning at 30 kHz and recorded with Bruker Avance III, 700 MHz SB US magnet; P9 = 1.80 µsec, d3 = 2.29 µsec; 6*(2/cnst31)/7 = (2*d3 + P20)*2.


Pulseprogram parameters for DUMBOdqR1445sq.ppm:

General  
PULPROG DUMBOdqR1445sq.ppm
TD 700
NS 64
DS 0
SWH [Hz] 20000.00
AQ [s] 0.0175500
RG 4
DW [µs] 25.000
DE [µs] 1.10
CNST3 1.2700000
CNST11 1.0000000
CNST31 30000.0000000
D1 [s] 5.00000000
d3 [s] 0.00000229
D5 [s] 0.000000100
d9 [s] 0.00000200
d31 [s] 0.00003333
inf1 [µs] 57.14
L0 0
L1 4
L3 1
L11 20
P9 [µs] 1.80
PL13 [dB] -1.50
ZGOPTNS  
acqu [s] 0.00000030
count 316
count1 128
cycle [s] 0.00005540
de [µs] 0.00
dead [s] 0.00000120
rest [s] 0.00004360
Channel f1  
NUC1 1H
P1 [µs] 2.30
P10 [µs] 24.00
P20 [µs] 24.00
PL1 [dB] 2.00
PL1W [W] 55.62974930
PL7 [dB] 6.00
PL7W [W] 22.14660263
PL12 [dB] 2.00
PL12W [W] 55.62974930
pul180 [µs] 9.52
SFO1 [MHz] 700.1312952
SP1 [dB] -1.50
SP2 [dB] 0.00
SP2W [W] 88.16721344
SPNAM1 dumbo_1+0
SPNAM2 dumbo_1+0
SPOAL1 0.500
SPOAL2 0.500
SPOFFS1 [Hz] 0.00
SPOFFS2 [Hz] 0.00

Acquisition parameters:

  F2 F1
Experiment    
PULPROG DUMBOdqR1445sq.ppm  
AQ_mod DQD  
FnMODE   undefined
TD 700 256
NS 64  
DS 0  
TD0 1  
Width    
SW [ppm] 28.5661 24.9966
SWH [Hz] 20000.00 17500.875
IN_F [µs]   57.14
AQ [s] 0.0175500 0.0073139
Nucleus1    
NUC1 1H 1H
O1 [Hz] 1295.24 1295.24
O1P [ppm] 1.850 1.850
SFO1 [MHz] 700.1312952 700.1312952
BF1 [MHz] 700.1300000 700.1300000


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
    Structural studies of biomaterials using double-quantum solid-state NMR spectroscopy,
    Annu. Rev. Phys. Chem. 54, 531-571 (2003).
    Abstract
     
  11. 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
     
  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).
    Abstract
     
  16. A. Wokaun and R. R. Ernst
    Selective detection of multiple quantum transitions in NMR by two-dimensional spectroscopy ,
    Chem. Phys. Lett. 52, 407-412 (1977).
    Abstract
     

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