DUMBOspindiff: spin diffusion pulse program




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Spin diffusion pulse sequence with DUMBO

Two-phase cycling is applied to the excitation pulse (1st prepulse P11) for filtering SQ coherences, non-phase cycling for the reconversion pulse (2nd prepulse P11), and four-phase cycling is applied to the detection pulse P1 for selecting the 0Q -> -1Q coherence order jump.


*** Outline ***


Code for Avance III spectrometers with topSpin2.1 operating system

;DUMBOspinddiff3.ppm
;modified after Leskes, Madhu and Vega, Chem. Phys. Lett. to remove center artefact
;using STATES-TPPI and digital mode acquisition
;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,

;p1 : proton detection pulse
;p11: excitation and reconversion proton pulses
;p9 : 1.7-4.5 usec, depending on probe deadtime

;d1 : recycle delay
;d5 : z filter delay

;l0 : 0 as initial t1
;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

;pl12: 1H power for pulses
;sp1 : 1H power for w-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

;FnMode: STATES-TPPI
;ns    : = 4n

;$COMMENT=homonuclear decoupling with w-dumbo
;$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 micorseconds
  "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+.1u"
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)"

1 ze                           ;acquire into a cleared memory
2 d1                           ;recycle delay
  1m rpp10
  1m rpp20
  10u reset1:f1                ;synchronise pulse and detection RF
  (p11 pl12 ph22):f1           ;excitation pulse

5 d3
  d3
  (p20:sp2 ph10^):f1           ;dumber-22
  d3
  d3
  (p20:sp2 ph10^):f1           ;dumber-22
  lo to 5 times l0

  (p11 pl12 ph23):f1           ;reconversion pulse
  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                  ;proton detection pulse at pl12
  .1u DWL_CLK_ON
7 dead
  acqu
  d9 RG_ON
  .1u RG_OFF                   ;take l11 complex data points
  (p10:sp1  ph20^):f1          ;w-dumbo, use 24 usec at 600 MHz or higher
  dead
  acqu
  d9 RG_ON
  .1u RG_OFF
  (p10:sp1  ph20^):f1
  lo to 7 times count          ;make sure td points are sampled

  rest
  1u  DWL_CLK_OFF
  1m
  rcyc=2
  d1 mc #0 to 2 F1PH(ip22, iu0)
  exit                         ;finished

ph0= 0
ph1= 0 1 2 3                   ;detection pulse phase
ph10=0 2
ph20=0 2

ph22=0 2                       ;excitation pulse phase
ph23=0                         ;reconversion pulse phase

ph30=0                         ;needed for acquisition, involved in RESETPHASE
ph31=ph22 + ph1                ;involved in STARTADC
                               ;the same data as ph31 = -ph22 + ph1
  

Example: 1H in Glycine with AV500

1H glycine spin diffusion spectrum, mixing time = 4 µseconds

1H spin diffusion spectrum of glycine in a 4-mm diameter, 12-µL HRMAS rotor spinning at 10 kHz; P10 = 36 µs and mixing time D5 = 4 µs.


Pulseprogram parameters for DUMBOspinddiff3.ppm:

General  
PULPROG DUMBOspinddiff3.ppm
TD 500
NS 8
DS 0
SWH [Hz] 20000.00
AQ [s] 0.0125750
RG 4
DW [µs] 25.000
DE [µs] 4.50
CNST11 0.0000000
D1 [s] 5.00000000
d3 [s] 0.00000280
D5 [s] 0.00000400
d9 [s] 0.00000300
inf1 [µs] 83.20
L0 0
L11 30
P9 [µs] 2.80
ST1CNT 100
acqu [s] 0.00000130
count 150
cycle [s] 0.00008330
dead [s] 0.00000120
rest [s] 0.00008000
Channel f1  
NUC1 1H
P1 [µs] 2.00
P10 [µs] 36.00
P11 [µs] 2.00
P20 [µs] 36.00
PL1 [dB] 3.80
PL12 [dB] 3.80
SFO1 [MHz] 500.2121980
SP1 [dB] 7.00
SP2 [dB] 7.00
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 DUMBOspinddiff3.ppm  
AQ_mod qsim  
FnMODE   States-TPPI
TD 500 200
NS 8  
DS 0  
TD0 1  
Width    
SW [ppm] 39.9830 24.0283
SWH [Hz] 20000.00 12019.231
IN_F [µs]   83.20
AQ [s] 0.0125750 0.0083200
Nucleus1    
NUC1 1H 1H
O1 [Hz] 12197.96 12197.96
O1P [ppm] 24.386 24.386
SFO1 [MHz] 500.2121980 500.2121980
BF1 [MHz] 500.2000000 500.2000000



1H glycine spin diffusion spectrum, mixing time = 2 milliseconds

1H spin diffusion spectrum of glycine in a 4-mm diameter, 12-µL HRMAS rotor spinning at 10 kHz; P10 = 36 µs and mixing time D5 = 20 ms.


Pulseprogram parameters for DUMBOspinddiff3.ppm:

General  
PULPROG DUMBOspinddiff3.ppm
TD 500
NS 16
DS 0
SWH [Hz] 20000.00
AQ [s] 0.0125750
RG 4
DW [µs] 25.000
DE [µs] 4.50
CNST11 0.0000000
D1 [s] 5.00000000
d3 [s] 0.00000280
D5 [s] 0.02000000
d9 [s] 0.00000300
inf1 [µs] 83.20
L0 0
L11 30
P9 [µs] 2.80
ST1CNT 100
acqu [s] 0.00000130
count 150
cycle [s] 0.00008330
dead [s] 0.00000120
rest [s] 0.00008000
Channel f1  
NUC1 1H
P1 [µs] 2.00
P10 [µs] 36.00
P11 [µs] 2.00
P20 [µs] 36.00
PL1 [dB] 3.80
PL12 [dB] 3.80
SFO1 [MHz] 500.2121980
SP1 [dB] 7.00
SP2 [dB] 7.00
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 DUMBOspinddiff3.ppm  
AQ_mod qsim  
FnMODE   States-TPPI
TD 500 200
NS 16  
DS 0  
TD0 1  
Width    
SW [ppm] 39.9830 24.0283
SWH [Hz] 20000.00 12019.231
IN_F [µs]   83.20
AQ [s] 0.0125750 0.0083200
Nucleus1    
NUC1 1H 1H
O1 [Hz] 12197.96 12197.96
O1P [ppm] 24.386 24.386
SFO1 [MHz] 500.2121980 500.2121980
BF1 [MHz] 500.2000000 500.2000000


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. Cristina Coelho, João Rocha, P. K. Madhu, and Luís Mafra
    Practical aspects of Lee-Goldburg based CRAMPS techniques for high-resolution 1H NMR spectroscopy in solids: Implementation and applications,
    J. Magn. Reson. 194, 264-282 (2008).
    Abstract
     
  3. Jiri Brus, Hana Petříčková, and Jiri Dybal
    Potential and limitations of 2D 1H-1H spin-exchange CRAMPS experiments to characterize structures of organic solids,
    Monatsh. Chem. 133, 1587-1612 (2002).
    Abstract
     

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Vanadium-51
Xenon-131
Zinc-67
Zirconium-91



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