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

*** Outline ***

• Code for Avance III spectrometers with topSpin2.1 operating system
• Example: ¹H in L-Tyrosine.HCl with AV700
• References

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