Z-filter pulse program from Bruker for 3QMAS of half-integer spin quadrupole nuclei

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Below NMR pulse program describes the z-filter approach for (1D and 2D) +3Q-MAS experiment applied to quadrupolar nuclei with half-integer spin.

Z-filter 3QMAS sequence and coherence transfer pathway for a spin I = 3/2

Fig. 1: Z-filter 3QMAS NMR pulse sequence and coherence transfer pathway.
The echo amplitude and the antiecho amplitude have the same sign.
The phase cyling for 3 strong pulses is discussed.

This NMR pulse program is for Bruker Avance spectrometers.

A pure absorption 2D spectrum is obtained with the shearing transformation.

Code for Avance III spectrometers

; mp3qzqf

; 3Q MAS pulse program for half-integer spin nuclei 
; 3-pulse experiment with zero quantum filter: 
; excitation(±3Q) - conversion(0Q) - tau - 90° selective - ACQ(-1Q) 
; 90° selective pulse should be determined first using Hahn-echo, 
; determination by single pulse excitation is also possible 
; Then optimise P2 and finally P1, 2 or more iterations for P1 and P2 
; may be needed.
; For processing shearing transformation may be requested,
; use AU program xfshear

;ns :  12*n
;d1 :  recycle delay
;p1 :  excitation pulse at pl11
;p2 :  conversion pulse at pl11
;p3 :  90 degree selective pulse at pl21
;pl1 :  = 120 db
;pl11 : power level for excitation and conversion pulses
;pl21 : power level for 180 degree selective pulse, ca. pl11 + 30 db
;d4 :  z-filter delay
;d0  : = 1u or longer
;in0 : 1 rotor period for synchronised experiment
;td1 : number of t1-experiments
;FnMODE : States
;MC2 : States

  ze                  ; clear memory, new data replace old data,
                      ; switch AD converter to replace mode,
                      ; perform DS before next acquisition,
1 d1                  ; recycle delay,
  10u pl11:f1         ; 10 microsecond delay,
                      ; set high power in f1 channel,
  (p1 ph1):f1         ; high-power excitation pulse,
  d0                  ; delay between pulses, t1 increment,
  (p2 ph2):f1         ; high-power conversion pulse,
  d4 pl21:f1          ; set low power in f1 channel,
  (p3 ph3):f1         ; low-power 90° pulse,
  go=1 ph31           ; signal acquisition,
                      ; loop to 1, ns times for averaging,
  d1 mc #0 to 1 F1PH(ip1, id0)
                      ; delay for disk I/O, store signal,
                      ; increase FID number,
                      ; delete memory data,
                      ; do not perform dummy scans
                      ; with next acquisition,
                      ; increment p1 pulse phase by 360°/12 for States procedure,
                        ; loop to 1, 1 time for States procedure,
                      ; increment time d0 by in0,
                        ; loop to 1, td1/2 time for 2D experiment
  exit                ; end of the pulse program

ph1=(12) 0                        ; excitation pulse phase
ph2=(6)  0 0 1 1 2 2 3 3 4 4 5 5  ; conversion pulse phase
ph3=     0 2                      ; 90° selective pulse phase
ph0=     0
ph31=    0 2 2 0                  ; receiver phase
  

If the third pulse must be a strong RF pulse for better excitation of off-resonance nuclei, the phase cyclings of ph1, ph2, ph3, and ph31 should be the following for spin I = 3/2. However, there is no harm in applying these phase cyclings concerning 3-strong pulse sequence even when the third pulse is a weak RF pulse.

; ns: 24*n
; pl21 = pl11
ph1=(12) 0 2 4 6 8 10               ; excitation pulse phase
ph2=     0                          ; conversion pulse phase
ph3=(4)  0 0 0 0 0 0  1 1 1 1 1 1 
         2 2 2 2 2 2  3 3 3 3 3 3   ; 90° pulse phase
ph0=     0
ph31=    0 2 0 2 0 2  1 3 1 3 1 3 
         2 0 2 0 2 0  3 1 3 1 3 1   ; receiver phase
  

Example: LZY-84 zeolite

90° pulse duration of 27Al in solution with zg

27Al spectra of reference solution versus the excitation pulse p1 duration (pl1 = 0.5 dB) in zg pulse program, acquired with a 4-mm diameter rotor, D1 = 1 sec recycle delay, and recorded with Bruker Avance III, 500 MHz WB US magnet.

90° pulse duration of 27Al in solution with zg with low power

27Al spectra of reference solution versus the excitation pulse p1 duration (pl1 = 24 dB) in zg pulse program.

Pulseprogram parameters for zg:

General  
PULPROG zg
TD 4604
NS 8
DS 0
SWH [Hz] 20000.00
AQ [s] 0.1151500
RG 128
DW [µs] 25.000
DE [µs] 6.50
D1 [s] 1.00000000
TD0 1
Channel f1  
NUC1 27Al
P1 [µs] 3.50
PL1 [dB] 0.50
PL1W [W] 234.39410400
SFO1 [MHz] 130.3270545

27Al FID of LZY84 zeolite

27Al MAS FID of LZY-84 zeolite, acquired with a 4-mm diameter rotor spinning at 15 kHz, D1 = 0.2 sec recycle delay, and recorded with Bruker Avance III, 500 MHz.

27Al spectrum of LZY84 zeolite

27Al MAS spectrum of LZY-84 zeolite, acquired with a 4-mm diameter rotor spinning at 15 kHz, D1 = 0.2 sec recycle delay, and recorded with Bruker Avance III, 500 MHz.

Pulseprogram parameters for zg:

General  
PULPROG zg
TD 4604
NS 24
DS 0
SWH [Hz] 50000.00
AQ [s] 0.0460900
RG 64
DW [µs] 10.000
DE [µs] 6.50
D1 [s] 0.20000000
TD0 1
Channel f1  
NUC1 27Al
P1 [µs] 2.00
PL1 [dB] 0.50
PL1W [W] 234.39410400
SFO1 [MHz] 130.3311212

27Al spectra of LZY84 zeolite versus the excitation pulse p2 duration

27Al MAS spectra of LZY-84 zeolite versus the excitation pulse p2 duration (pl11 = 0.5 dB) in mp3qzqf pulse program, acquired with a 4-mm diameter rotor spinning at 15 kHz, D1 = 0.2 sec recycle delay, and recorded with Bruker Avance III, 500 MHz.

Pulseprogram parameters for mp3qzqf:

General  
PULPROG mp3qzqf
TD 4604
NS 120
DS 0
SWH [Hz] 50000.00
AQ [s] 0.0460900
RG 64
DW [µs] 10.000
DE [µs] 6.50
CNST11 0.0000000
D0 [s] 0.00000300
D1 [s] 0.20000000
D4 0.00002000
Channel f1  
NUC1 27Al
P1 [µs] 5.00
P2 [µs] 2.00
P3 [µs] 16.00
PL1 [dB] 120
PL1W [W] 0.00000000
PL11 [dB] 0.50
PL11W [W] 234.39410400
PL21 [dB] 18.00
PL21W [W] 4.16818190
SFO1 [MHz] 130.3311212

27Al spectra of LZY84 zeolite versus the excitation pulse p1 duration

27Al MAS spectra of LZY-84 zeolite versus the excitation pulse p1 duration (pl11 = 0.5 dB) in mp3qzqf pulse program.

Pulseprogram parameters for mp3qzqf:

General  
PULPROG mp3qzqf
TD 4604
NS 120
DS 0
SWH [Hz] 50000.00
AQ [s] 0.0460900
RG 64
DW [µs] 10.000
DE [µs] 6.50
CNST11 0.0000000
D0 [s] 0.00000300
D1 [s] 0.20000000
D4 0.00002000
Channel f1  
NUC1 27Al
P1 [µs] 6.00
P2 [µs] 2.00
P3 [µs] 16.00
PL1 [dB] 120
PL1W [W] 0.00000000
PL11 [dB] 0.50
PL11W [W] 234.39410400
PL21 [dB] 18.00
PL21W [W] 4.16818190
SFO1 [MHz] 130.3311212

27Al spectra of LZY84 zeolite versus the excitation pulse p3 duration

27Al MAS spectra of LZY-84 zeolite versus the excitation pulse p3 duration (pl21 = 24 dB) in mp3qzqf pulse program.

Pulseprogram parameters for mp3qzqf:

General  
PULPROG mp3qzqf
TD 4604
NS 120
DS 0
SWH [Hz] 50000.00
AQ [s] 0.0460900
RG 64
DW [µs] 10.000
DE [µs] 6.50
CNST11 0.0000000
D0 [s] 0.00000300
D1 [s] 0.20000000
D4 0.00002000
Channel f1  
NUC1 27Al
P1 [µs] 6.00
P2 [µs] 2.00
P3 [µs] 18.00
PL1 [dB] 120
PL1W [W] 0.00000000
PL11 [dB] 0.50
PL11W [W] 234.39410400
PL21 [dB] 24.00
PL21W [W] 1.04700005
SFO1 [MHz] 130.3311212

27Al 3QMAS FID of LZY84 zeolite

27Al 3QMAS series of FID of LZY-84 zeolite acquired with a 4-mm diameter rotor spinning at 15 kHz, D1 = 0.2 sec recycle delay, and recorded with Bruker Avance III, 500 MHz.

27Al 3QMAS spectrum of LZY84 zeolite

Xfsheared 27Al 3QMAS spectrum of LZY-84 zeolite acquired with a 4-mm diameter rotor spinning at 15 kHz, D1 = 0.2 sec recycle delay, and recorded with Bruker Avance III, 500 MHz.

27Al 3QMAS spectrum of LZY84 zeolite

Zoomed 27Al 3QMAS spectrum of LZY-84 zeolite.

Pulseprogram parameters for mp3qzqf:

General  
PULPROG mp3qzqf
TD 4604
NS 120
DS 0
SWH [Hz] 50000.00
AQ [s] 0.0460900
RG 64
DW [µs] 10.000
DE [µs] 6.50
CNST11 0.0000000
D0 [s] 0.00000300
D1 [s] 0.20000000
D4 0.00002000
IN0 [s] 0.00002000
ST1CNT 128
Channel f1  
NUC1 27Al
P1 [µs] 6.00
P2 [µs] 2.00
P3 [µs] 18.00
PL1 [dB] 120
PL1W [W] 0.00000000
PL11 [dB] 0.50
PL11W [W] 234.39410400
PL21 [dB] 24.00
PL21W [W] 1.04700005
SFO1 [MHz] 130.3311212

Acquisition parameters:

  F2 F1
Experiment    
PULPROG mp3qzqf  
AQ_mod DQD  
FnMODE   States
TD 4608 256
NS 128  
DS 0  
TD0 1  
Width    
SW [ppm] 383.6382 383.6382
SWH [Hz] 50000.000 50000.000
IN_F [µs]   20.00
AQ [s] 0.0460900 0.0025600
Nucleus1    
NUC1 27Al  
O1 [Hz] 2529.25 2529.25
O1P [ppm] 19.407 19.407
SFO1 [MHz] 130.3311212 130.3311212
BF1 [MHz] 130.3285920 130.3285920

Processing parameters:

  F2 F1
Reference    
SI 2048 512
SF [MHz] 130.3270970 184.6300540
OFFSET [ppm] 222.70329 166.28419
SR [Hz] -1495.03 -2117.96
Window Function    
WDW EM QSINE
LB [Hz] 20.00 30.00
SSB 0 3
Nucleus1    
Fourier transform    
TDeff 512 160

Solid-state NMR bibliography for:

Aluminum-27
Antimony-121/123
Arsenic-75
Barium-135/137
Beryllium-9
Bismuth-209
Boron-11
Bromine-79/81
Calcium-43
Cesium-133
Chlorine-35/37
Chromium-53
Cobalt-59
Copper-63/65
Deuterium-2
Gallium-69/71
Germanium-73
Gold-197
Hafnium-177/179
Indium-113/115
Iodine-127
Iridium-191/193
Krypton-83
Lanthanum-139
Lithium-7
Magnesium-25
Manganese-55
Mercury-201
Molybdenum-95/97
Neon-21
Nickel-61
Niobium-93
Nitrogen-14
Osmium-189
Oxygen-17
Palladium-105
Potassium-39/41
Rhenium-185/187
Rubidium-85/87
Ruthenium-99/101
Scandium-45
Sodium-23
Strontium-87
Sulfur-33
Tantalum-181
Titanium-47/49
Vanadium-51
Xenon-131
Zinc-67
Zirconium-91
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