Z-filter pulse program from Bruker for 3QMAS of half-integer spin quadrupole nuclei
Z-filter pulse program from Bruker for 3QMAS of half-integer spin quadrupole nuclei
Below NMR pulse program describes the z-filter approach for (1D and 2D) +3Q-MAS experiment applied to quadrupolar nuclei with half-integer spin.
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.
; 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
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.
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 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 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 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 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 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 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.
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.
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 |