Selective INEPT
G. Pearson (gpearson@blue.weeg.uiowa.edu)
Tue, 23 Jul 1996 16:46:25 -0500
FWIW, here is a copy of my pulse program to do selective INEPT on a WM-360
with Aspect 2000 with 3-clock timer and on an AC-300 with Aspect 3000 with
process controller. I also have some suggestions for setup & pulse
calibration. The pulse program should work OK on any WM, AM, or AC
spectrometer with either Aspect 2000 or 3000.
I gather that many people do not know how to make the selective INEPT
experiment work on some older Bruker machines, such as WM, AM, and AC, with
Aspect 3000 computers. This is too bad, because it's a good experiment, and
it _CAN_ be done routinely on these instruments.
---------------------------------------------------------------
Gerald A. Pearson INTERNET: gerald-pearson@uiowa.edu
Chem. Dept., Univ. of Iowa OFFICE: 319-335-1336
Iowa City, IA 52242-1219, USA LABS: -1332, -0073 FAX -1270
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From: "G. Pearson" <gpearson@blue.weeg.uiowa.edu>
Date: Fri, 12 Jul 1996 19:18:23 -0500
To: pauli@uni-muenster.de
Subject: Re: Selective INEPT
Cc: center@bruker.com, gerald-pearson@uiowa.edu
Guido Pauli:
^^^^^^^^^^^^
My selective INEPT pulse program works equally well on either an Aspect 3000
with process controller, or an Aspect 2000 with 3-clock timer.
One way to do the pulse calibration is to simply try a series of different
values of P1, and locate where the signal is maximum. The actual value of P1
will be somewhat longer than 3/90 of a single long 90-degree decoupler pulse.
A convenient tune-up sample is acetic acid, transferring magnetization from
the methyl protons to the carbonyl carbon. I forget the exact value of JCH,
but it's only a few Hz.
BRUKER people:
^^^^^^^^^^^^^^
Would you please forward this message to the software people, so they can
make it available to others?
-- Gerry
---------------------------------------------------------------
Gerald A. Pearson INTERNET: gerald-pearson@uiowa.edu
Chem. Dept., Univ. of Iowa OFFICE: 319-335-1336
Iowa City, IA 52242-1219, USA LABS: -1332, -0073 FAX -1270
---------------------------------------------------------------
> From: Guido Pauli <pauli@adonis.uni-muenster.de>
> Newsgroups: sci.techniques.mag-resonance
> Subject: Selective INEPT
> Date: 11 Jul 1996 17:28:41 GMT
>
> Qe: From where can I get the necessary pulse program for Bruker Aspect
> 2000/3000
> (DISNMR) to perform a Selective INEPT? Any help very much appreciated!
>
> ------------------------------------------------------
> Guido Pauli
> Institut fuer Pharmazeutische Biologie und Phytochemie
> 48149 Muenster - Germany
> eMail: pauli@uni-muenster.de
> ------------------------------------------------------
------ FILE: SELINEPT.ACQ
; SELINEPT.ACQ 09-AUG-90 G.A.PEARSON
; CHEM.DEPT., UNIV. OF IOWA, IOWA CITY, IA 52242 USA
; SELECTIVE INEPT, USING WEAK, FREQUENCY-SELECTIVE PROTON PULSE
; TRAINS. OPTIMIZE EXPERIMENT FOR SEEING LONG-RANGE C-H COUPLINGS.
; RE: AD BAX, J.MAGN.RESONANCE 57, 314-318 (1984)
; HARDWARE: AC-300, ASPECT 3000 RUNNING DISR89, PROCESS CONTROLLER,
; LO-POWER DECOUPLER. PULSE TRAINS ARE NEEDED BECAUSE THE
; THE MINIMUM DECOUPLER POWER AVAILABLE (30L) IS STILL TOO
; HIGH (BY 8 DB) TO YIELD THE DESIRED SELECTIVITY WITH THE
; DECOUPLER CONTINUOUSLY ON DURING THE PULSES.
; -- ON OUR OLD WM-360, PULSE TRAINS ARE NEEDED TO AVOID
; SWITCHING BETWEEN THE HIGH- AND LOW-POWER DECOUPLER RANGES
; DURING THE PULSE SEQUENCE. ON THAT HARDWARE, THE SWITCHING
; INVOLVES THE USE OF A MECHANICAL RELAY, SO THE SWITCHING
; WOULD BE UNRELIABLE ON MILLISECOND TIME SCALES AND/OR THE
; RELAY MIGHT WEAR OUT RAPIDLY.
; LAST UPDATED 12-SEPT-90
;====================================================================
;
; 90 180 90 180 BB DECOUPLE
; H-1 -------II--------II-II--------II-----II-II-----##############
; D1 D2 D2 D3 D3
;
; 180 90 180 ACQUIRE FID
; C-13 -------------------I-----------I-------I-------**************
;
;====================================================================
; ------ NOTES ------
; PW = RD = 0
; P1 = PROTON 3-DEGREE (90/30) PULSE -- 8.5 MICROSECONDS ON OUR
; AC-300 WITH THE QUAD PROBE, AND THE DECOUPLER POWER
; SET TO S1 = 0L. -- 4.9 USEC ON OUR WM-360 WITH THE
; 5 MM BB PROBE, AND THE DECOUPLER SET TO S1 = 20H.
; P3, P4 = CARBON 90, 180
; D1 = RELAXATION DELAY.
; D2 = HALF OF PROTON EVOLUTION TIME, MINUS HALF THE SUM OF THE
; WIDTHS OF TWO 45-DEG SOFT PROTON PULSES.
; = 0.25/JCH - ( 15*(D4+P1) + 15*(D5+P1) )
; = 0.25/JCH - 0.0099 SEC.
; D3 = HALF OF C-13 EVOLUTION TIME, MINUS 1/4 OF SOFT PROTON 180.
; [ 1/4 OF SOFT 180 = 15*(P1+D9*(1+0.005*VD)) = 0.0049 SEC. ]
; = 0.250/JCH - 0.0049 SEC FOR METHINE PROTONS
; = 0.125/JCH - 0.0049 FOR METHYLENE PROTONS
; = 0.100/JCH - 0.0049 FOR METHYL PROTONS
; A FEW POSSIBLE SETS OF DELAYS ARE:
; ------- ------ ------- -------- --------
; JCH D2 D3 (CH) D3 (CH2) D3 (CH3)
; ------- ------ ------- -------- --------
; 11 HZ 0.0128 0.0178 0.0065 0,0042
; 9 0.0179 0.0229 0.0090 0.0062
; 7 0.0258 0.0308 0.0130 0.0094
; 5 0.0401 0.0451 0.0201 0.0151
; 4 0.0526 0.0576 0.0264 0.0201
; 3 0.0734 0.0784 0.0368 0.0284
; 2.5 0.0901 0.0951 0.0451 0.0351
; NOTE: IF P1 IS NOT = 8.5 MICROSEC, THEN THESE VALUES FOR
; D2 AND D3 SHOULD BE ADJUSTED SLIGHTLY.
;
; D4 = 0.00034 = 340 USEC PULSE SPACING FOR PROTON 90 PULSE TRAINS.
; D5 = 0.0003 = 300 USEC PULSE SPACING FOR THE FIRST PROTON 180.
; D9 = 0.0003 = 300 USEC MINIMUM PULSE SPACING FOR THE SECOND PROTON
; 180. THIS IS PSEUDO-RANDOMLY VARIED BY 13% BY:
; V9 = 13 -- PERCENT RANDOM VARIATION OF D9.
;
; THIS CHOICE OF D4 & D5 PUTS THE PULSE-TRAIN SIDEBANDS 2869 HZ AND
; 3241 HZ RESPECTIVELY FROM THE PROTON TRANSMITTER, THUS PREVENTING
; SPURIOUS SIGNALS ARISING FROM PROTONS EXCITED BY THE PULSE-TRAIN
; SIDEBANDS. ANY PROTON WHICH SEES A SIDEBAND OF A 90-DEG PULSE IS
; 372.5 HZ OFF-RESONANCE FOR THE FIRST PROTON REFOCUS PULSE, AND
; VICE-VERSA. SINCE A PROTON MUST SEE ALL PULSES IN THE INEPT
; SEQUENCE IN ORDER TO GIVE RISE TO A CARBON SIGNAL, ONLY PROTONS AT
; THE CENTERBAND CAN CONTRIBUTE TO THE SIGNAL. ONE REMAINING
; CONCERN IS THAT A VALID SIGNAL COULD GET ACCIDENTLY WIPED OUT IF
; THE CARBON IS LONG-RANGE COUPLED TO A PROTON WHICH HAPPENS TO SIT
; ON A SIDEBAND OF THE SECOND 180-DEGREE PROTON PULSE TRAIN.
; WE PREVENT SUCH A NASTY COINCIDENCE FROM SERIOUSLY ATTENUATING
; ANY DESIRED SIGNALS BY RANDOMLY VARYING THE SIDEBAND SEPARATION
; BY ABOUT 13%. THIS CAUSES THE SIDEBAND TO MISS THE OFFENDING
; PROTON MOST OF THE TIME.
;
; S1 CHOSEN SO THAT THE INDIVIDUAL PULSES IN THE PULSE TRAINS
; ARE AT LEAST A FEW MICROSECONDS LONG.
; = 0L ON OUR AC-300, TO MINIMIZE OVERSHOOT AND RINGING OF THE
; DECOUPLER-PULSE ENVELOPE.
; = 20H ON OUR WM-360, TO AVOID CHANGING THE DECOUPLER-POWER
; RANGE DURING THE PULSE SEQUENCE.
; S2 = 12H, OR SOME SUCH, TO GIVE GOOD BROADBAND DECOUPLING.
; S3 = DUTY-CYCLE AVERAGE OF DECOUPLER POWER. FOR EXAMPLE,
; IF AQ = 0.8192 AND D1 = 7.37 SEC AND S2 = 12H,
; THEN THE DUTY CYCLE IS AQ / (AQ + D1) = 0.100 = 10.0%, SO
; S3 = 12H - 10 * LOG (AQ/(AQ+D1)) = 12H + 10 DB = 22H
; DP = WHATEVER YOU CALCULATED FOR S3.
; BB SHOULD BE SELECTED TO WARM THE PROBE TO ITS THERMAL STEADY
; STATE BEFORE STARTING THE EXPERIMENT.
; NS = 64 SCANS RECOMMENDED (OR SOME MULTIPLE OF 64, IF YOU MUST)
; DS = 1 DUMMY SCAN RECOMMENDED.
; NE = NUMBER OF DIFFERENT FID'S TO ACQUIRE IN THE EXPERIMENT.
; VC = NUMBER OF TIMES TO INTERLEAVE.
; TOTAL TIME FOR THE EXPERIMENT:
; VC * NE * (ND+DS) * (D1 + AQ + 2*(D2+D3))
; = APPROX. VC * NE * 8.9 MINUTES, USING THE PARAMETERS
; IN THE SELINEPT.JOBP FILE.
;
; R E C O M M E N D A T I O N : SET NS = 64 FOR ALL THE FID'S,
; SET THE VC TO GET A MUCH LONGER EXPERIMENT TIME THAN YOU
; NEED, AND THEN HALT THE EXPERIMENT WITH A CONTROL/H.
;
; BEFORE YOU START THE EXPERIMENT,
; RJ & PJ SELINEPT.JOBP AND THEN II & ZE. THIS IS A STARTING
; SET OF PARAMETERS OPTIMIZED FOR THE QUAD PROBE, A CH3 (METHYL)
; PROTON WITH JCH = 7 HZ, A 7.37-SECOND RELAXATION DELAY (GOOD FOR
; MOST TYPICAL PROTONS), AND NS = 64. WITH THESE PARAMETERS, IT
; TAKES 8.9 MINUTES TO "UPDATE" EACH FID.
; MAKE ANY NECESSARY CHANGES TO THE PARAMETERS, AND STORE NE
; BLANK FID'S ON THE DISK, WITH THE SAME FILENAME, AND EXTENSIONS
; .001, .002, .003, ETC. THE PARAMETERS WILL DIFFER ONLY IN THE
; VALUES FOR O2, D2, AND D3. THEN SET NE = THE NUMBER OF
; FILES. THEN DO A VC AND SET THE NUMBER OF TIMES TO INTERLEAVE.
; LA SELINEPT.ACQ TO GET A LISTING OF THE VALUES OF THE
; AUTOMATION PARAMETERS, TO VERIFY THAT YOU DID EVERYTHING OK
; AU SELINEPT.ACQ TO START THE EXPERIMENT. WHEN THE PROGRAM
; ASKS YOU FOR A FILENAME, TYPE IN THE NAME OF THE BLANK FID'S
; WHICH YOU'VE JUST STORED, WITHOUT ANY EXTENSION.
;==================================================================
;------------------ RESET FILE POINTER FOR EACH INTERLEAVE
10 RF #1.001
;------------- READ THE FID AND SET INSTRUMENT PARAMETERS
20 RE #1
II
CW ; NEEDED TO MAKE SURE THAT THE HARDWARE DOES NOT
; MESS UP THE PULSE SEQUENCE, IN CASE BB IS SET
; IN THE FID FILE. NECESSARY ON OUR AC-300.
; NOT NECESSARY ON OUR WM-360, BUT NOT HARMFUL.
30 D1 S1 DO ; RELAXATION DELAY, DECOUPLER OFF, SET THE
; DECOUPLER POWER FOR SELECTIVE PULSE TRAINS.
;------------- PROTON 90 -- PREPARATION
40 (P1 PH1):D ; THIRTY 3-DEGREE PULSES, SEPARATED BY D4.
D4
LO TO 40 TIMES 30
D2
;------------- "SIMULTANEOUS" CARBON & PROTON 180'S TO REFOCUS
;------------- SHIFTS, BUT LONG-RANGE C-13 COUPLINGS TO THE SELECTED
;------------- PROTON CONTINUE TO EVOLVE TO GIVE ANTI-PARALLEL
;------------- DOUBLETS.
50 (P1 PH2):D
D5
LO TO 50 TIMES 30
P4 PH5 ; C-13 INVERSION
60 (P1 PH2):D
D5
LO TO 60 TIMES 30
D2
;------------ POLARIZATION TRANSFER: SELECTIVE PROTON 90, FOLLOWED
;------------ BY NON-SELECTIVE C-13 90.
70 (P1 PH3):D
D4
LO TO 70 TIMES 30
P3 PH5
D3
;------------- SIMULTANEOUS SOFT PROTON AND HARD C-13 180-DEGREE
;------------- PULSES REFOCUS EVERYTHING EXCEPT SPLITTING DUE TO
;------------- LONG-RANGE COUPLINGS WITH THE SELECTED PROTON.
80 (P1 PH4):D
D9
LO TO 80 TIMES 30
P4 PH5
90 (P1 PH4):D
D9
LO TO 90 TIMES 30
D3 S2 ; PREPARE FOR HIGHER POWER BROADBAND
; PROTON DECOUPLING.
GO=30 PH7 BB ; ACQUIRE C-13 FID WITH BB DECOUPLING.
; N O T E : THIS COULD BE CHANGED TO
; COMPOSITE PULSE DECOUPLING, BY CHANGING
; "BB" TO "CPD". P9 WOULD THEN NEED TO BE
; SET PROPERLY, AND S2, S3, & DP WOULD NEED
; TO BE APPROPRIATELY CHANGED.
D3 S3 ; LOWER DECOUPLER POWER TO DUTY-CYCLE AVERAGE BEFORE
WR #1 ; WRITING THE UPDATED FID BACK TO DISK.
IF #1 ; THEN POINT TO THE NEXT FID,
IN=20 ; AND LOOP BACK TO UPDATE THAT ONE. CONTINUE UNTIL
; ALL NE FID'S HAVE BEEN UPDATED.
LO TO 10 TIMES C ; REPEAT (INTERLEAVE) C ("VC") TIMES
D2 DO
EXIT ;EXIT WITH DEC. OFF
;===================================================================
; ----- PHASE PROGRAMS -----
PH1=B0 B2 ; PROTON PREPARATION
PH2= B0 B0 B1 B1 B2 B2 B3 B3 ; PROTON REFOCUS
PH3= B1 ; POLARIZATION TRANSFER FROM PROTON
PH4= B0 B0 B0 B0 B0 B0 B0 B0 ; PROTON INVERSION
B0 B0 B0 B0 B0 B0 B0 B0
B1 B1 B1 B1 B1 B1 B1 B1
B1 B1 B1 B1 B1 B1 B1 B1
B2 B2 B2 B2 B2 B2 B2 B2
B2 B2 B2 B2 B2 B2 B2 B2
B3 B3 B3 B3 B3 B3 B3 B3
B3 B3 B3 B3 B3 B3 B3 B3
PH5= A0 A0 A0 A0 A1 A1 A1 A1 ; ALL C-13 PULSES
A1 A1 A1 A1 A0 A0 A0 A0
PH7= R0 R2 R2 R0 R1 R3 R3 R1 ; C-13 RECEIVER
R1 R3 R3 R1 R0 R2 R2 R0
;===================================================================
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