; SRI-FESTA experiment ; ; Doubly selective refocused INEPT - TOCSY (19F - 1H correlation and 1H-1H TOCSY transfer) ; using selective 90 19F pulse for excitation ; using selective 180 19F pulse for refocusing (optional) ; using selective 180 1H pulse for refocusing ; using PFG for CTP selection ; homonuclear Hartman-Hahn transfer using DIPSI2 sequence for mixing with zero quantum suppression (optional) ; For QNP-operation (F-19 via X-QNP output of switchbox) ; ; Developed by: ; NMR Methodology Group ; University of Manchester ; ; L. Castaņar, P. Moutzouri, T. Barbosa, C. Tormena, R. Rittner, A. Phillips, S. Coombes, M. Nilsson, G. A. Morris. ; Anal. Chem., 2018, 90, 8, 5445-5450 ; DOI: 10.1021/acs.analchem.8b00753 ; ; Options: ; [cnst1 = 0] without 1H purge pulses before d1 ; [cnst1 = 1] with 1H purge pulses before d1 ; [cnst5 = 0] with 180 19F hard pulses ; [cnst5 = 1] with 180 19F selective pulses ; [cnst6 = 0] without TOCSY (SRI-SME) ; [cnst6 = 1] with TOCSY (SRI-FESTA) ;$CLASS=HighRes ;$DIM=1D ;$TYPE= ;$SUBTYPE= ;$COMMENT= #include #include #include "d2=1s/(cnst2*4*cnst3)" "d3=1s/(cnst2*4*cnst4)" "d13 = 20u" "d16 = 200u" "cnst10=2/3.1415" "DELTA1=d2-p16-d16-d13-(p3*cnst10)" "DELTA2=d2-d13-(p3*cnst10)-2*p16-2*d16" "DELTA3=d3-p16-d16-(p3*cnst10)-d13" "DELTA4=d3-d13-(p3*cnst10)-2*d16-2*p16" "DELTA11=d2-p16-d16-(p11*cnst10)-d13" "DELTA12=d2-d13-(p11*cnst10)-2*p16-2*d16" "DELTA13=d3-p16-d16-(p11*cnst10)-d13" "DELTA14=d3-d13-(p11*cnst10)-2*d16-2*p16" "p2=p1*2" "p4=p3*2" "spoff11=0" "spoff12=bf1*(cnst12/1000000)-o1" "spoff15=0" "spoff29=0" "FACTOR1=(d9/(p6*115.112))/2" "l1=FACTOR1*2" "acqt0=-p1*2/3.1416" 1 ze d13 QNP_X 30m pl12:f2 2 30m do:f2 d13 BLKGRAD if "cnst1 == 1" ;Purge pulses { d13 UNBLKGRAD d13 SWITO_H d13 pl1:f1 p16:gp20 d16 (p1 ph20):f1 (p1 ph21):f1 p16:gp21 d16 d13 BLKGRAD } else { } d1 ;F - H AP transfer d13 UNBLKGRAD d13 SWITO_F d13 pl0:f2 (p11:sp11 ph1):f2 if "cnst5==0" { DELTA1 p16:gp5 d16 pl2:f2 (p3 ph3):f2 d13 SWITO_H pl0:f1 (p12:sp12 ph2):f1 d13 SWITO_F pl2:f2 (p3 ph3):f2 p16:gp5 d16 DELTA2 p16:gp1 d16 } else { DELTA11 p16:gp5 d16 pl0:f2 (p11:sp11 ph3 ):f2 d13 SWITO_H pl0:f1 (p12:sp12 ph2):f1 d13 SWITO_F pl0:f2 (p11:sp11 ph3 ):f2 p16:gp5 d16 DELTA12 p16:gp1 d16 } d13 pl2:f2 pl1:f1 (p3 ph4):f2 p16:gp2 d16 SWITO_H (p1 ph5):f1 if "cnst5==0" { DELTA3 ;IP transfer p16:gp3 d16 SWITO_F pl2:f2 (p3 ph7):f2 d13 SWITO_H pl0:f1 (p12:sp12 ph6) :f1 d13 SWITO_F pl2:f2 (p3 ph7):f2 p16:gp3 d16 DELTA4 p16:gp1*0.9407 d16 } else { DELTA13 ;IP transfer p16:gp3 d16 SWITO_F pl0:f2 (p11:sp11 ph7):f2 d13 SWITO_H pl0:f1 (p12:sp12 ph6):f1 d13 SWITO_F pl0:f2 (p11:sp11 ph7):f2 p16:gp3 d16 DELTA14 p16:gp1*0.9407 d16 } if "cnst6 == 1" ;TOCSY block with ZQF { d13 SWITO_H pl1:f1 (p1 ph8):f1 10u gron0 pl0:f1 (p32:sp29 ph9):f1 10u groff d16 pl10:f1 ;begin DIPSI2 4 p6*3.556 ph23 p6*4.556 ph25 p6*3.222 ph23 p6*3.167 ph25 p6*0.333 ph23 p6*2.722 ph25 p6*4.167 ph23 p6*2.944 ph25 p6*4.111 ph23 p6*3.556 ph25 p6*4.556 ph23 p6*3.222 ph25 p6*3.167 ph23 p6*0.333 ph25 p6*2.722 ph23 p6*4.167 ph25 p6*2.944 ph23 p6*4.111 ph25 p6*3.556 ph25 p6*4.556 ph23 p6*3.222 ph25 p6*3.167 ph23 p6*0.333 ph25 p6*2.722 ph23 p6*4.167 ph25 p6*2.944 ph23 p6*4.111 ph25 p6*3.556 ph23 p6*4.556 ph25 p6*3.222 ph23 p6*3.167 ph25 p6*0.333 ph23 p6*2.722 ph25 p6*4.167 ph23 p6*2.944 ph25 p6*4.111 ph23 lo to 4 times l1 ;end DIPSI2 p16:gp4 d16 pl0:f1 10u gron0*1.333 (p32*0.75:sp29 ph9):f1 10u groff d16 pl1:f1 (p1 ph10):f1 } else { } d13 SWITO_F pl12:f2 go=2 ph31 cpd2:f2 30m do:f2 mc #0 to 2 F0(zd) d13 BLKGRAD exit ph1=0 2 2 0 ph2=0 ph3=0 ph4=1 ph5=0 ph6=0 ph7=0 ph8=1 ph9=0 ph10=0 ph20=0 ph21=1 ph23=3 ph25=1 ph31=0 2 2 0 ;POWER LEVEL ;pl0 : zero power (0 W) ;pl1 : f1 channel - power level for pulse (default) ;pl2 : f2 channel - power level for pulse (default) ;pl10 : f1 channel - power level for TOCSY-spinlock ;pl12 : f2 channel - power level for CPD/BB decoupling ;sp11 : f2 channel - power level of excitation shaped pulse ;sp12 : f1 channel - power level of refocusing shaped pulse ;sp12 : f2 channel - power level of refocusing shaped pulse ;sp29 : f1 channel - power level of adiabatic pulse of ZQF element ;PULSE DURATION ;p1 : f1 channel - 90 degree high power pulse ;p2 : f1 channel - 180 degree high power pulse ;p3 : f2 channel - 90 degree high power pulse ;p4 : f2 channel - 180 degree high power pulse ;p6 : f1 channel - 90 degree low power pulse for DIPSI element ;p11: f2 channel - 90 degree low power shaped pulse ; choose p11 according to desired selectivity ;p12: f1 channel - 180 degree low power shaped pulse ; choose p12 according to desired selectivity ;p13: f2 channel - 180 degree low power shaped pulse ; choose p13 according to desired selectivity ;p32: f1 channel - 180 degree shaped pulse (adiabatic) [20 msec] ;GRADIENT DURATION ;p16: duration of CTP gradients [0.8 msec] ;DELAY ;d1 : relaxation delay; 1-5 * T1 ;d2 : 1/(nH*4*J(XH)) ;d3 : 1/(nF*4*J(XH)) ;d9 : TOCSY mixing time ;d12: delay for QNP switch [20 usec] ;d13: delay for power switch [20 usec] ;d16: delay for gradient recovery [200 usec] ;PULSE SHAPE ;spnam11 : f2 channel - file name for the selective 90 exciation shaped pulse [Gauss] ;spnam12 : f1 channel - file name for the selective 180 refocusing shaped pulse [Rsnob] ;spnam13 : f2 channel - file name for the selective 180 refocusing shaped pulse [Rsnob] ;spnam29 : f1 channel - file name for the adiabatic shaped pulse using in ZQF [Crp60,20,20.10] ; smoothed chirp (sweepwidth, 20% smoothing, 10000 points) ;GRADIENT SHAPE ;gpnam1 : SMSQ10.100 ;gpnam2 : SMSQ10.100 ;gpnam3 : SMSQ10.100 ;gpnam4 : SMSQ10.100 ;gpnam5 : SMSQ10.100 ;gpnam20: SMSQ10.100 ;gpnam21: SMSQ10.100 ;GRADIENT STRENGTH ;gpz0 : ZQF gradient [3%] ;gpz1 : F-H CTP gradient [47%] ;gpz2 : homospoil gradient [37%] ;gpz3 : 180 1H CTP gradient [41%] ;gpz4 : homospoil gradient TOCSY [17%] ;gpz5 : 180 1H CTP gradient [33%] ;gpz20 : homospoil gradient purge pulses [53%] ;gpz21 : homospoil gradient purge pulses [59%] ;CONSTANTS ;cnst1 : 0 (--) / 1 (Purge pulses) ;cnst2 : J(XH) ;cnst3 : number of protons coupled with fluorine ;cnst4 : number of fluorines coupled with protons ;cnst5 : 0 (19F 180 hard pulses) / 1 (19F 180 selective pulses) ;cnst6 : 0 (--) / 1 (ZQF-TOCSY) ;cnst12: chemical shift for selective 1H pulse (offset, in ppm) ;OTHER ;ns: 2 * n, total number of scans: NS * TD0 ;ds: 2 ;set O2 on resonance to the 19F signal of interest ;cpd2: p5m4sp180 ;l1: loop for DIPSI cycle: ((p6*115.112) * l1) = mixing time ;if any DELTA become negative try to reduce the gradient duration or selective pulse duration