;1.6) Program: SPIDER (Saturation-Pulse-Induced Dipolar Exchange with Recoupling) ;Description: Selects C bonded to N ;Requires: !!!!; 1H-14N-13C triple-resonance equipment, 5 kHz MAS ;Reference(s): KSR & Mao, Chem. Phys. Lett. 359, 403-411 (2002); KSR, Mao, Olk, Proc. Nat. ; Acad. Sci. 101, 6351-6354 (2004). ;srspiderech.to (XwinNMR 2.6) ;from srspider.toss ;from ercodexmh.toss ;keep transverse component "alive" during the first "tm" ;of l14*2tr total duration, e.g. l14 = 2 at 5 kHz ;under p14=3u pulse, p24=6u delay 14N pulses ;(cpd3 = srp14dp24.f3) at pl13 = 2 dB ;with fq7 = fq6 Hz Bloch-Siegert shift compensation ;l0 = 6 at 5 kHz for directly bonded ;set p1, p2 (and/or pl11) to maximize the reference intensity ;reduced (64-step) Detlef's phase cycle put in 5-24-2000 ;centerband-only detection of exchange ; with TOSS before detection ;cpd2 = tppm.mh for decoupling (pl12 = 6dB with p18 = 8.2u) ;with multiple power levels (low power CP): ; e.g. 13C CP: pl1 = 8.7 for 3.7u CP, pl11 = 8.3 for 3.4u 90 ; 1H: 90 with pl2 = 5.1; CP with pl3; ;DD during CODEX: pl22; DD during detection: pl12 define delay cd15mp1 define delay cd15m1h define delay cd15mp2 define delay Ltr define delay d29rest "l1=aq/(p8*2)" "p2=2*p1" "d15=0.25s/l31" "cd15mp1=0.25s/l31-p1-3u-2u" "cd15m1h=0.25s/l31-p1-p1/2-2u" "cd15mp2=0.25s/l31-p2-4u" "Ltr=l14*1s/l31-p2/2-p1/2-2u" ;Ltr with 14N pulses "d25=(1s/l31)*0.1226-(p2/2)-2u" ; TOSS DELAYS "d26=(1s/l31)*0.0773-p2" "d27=(1s/l31)*0.2236-p2-4u" "d28=(1s/l31)*1.0433-p2-4u" "d29=(1s/l31)*0.7744-(p2/2)-2u-d13" "d29rest=d29-d14" 1 ze 2 d1 ;recycle delay 10u pl1:f1 ;preselect pl1 drive power level for F1 10u pl2:f2 ;preselect pl2 drive power for F2 10u fq6:f1 ;13C on resonance 1u:f2 ph1 1u:f1 ph2 rpp5 ;reset phase list for xy-8 ; trigpe1 ;record phase p3:f2 ph1 ;proton 90 pulse d19 ;allow time for the phase shift on F2 (p15 ph2):f1 (p15 ph23):f2 ;contact pulse 1u cw:f2 ;turn on F2 decoupling 1u pl22:f2 ;set decoupling drive power level 1u pl11:f1 ;13C power level for pulses cd15mp1 ;tr/4 d15:f1 ph5 ;tr/4 2u pl23:f2 p2:f1 ph5^ ;13C 180 deg. pulse 2u pl22:f2 d15 3 cd15mp2:f1 ph5 2u pl23:f2 p2:f1 ph5^ ;13C 180 deg. pulse 2u pl22:f2 d15 lo to 3 times l0 ;an even number cd15m1h:f1 ph8 pl13:f3 ;preselect pl13 drive power level for F3 ;tr/4 p1:f1 ph8 ;z- and transverse period (used to be tm) 2u cpd3:f3 fq7:f1 ;pulses on 14N (srp14dp24.f3) to make Nz tranverse ;ca. +80-Hz 13C frequency switch to compensate Bloch-Siegert shift Ltr ;Ltr p2:f1 ph10 ;refocus transverse Ltr 2u do:f3 fq6:f1 p1:f1 ph9 cd15m1h pl14:f3 ;tr/4 pl14=120 dB to switch off 14N power 4 d15:f1 ph5 2u pl23:f2 p2:f1 ph5^ ;13C 180 deg. pulse 2u pl22:f2 cd15mp2 lo to 4 times l0 ;an even number d15:f1 ph5 ;tr/4 2u pl23:f2 p2:f1 ph5^ ;13C 180 deg. pulse 2u pl22:f2 d15 cd15mp1:f1 ph3 ;tr/4 2u p1:f1 ph3 ; (second) z-filter d16 do:f2 d18 ; delay for gamma integral d18=k*tr/K 2u cpd2:f2 pl12:f2 p1:f1 ph4 d25:f1 ph13 ; TOSS ACQUISITION 2u pl23:f2 p2:f1 ph13 ;180 13C #1 ; 2u pl12:f2 ;d26 is too short for the switch d26:f1 ph14 ; ; 2u pl23:f2 p2:f1 ph14 ;180 13C #2 2u pl12:f2 d27:f1 ph15 ; 2u pl23:f2 p2:f1 ph15 ;180 13C #3 2u pl12:f2 d28:f1 ph16 ; 2u pl23:f2 p2:f1 ph16 ;180 13C #4 2u pl12:f2 d14 do:f2 ;gated decoupling d29rest cpd2:f2 ; 8u:f1 ph0 ;dead time delay, reset RF phase to detect 1u adc ph31 ;start ADC with ph31 signal routing aq ;allow time for data sampling 1m do:f2 ;turn decoupler off rcyc=2 ;do NS scans 10m id18 ;increment d18 by in18 //gamma integral// lo to 2 times l5 12 10m dd18 ;increment d18 by in18 //gamma integral// lo to 12 times l5 wr #0 exit ph0= 0 ;reference phase for detection ph1= +x -x ;1H 90 excitation ph2= +x ;13C CP ph3= -y -y -y -y -y -y -y -y ;store for 2nd z period -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y -y ph4= +y +y -x -x -y -y +x +x ;readout after 2nd z period ph5= +x +y +x +y +y +x +y +x ;xy-8 -x -y -x -y -y -x -y -x ph7= +x +y -x -y ;14N pulses ph8= -y -y -y -y -y -y -y -y ; cosine store for tm -y -y -y -y -y -y -y -y ; cosine -x -x -x -x -x -x -x -x ; sine -x -x -x -x -x -x -x -x ; sine +y +y +y +y +y +y +y +y ;-z cosine +y +y +y +y +y +y +y +y ;-z cosine +x +x +x +x +x +x +x +x ;-z sine +x +x +x +x +x +x +x +x ;-z sine ph9= +y +y +y +y +y +y +y +y ;read-out after tm -y -y -y -y -y -y -y -y +x +x +x +x +x +x +x +x -x -x -x -x -x -x -x -x +y +y +y +y +y +y +y +y ;read-out after tm -y -y -y -y -y -y -y -y +x +x +x +x +x +x +x +x -x -x -x -x -x -x -x -x ph10=+x +x +x +x +x +x +x +x ;180 to refocus transverse +y +y +y +y +y +y +y +y ;compare ph9 in detail -y -y -y -y -y -y -y -y -x -x -x -x -x -x -x -x +y +y +y +y +y +y +y +y ;compare ph9 in detail +x +x +x +x +x +x +x +x -x -x -x -x -x -x -x -x -y -y -y -y -y -y -y -y ph13=+y +y -x -x -y -y +x +x ;180 13C #1; TOSS ACQ ph14=-y -y +x +x +y +y -x -x ;180 13C #2 ph15=+y +y -x -x -y -y +x +x ;180 13C #3 -y -y +x +x +y +y -x -x ph16=-x -x +y +y +x +x -y -y ;180 13C #4 +x +x -y -y -x -x +y +y ph23=+y ;1H CP ph31= 0 2 1 3 2 0 3 1 ;Receiver phase 2 0 3 1 0 2 1 3 0 2 1 3 2 0 3 1 2 0 3 1 0 2 1 3 2 0 3 1 0 2 1 3 0 2 1 3 2 0 3 1 2 0 3 1 0 2 1 3 0 2 1 3 2 0 3 1