FMP Berlin, N

MR facility

Spektometerblätter

21.01.2016

www.fmp-berlin.de/schm

ieder/nmr_stuff.htm

spectrum referencing,

SR/SF-values from D

SS

spectrum referencing,

SR/SF-values from D

SS

temperature calibration using methanol

TBVT : 280, 285, 290, 295, 300, 305, 310, 315, 320 [K]

= (OH) - (CH3)

Treal [K] = 403 - 29.53- 23.87 ()2

[ppm] T [K]

1.73 280

1.64 290

1.55 300

1.45 310

1.35 320

temperature calibration using methanol

Linear fitting of T(BVT) vs. T(real) and vice versa

results in two calibration curves

temperature calibrationfmp600 RT-QXI (Z8654/0007), 03.04.2013

Treal = -17.307 + 1.0589 x TBVT

300 K at BVT is 300.36 K

TBVT = 16.344 + 0.9444 x Treal

300 K: set BVT to 299.66 K

Treal = 9.337 + 0.96 x TBVT

300 K at BVT is 297.34 K

TBVT = -9.726 + 1.0417 x Treal

300 K: set BVT to 302.78 K

Treal = 8.6678 + 0.9488 x TBVT

300 K at BVT is 293.31 K

TBVT = -9.136 + 1,0540 x Treal

300 K: set BVT to 307.06 K

psf600 CP-TXI (Z44866/0019), 08.04.2013

sel600 CP-TCI (Z75812/0039), 09.04.2013

Treal = -21.561 + 1.0736 x TBVT

300 K at BVT is 300.52 K

TBVT = 20.083 + 0.9314 x Treal

300 K: set BVT to 299.50 K

RT-BBFO (Z114607/0090), 02.04.2013

temperature calibration

av750 CP-TCI (Z44915/0001), 17.04.2013

Treal = 7,9615 + 0.9505 x TBVT

300 K at BVT is 293.11 K

TBVT = -8.376 + 1.0521 x Treal

300 K: set BVT to 307.25 K

Treal = 5.6765 + 0.9709 x TBVT

300 K at BVT is 296.95 K

TBVT = -5.8466 + 1.03 x Treal

300 K: set BVT to 303.15 K

RT-TXI (Z8344/0003), 23.08.2011Treal = 0.0 + 1.00 x TBVT

300 K at BVT is 300.00 K

TBVT = 0.0 + 1.0 x Treal

300 K: set BVT to 300.00 K

av900 CP-TCI (Z44910/0015), 11.04.2013

carrier-values for protons

o1

400 MHz 1880 Hz

600 MHz 2820 Hz

700 MHz 3280 Hz

750 MHz 3520 Hz

900 MHz 4230 Hz

carrier-values for nitrogens

o3

400 (40) MHz 4850 Hz

600 (60) MHz 7250 Hz

700 (70) MHz 8400 Hz

750 (76) MHz 9000 Hz

900 (91) MHz 11000 Hz

carrier-values for deuterium

o4

400 MHz 210 Hz

600 MHz 320 Hz

700 MHz 370 Hz

750 MHz 400 Hz

900 MHz 480 Hz

carrier-values for carbon

17000 11500 5500 40004500

center of CO region ~175 ppm

7000

center of aliphaticregion ~40 ppm

center of Cregion ~45 ppm

center for decoupling ~70 ppm

400 MHz (100 MHz)

center for HMBC~100 ppm

center of Cregion ~55 ppm

composite pulse CO/C ~115 ppm

10000

carrier-values for carbon

26000 17000 8000 58006500

center of CO region ~175 ppm

10250

center of aliphaticregion ~40 ppm

center of Cregion ~45 ppm

center for decoupling ~70 ppm

600 MHz (150 MHz)

center for HMBC~100 ppm

center of Cregion ~55 ppm

14750

composite pulse CO/C ~115 ppm

carrier-values for carbon

30750 20250 9750 70008000

center of CO region ~175 ppm

12250

center of aliphaticregion ~40 ppm

center of Cregion ~45 ppm

center for decoupling ~70 ppm

700 MHz (175 MHz)

center for HMBC~100 ppm

center of Cregion ~55 ppm

17500

composite pulse CO/C ~115 ppm

carrier-values for carbon

32500 21250 10000 76008125

center of CO region ~175 ppm

12800

center of aliphaticregion ~40 ppm

center of Cregion ~45 ppm

center for decoupling ~70 ppm

750 MHz (188 MHz)

center for HMBC~100 ppm

center of Cregion ~55 ppm

18500

composite pulse CO/C ~115 ppm

carrier-values for carbon

38800 25400 11800 84009600

center of CO region ~175 ppm

15200

center of aliphaticregion ~40 ppm

center of Cregion ~45 ppm

center for decoupling ~70 ppm

900 MHz (225 MHz)

center for HMBC~100 ppm

center of Cregion ~55 ppm

22000

composite pulse CO/C ~115 ppm

400 MHz 600 MHz 700 MHz 750 MHz 900 MHz

(C,CO)120 ppm

12000 Hz 18000 Hz 21000 Hz 22500 Hz 27000 Hz

(C,CO)130 ppm

13000 Hz 19500 Hz 22750 Hz 24375 Hz 29200 Hz

B1 p B1 p B1 p B1 p B1 p

90°, 120 ppm n=1 3.1 81 4.7 54 5.4 46 5.8 43 7.0 36

90°, 130 ppm n=1 3.3 75 5.0 49 5.9 43 6.3 40 7.6 33

180°, 120 ppm n=1 6.9 72 10.4 48 12.1 41 13.0 38 15.6 32

n=2 3.1 162 4.7 108 5.4 92 5.8 86 7.0 72

180°, 130 ppm n=1 7.5 67 11.3 44 13.1 38 14.0 35 16.9 30

n=2 3.3 150 5.0 98 5.9 86 6.3 80 7.6 66

Semi-selective rectangular pulses

Semi-selective rectangular pulses

center CO-region at 175 ppmcenter C-region at 55 ppmcenter C-region at 45 ppm

90° pulses1.null (n=1) at B1 = / 15180° pulses1.null (n=1) at B1 = / 32.null (n=2) at B1 = / 15

eff [°]

/ B1

3 15 = 90° = 180°

J coupling constants in proteins

90 Hz

55 Hz 15 Hz

35 Hz11 Hz

7 Hz

140 HzH

HR

H H

CC

C

O

O

N

HC

R

N

H

CC

phc1 = (t1)0 * sw * (-360°)

phc0 = -0.5 * phc1(t1)0 first value for evolution time (including pulses)

Two scenarios are desirable1. phc1 = 0°, phc0 = 0°, first point multiplied by 0.5

folded peaks have same sign as unfolded 2. phc1 = -180°, phc0 = 90°, first point multiplied by 1

folded peaks have opposite sign as unfolded If that is not possible try to achieve phc1 = n * (-360°) and phc0 = n * 180°and use linear prediction to get back to 1. or 2.

Phase correction in the indirect dimension

Phase correction in the indirect dimension“homonuclear spectra”

H90x 90x

t1

p1 p1d0

px

= (2/px

“d0 = n*(in0/2) – 1.28*p1”

phc1 = -360°*[(d0 + 1.28*p1)/in0]

phc0 = -½*phc1

px

Phase correction in the indirect dimension“heteronuclear spectra”

px

= (2/px

“d0 = (n*in0 – 1.28*p1 – p4) /2” phc1 = -180°*[(2*d0 + 1.28*p1 + p4)/in0]

phc0 = -½*phc1

px

H

X

90x 90x

180x

t1/2 t1/2

p1 p1d0 d0

p4

SHared Incrementation Times (SHIT)

H

X

90x 90x

180x

t1a

180x

t1b t1

c

(t1a)0 = /2, t1

a = 1/(2*sw)(t1

b)0 = 0, t1b = t1

a + t1c

(t1c)0 = /2, t1

c = -/2(n-1)

= 1/2J, t1x = increment

(t1x)0 = first value

n number of complex datapoints

sw t1a t1

b(32) t1c(32) t1

b(48) t1c(48) t1

b(64) t1c(64)

3012 166 110 -56 129 -37 139 -27

4000 125 69 -56 88 -37 98 -27

5000 100 44 -56 63 -37 73 -27

6250 80 24 -56 43 -37 53 -27

8333 60 4 -56 23 -37 33 -27

10000 50 0 -50 13 -37 23 -27

sw t1a t1

b(32) t1c(32) t1

b(48) t1c(48) t1

b(64) t1c(64)

3012 166 78 -88 108 -58 123 -43

4000 125 37 -88 67 -58 82 -43

5000 100 12 -88 42 -58 57 -43

6250 80 0 -80 22 -58 37 -43

8333 60 0 -80 2 -58 17 -43

10000 50 0 -80 0 -50 7 -43

= 3.5 msec = 5.5 msec

dB-calculations, pulses correspond to voltage

voltage to power

P(W) =[U(VP-P)]2

400

NMR solvents

Productoperators: calculation

rules(1)

Productoperators: calculation

rules(2)

Product operators: trigonometry

NMR-Facility ( Räume NMR-I)

D1.01D1.04

D1.03

D1.02

D1.05/6

D1.07

NMR-Facility ( Räume NMR-II)

E 1.09

E 1.06

E 1.05

E 1.02

E 1.03

E 1.10

E 1.01

E 1.08

E 1.07

E 1.12

E 1.11

NMR-Facility (Spektrometer)

Spektrometer Raum Tel Netzwerk HH-Nummer Datendisk

AV 300 TRH 3.34 (70)2916 av300.mdc-berlin.de(141.80.190.56) HH007604 /r

AV 400 WB (MRI) B 0.03/04 529 (528) (mri-)av400.fmp-berlin.de (194.95.129.217/(236)) HH005102 /z

AV 400 WB (DNP) E 1.12 546 (549) av400dnp.fmp-berlin.de(194.95.129.228) HH004106 /q

AV 600 (FMP) D 1.04 533 fmp600.fmp-berlin.de(194.95.129.211) 10063006 /x

AV 600 (PSF) D 1.05/06 534 psf600.fmp-berlin.de(194.95.129.235) 10012991 /v

AV 600 (SEL) D 1.02 531 sel600.fmp-berlin.de(194.95.129.234) HH002008 /p

AV 600 WB E 1.06 541 (542) av600.fmp-berlin.de(194.95.129.230) HH001802 /y

AV 700 WB E 1.06 540 (545) av700.fmp-berlin.de(194.95.129.233) HH005904 /s

AV750 D 1.07 532 fmp750.fmp-berlin.de(194.95.129.215) HH009806 /w

AV800 E 1.11 547 (548) av800.fmp-berlin.de(194.95.129.212) 10062996 /m

AV 900 E 1.07-09 540 (543,544) av900.fmp-berlin.de(194.95.129.231) HH005701 /t

NMR-Spektrometer