2004/03/31

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1 PFG-NMR 004/11/3 006/05/05 PFG calibration Radiation-Damping PGSE-NMR JEOL Hahn NMR Radiation Damping JEOL Einstein NMR NMR NMR NMR (artifact) DOSY Diffusion Ordered Spectroscopy 1

2 NMR University of Western Sydney Prof. W. S. Price STA fellow PFG JEOL JEOL 1997 JEOL 10 T/m (1,000 gauss/cm) PFG 19 F/ 1 H T/m PFG 15 N NMR 1983 JEOL Oxford 4.7T SCM JEOL GSH-00 (1991 ) 1996 TecMag Galaxy-MacNMR 00 TecMag Apollo-NTNMR JEOL JEOL 004 NMR NMR 70MHz SCM(6.3T) 1 H tuning 1 H 19 F tuning Apollo 1 H/ 19 F 10, NMR Dr. W. S. Price discussion

3 .1 Hahn Fick NMR Pulsed-filed Gradient Spin-Echo NMR, PGSE NMR m s -1 5 o C.30x10-9 m s -1 SI.30x10-5 cm s -1 NMR NMR Hahn Hahn PFG Hahn o o - -Echo RF x x y RF 90 y xy xy y T T xy z- RF T1 xy RF x 3

4 x- x xy xy 180 RF ( ) xy -y xy z- z,6 z 1 x z y z y 3 x RF (90 ) z τ z PFG 4 y 5 x RF ( 0 ) τ z PFG y 6 x Hahn 4

5 . Hahn PFG T/m gauss/cm 0.1ms 10ms PFG Hahn PFG Hahn PFG PFG 1 PFG xy z z- z- SCM PFG 180 xy- PFG PFG xy PFG PFG PFG PFG T1 T NMR T1 T T1 T T1 T PGSE-NMR

6 .3 Stejskal E. O. Stejskal and J. E. Tanner, Spin diffusion measurements: Spin echoes in the presence of a time-dependent field gradient, J. Chem. Phys. 4, 88-9 (1965). PFG PFG PFG E S0 E( δ, g, ) = S S 0 = exp( γ g δ D( δ / 3)) (1) 0-1 at 50 o C.1x10-10 m s -1 Li ( 7 Li) PF 6 ( 19 F) EC ( 1 H) DEC ( 1 H) ln(e/eo) x10-10 m s x10-10 m s x10-10 m s x10 9 1x10 10 γ δ g ( δ/3) 3 LiPF6 EC/DEC 4.7T wide-bore SCM ( 1 H NMR MHz) 50 o C ( ) 3mm 1H NMR g = 1.7 T/m, = 50 ms, δ = 0 1 ms 19F NMR g = 1.7 T/m, = 50 ms, δ = 0 1 ms g =.61 T/m, = 0 ms, δ = 0 1 ms ( ) 7Li NMR g =.61 T/m, = 50 ms, δ = 0 ms g = 3.95 T/m, = 0 ms, δ = 0 ms Ethylene carbonate (EC) Diethyl carbonate (DEC) 0:80(v/v) 1M LiPF 6 6

7 3. PFG calibration PFG calibration NMR Weingärtner H. Weingärtner, Self Diffusion in Liquid Water. A Reassessment Z. Phys. Chem. NF (Leipzig) 13, (198). Weingärtner 5 o C (98.15 K).30 x 10-9 m s -1 ( cm /s) 5 o C 30 o C calibration 30 o C.55 x10-9 m s -1 PFG calibration 5mm 5mm PFG PFG 40 mm (spinning rate = 0 Spinning OFF ) Galaxy-MacNMR FID-shimming GSX BMS-005J 5mm 3 Hz 10 Hz SCM PFG SCM T1 Stejskal E( δ, g, ) = S S 0 = exp( γ g δ D( δ / 3)) 7

8 Stejskal D PFG T/m PFG ms PFG ms PFG PFG, D PFG Hahn T1 T D T1 T 90 1 PFG 0.5ms 0ms 100ms 50ms 0.05, 0.,.09, 1ms(10 ) S/N calibration calibration T1 00 MHz 30 o C 3 s SCM T1 T1 5 1 T/m (100 Gauss/cm) PFG.05 ~ 1ms( ) 50 ms tuning 90 Sterjskal =0 ( =0.05ms) S0 ln( S S 0 ) = g δ D( δ /3) T/m ms m s -1 S R S/So NMR, 8

9 .55 x 10-9 m s Pure H O at 30 o C - -3 ln(s/so) Parameter Value Error A B -.56E E R SD N P < γ=0.85 T/m = 50 ms δ= ms 0 1x10 9 x10 9 3x10 9 γ δ g ( δ/3) 4 30 o C g=0.85t/m PFG calibration 1 H NMR DO H NMR H NMR DO H NMR 1 H NMR 1/6 6 PFG Weingärtner DO 5 o C 1.87 x 10-9 m s -1 HO/DO.11 x 10-9 m s -1 H/D PFG DO JEOL 1 H NMR 30 o C.15 x10-9 m s -1 H NMR.10 x10-9 m s -1 H NMR T1 = 0.51s 1 H NMR Sterjskal S 8 ln( ) = g δ D( δ /3) S 0 1 T/m 9

10 PFG PFG PFG Sterjskal E( δ, g, ) = exp( γ g δ D(4 δ ) / π ) / % digital NMR PFG PFG Hahn 90 o o - -Echo T T T T1 T T xy- xy- T T1 T1 T D, Li, 3 Na, 7 Al T T1 Stimulated Echo Pulse Sequence STE STE Hahn T 1 T1 1 PFG 10

11 PFG 16 STE PFG Hahn T 7 Li T STE Hahn T =5 ms NMR 0 ms 4 ms T PFG T Sterjskal PFG PFG JEOL 0T/m PFG NMR PFG-NMR ) PFG NMR HNMR 13 CNMR T1 T H NMR 13 C NMR H 13 CNMR LiBF4 LiPF6 BF4 19 F NMR 11 B NMR BF4 11 B NMR 19 F NMR PF6 19 F NMR 31 P 710Hz doublet 31 P NMR 6 F 6 F 1 P 31 P NMR 19 F NMR 31 P NMR 1 H NMR H NMR BF4 19 F NMR 11 B NMR 005 ENC Experimental NMR Conference 19F 11 B one-bond-coupling 1 H NMR 1 H- 1 H J-coupling Hahn 11

12 J-modulation J Hz cps cycle per second J = 7 Hz 1/πJ 0.03 s = 3 ms J Hahn =5 ms CH3CH J- xy- J eddy current effect PFG FID P0 P1 (1) S (power-spectrum) (1) NMR FID ADC Analogue-Digital Converter FID NMR NMR FT SN ADC NMR T1 (pulse-delay) T S/N 1H NMR 19 F NMR Radiation-Dumping X.-A. Mao and C.-H. Ye, Understanding Radiation Damping in a Simple Way, Concepts in Magnetic Resonance, 9, (1997). HO Tuning 90 1

13 40Hz Tuning 90 FID FID 90 Tuning T-SCM (00MHz- 1 HNMR) 6.35T-SCM (70MHz- 1 HNMR) Radiation-dumping ( ) NMR NMR NMR 100 NMR TMS NMR NMR T1 FID BF NMR St. Andrews 500 MHz SCM Kent 19 F NMR St. Andrew 1.76 x

14 m s o C 1.8 x m s -1 PFG.8 x m s x m s -1 1% PFG Doty calibration ( 1 H-NMR ) Kent Ph.D 19 F NMR NMR 1 H 19 F 7 Li NMR SCM 7 L inmr 00 JEOL AL400 14T/m PFG multi-probe NMR NMR 4.7T-wide-bore SCM NMR 9.4T-narrow-bore SCM 30 o C 50 o C 70 o C 80 o C 60 o C 40 o C CH3O(OCHCHO)nCH (n= 50) neat n= diglyme DG (n=3 50) 00 K. Hayamizu, E. Akiba, T. Bando and Y.Aihara, 1 H, 7 Li and 19 F NMR and ionic conductivity studies for liquid electrolytes composed of glymes and polyetheneglycol dimethyl ethers of CH 3 O(CH CH O) n CH 3 (n=3 to 50) doped with LiN(SO CF 3 ) J. Chem. Phys. 117, (00). n=3 triglyme(tg) DG 5 o C DG 6 DG BMS-005J 5mm 14

15 60 DG 5mm-height sample tube 70 o C 50 D apparent (10-10 m s -1 ) o C 50 o C 40 o C 0 o C (ms) artifact DG 0 7 Li 19 F 1H artifact artifact calibration 5 mm 7 5 mm DG 5 o C 1.01 mpas mpas ms 50 ms 50 o C 100 o C DG bp 16 o C mm K. Hayamizu, W. S. Price, A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples, J. Magn. Reson. 167 (004)

16 5 mm mm Insert mm 3 mm 4 mm Outer tube 7 mm-30ms mm-50ms D (x10-10 m s -1 ) o C mm-50ms 3mm-50ms 4mm-30ms 4mm-50ms 5mm-30ms 5mm-50ms 30 o C D x10-10 m s /T DG 1000/T -40 o C 8 DG 16

17 7. JEOL NMR 10 H O.30 x10-9 m s -1 at 5 o C D HO (10-9 m s -1 ) 1.55 x 10-9 m s -1 at 30 o C 0 o C JEOL KH-0T KH-10T Weingartner WSP /T 9 JEOL KH-0T T/m PFG mm NMR KH-10T T /m PFG 5mm Weingärtner WSP W. S. Price, H. Ide, Y. Arata, Self-Diffusion of Supercooled Water to 38K Using PGSE NMR Diffusion Measurements, J. Phys. Chem. A, 103, (1999). 17

18 1 H NMR 19 F NMR DEC diethylcarbonate LiN(SO(CF3)) (LiTFSI ) 1M 30 o C ( 1 H NMR) 30 o C 10 1M LiTFSI in DEC (3mm-height) Solvent ( 1 H NMR) D (10-10 m s -1 ) 1 80 o C -40 o C Probes 10T-multi 10T-F/H 0T-multi 10T-F/H 0T-multi 30 o C Anion( 19 F NMR) /T T-multi-probe PFG (0.1ms-0.5ms) 1998 F/H-probe H 1 H 90 o H NMR 1 H NMR 19 F NMR tuning 003 0T-multi-probe H, F, Li PFG PFG PFG 10 JEOL 18

19 Radiation Damping NMR RF NMR Radiation Damping Radiation Damping Radiation Damping Radiation Damping RF 19

20 Z Z Y Y (Y) FID FID Radiation Damping 0

LC-MS LC-MS NMR NMR LC-NMR [1] LC-NMR LC-NMR LC-NMR NMR [2] LC-NMR MHz NMR HPLC NMR LC-NMR LC-NMR LC-NMR WET water suppression enhanced through T1 eff

LC-MS LC-MS NMR NMR LC-NMR [1] LC-NMR LC-NMR LC-NMR NMR [2] LC-NMR MHz NMR HPLC NMR LC-NMR LC-NMR LC-NMR WET water suppression enhanced through T1 eff Technical Review LC-NMR How do you use liquid chromatography-nuclear magnetic resonance (LC-NMR) effectively for structural determinations of pharmaceutical impurities and metabolites? Toray Research Center,