1. 核磁共振光譜與影像導論
Introduction to NMR Spectroscopy and Imaging Lecture 08 Introduction to Solid State NMR (Spring Term, 2011) Department of Chemistry National Sun Yat-sen University

2. Introduction to Solid State NMR
8.0 Summary of internal interactions in solid state NMR
8.1 Typical lineshapes for static samples
8.2 Magic-angle-spinning (MAS)
8.3 Cross polarization (CP) and CPMAS
8.4 Homonuclear and heteronuclear correlations (COSY/HETCOR)
8.5 Multi-quantum MAS (MQMAS) of quadrupole spins

3. The major interactions in solid state NMR spectroscopy.

4. Single Crystal or Polycrystalline (Powder) Samples

5. (Static) Powder Patterns

6. Powder spectrum
iso , δ,

7. Magic Angle Spinning (MAS)
Θ=54.74° B0

8. Magic Angle Spinning (MAS)
54.74o

9. Coordinate Systems 33 11 22 Z X Y

11. Magic-Angle-Spinning Spectrum

12. MAS for spin 1/2 nuclei

14. The Quadrupolar Majority

15. 2H MAS HZ HZ + HQ HZ + HQ (powder)
Experimental (A) and simulated (B and C) 2H MAS NMR
spectra (14.1 T) of KD2PO4 using ωr= 7:0 kHz. The
simulated spectrum in (B) employs the optimized 2H
quadrupole coupling and CSA parameters listed below
whereas the simulation in (C) only considers the quadrupole
coupling interaction. The asterisk indicates the isotropic peak.

16. Spin-3/2
23Na ( MHz) NMR spectra of NaN03 recorded using (a) static and
(b) MAS (v, = 4820 Hz) conditions ( 16 scans). The central transition is cut off at (a) 1/4 and (b) 1/13 of its total height.

17. JORGEN SKIBSTED, NIELS CHR. NIELSEN, HENRIK BILDME, HANS J
JORGEN SKIBSTED, NIELS CHR. NIELSEN, HENRIK BILDME, HANS J. JAKOBSEN, JMR, 95, 88(1991)

18. Spin-5/2
27AI ( MHz) MAS NMR spectra of the central and satellite transitions for α-Al2O3. The
ppm scale is referenced to an external sample of 1 .0 M AlCl3, in H2O. (a) Experimental spectrum showing the relative intensities of the central and satellite transitions and observed using a Varian VXR-400 S wideline spectrometer; ωr= 7525 Hz, spectral width SW = 1 .0 MHz, pulse width pw = 1 .0 μs (π /4 solid pulse), and number of transients nt= (b) Spectrum in (a) with the vertical scale expanded by a factor of ten; the inset shows expansion of a region where the second-order quadrupolar shift between the (±5/2, ±3/2) and the (±3/2, ±1/2) satellite transitions is clearly observed (see text). (c) Simulated MAS spectrum for the satellite transitions in (b) obtained using QCC = 2.38 MHz, η = 0.00, ωr= 7525 Hz, and Gaussian linewidths of 900 and I 175 Hz for the (±3/2, ±1/2) and (±5/2, ±3/2) transitions. respectively.
HANS J. JAKOBSEN, JORGEN SKIBSTED, HENRIK BILDSBE, ANDNIELS CHR .NIELSEN,JMR 85,173(1989)

19. 51V MAS (HQ+HCSA) Question: is it possible to suppress the sidebands
of a satellite transition MAS spectrum?
“Answer”: Not done yet, but it’s an interesting topic.

21. Sensitivity
High Fields
Labeled samples CP
CPMAS

22. Cross Polarization
CPMAS─one of the most important solid state NMR techniques.
CP contact time: several hundred microseconds to tens of milliseconds.
Purpose: To enhance the sensitivity of the lower γ spins such as carbon-13. maximal enhancement factor: γI/γS
Other advantages: Shorter recycle delay time
Distinguish the interconnectivity of nuclear spins such as the protonation of a certain carbon nucleus.

23. CP Pulse Sequence

25. 1H-13C CPMAS spectrum of (a) mixed lactose, (b) -lactose and (c) anhydrous stable -lactose.
The lines marked by asterisks are assigned to the residual amorphous lactose

26. Sodium silicate glasses
Static 17O NMR spectra
bridging (BO) and
non-bridging (NBO)
oxygens
Na2Si2O5
Na2Si3O7
Na2Si4O9
NBO BO
ppm

27. Structure of glasses (I)
NBO BO

28. 29Si NMR spectra for sodium silicate glasses
static MAS Q4
mole %
Na2O 34 37 41 Q3 Q2
Q3 + Q2
ppm

29. Structure of glasses (II)Q4 Q2 Q3 Q1

30. 1H-29Si CPMAS intensity as a function of contact timeQ2 Q3 Q4
Different sites in a Na2Si4O9 glass with 9.1 wt% H2O
contact time (ms)

31. Ramp CP (Matching Condition Satisfied at High Speeds)
Acquisition X CP
decoupling 1H

32. Homonuclear correlation

33. Homonuclear correlation : establishing connectivities

34. Dipolar - Chemical Shift Correlation

35. Magic Angle (54.7 ) Spinning
Multi-Quantum Magic-Angle Spinning (MQMAS)
(for half-integr quadrupolar spins)
          
Magic Angle
(54.7 ) Spinning
MQC SQC o
θM θM

36. 17O-MQMAS spectrum of the silicate coesite

37. Applications Polymers Glasses Porous materials Liquid crystals
Biomolecules
Tissues
Soil, plants, animals, ....