C8951 Solid-State NMR Spectroscopy - Basic Principles and Application in Chemistry.

Faculty of Science
autumn 2017
Extent and Intensity
1/0/0. 1 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
Ing. Jiří Brus, Dr. (lecturer)
prof. RNDr. Radek Marek, Ph.D. (lecturer)
Guaranteed by
prof. RNDr. Radek Marek, Ph.D.
National Centre for Biomolecular Research - Faculty of Science
Supplier department: National Centre for Biomolecular Research - Faculty of Science
Prerequisites
basic knowledge of physics, chemistry, and NMR in solution
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
there are 11 fields of study the course is directly associated with, display
Course objectives
The aim of this course is to explain basic principles of solid-state NMR spectroscopy. Current trends in solid-state NMR spectroscopy providing precise data for structure determination and dynamics will be introduced and discussed in detail. This involves recent methodology and hardware development resulting in a significant increase in resolution and selectivity of solid-state NMR. Basic principles of traditional and recently developed "averaging" techniques will be demonstrated followed by the introduction to multi-dimensional correlation and separation experiments as well as the NMR of quadrupolar nuclei.
Learning outcomes
Student will be able to:
- use basic 1D methods of NMR spectroscopy to characterize molecular structure in solid state;
- apply solid state NMR methods to determine supramolecular assembly of solid materials;
- analyze basic 1D NMR spectra of solid samples;
- select appropriate NMR experiments for characterizing pharmaceutical substances, polymorphs, hydrates.
Syllabus
  • 1. Introduction into Solid-State NMR spectroscopy: General overview of nuclear interactions with magnetic field; anisotropy of nuclear interactions broadening of NMR spectra in solid state. Basic principles of averaging of anisotropy interactions (Magic Angle Spinning MAS, Dipolar Decoupling DD). Basic differences between solution-state and solid-state NMR spectra (homogeneous and inhomogeneous broadening order vs. disorder). Frictional heating of samples dramatic increase in temperature. 2. Analysis of anisotropy of nuclear interactions techniques of averaging of anisotropy interactions: Detail description of nuclear interactions: chemical shift anisotropy (CSA), dipolar interactions (direct through-space interactions), quadrupolar interactions. Analysis of techniques leading to averaging of the anisotropic interactions: Magic Angle Spinning (MAS), heteronuclear dipolar decoupling (cw, TPPM, XiX), homonuclear dipolar decoupling (WHH-4, BR-24, FSLG, PMLG), double rotation and dynamic angle spinning (DOR, DAS). 3. Techniques of polarization transfer: Heteronuclear (1H-13C, 1H-X) polarization transfer; increase in sensitivity of NMR experiments cross-polarization (CP); dynamics of CP; Hartmann-Hahn condition influence of MAS speed on the sensitivity and experimental setup. Cross-polarization involving quadrupolar nuclei with half-integer spin higher than . Homonuclear polarization transfer 1H-1H spin diffusion (efficient tool to evaluate degree of mixing and size of particles in heterogeneous systems). 4. Spectral editing techniques: Suppression of spinning side-bands (TOSS, SELTICS); suppression of 13C NMR signals of carbons with directly bonded hydrogen atoms due to rapid loss of 13C coherence (NQS); editing techniques based on different cross-polarization dynamics due to various strength of 13C-1H heteronuclear dipolar couplings in C, CH, CH2, a CH3 (CPPI); influence of segmental dynamics; editing techniques based on the evolution of J spin-spin couplings (SoS-APT); manipulation with a spin system (evolution of single-quantum or multiple-quantum coherences). Application on simple and complex systems (e.g. Gly, Ala, simvastatin). 5. Heteronuclear 1H-X separation experiments (Wide-Line Separation structure and segmental dynamics): Simple separation of 1H-1H dipolar interactions according to 13C chemical shifts qualitative evaluation of segmental dynamics; insertion of spin-diffusion period (determination of the size of domains in heterogeneous systems); location of water molecules along polymer chains. Separation of heteronuclear 1H-13C dipolar interactions according to 13C chemical shifts quantitative evaluation of segmental dynamics determination of amplitude of reorientation of basic structure units (CH, CH2). Applications on polymer blends (polyethyleneoxide-polycarbonate), networks (polyimide-polydimethylsiloxane), polypeptides, nanocomposites and inorganic materials. 6. Heteronuclear 1H-X correlation experiments: Through-space correlations induced by dipolar interactions; one-bond correlations; identification of long-range spin-pairs; measurement of interatomic distances (3D HETCOR); comparison with experiments employing indirect spin-spin interactions (sensitivity vs. selectivity, 1H-13C HMQS-J-MAS). Inverse experiments (1H detected) and gradient selection of coherences. Application on medium-size molecules (simvastatin). 7. Homonuclear 1H-1H correlation experiments: Principles and troubleshooting of 1H-1H COSY in solid-state NMR (why it is so complicated?) relatively small spectral resolution; spin diffusion instead evolution of J couplings during a mixing period; evaluation of homogeneity and miscibility of mixtures, complexes, aggregates, etc. Determination of size of domains and particles in heterogeneous systems; precise measurement of 1H-1H interatomic distances. Enhancement of spectral resolution 3D 1H-1H-13C experiment. Applications on polymer blends (polyethylenoxid-polycarbonate), polymer complexes (polyethyleneoxide-small organic molecules), networks (polyimide-polydimethylsiloxane), nanocomposites, inorganic materials and simvastatin. 8. Double-quantum 1H-1H correlation techniques - detection of hydrogen bonds and pi-pi interactions: Ultra-fast MAS significant enhancement in spectral resolution (limitation substantial frictional heating of the sample); basic principle of excitation and reconversion of double-quantum coherence (back-to-back BABA sequence). Measurement of 1H-1H interatomic distances. 9. Enhancement in spectral resolution X-X a X-Y correlations: INADEQUATE at natural isotopic abundance (medium-size spin systems up to 25-30 carbon atoms; optimization of heteronuclear decoupling transverse dephasing optimized INADEQUATE; DQF-COSY simple modification. Techniques suitable for uniformly labeled samples: 13C-13C PDSD proton-driven spin diffusion, double-quantum techniques based on recoupling sequences like C7 and PC7. Basic concept of double cross-polarization experiments; suppression of polarization transfer back to 1H spin system Lee-Goldburg decoupling. 10. Backbone and side-chain signal assignment of proteins and polypeptides, determination of global conformation: Basic experimental procedures leading to sequential 13C and 15N signal assignment and subsequent measurement of interatomic distances and torsion angles (polypeptides and small proteins). 2D and 3D techniques for determination of intra-residual spin connectivity C'-Calpha-Cbeta and N-Calpha-Cbeta and inter-residual connectivity Calpha-Calpha and N-Calpha-Cbeta. Appropriate selection of mixing period single-quantum or multiple-quantum? What about NOE? Sample preparation. 11. Quadrupolar nuclei: Spectra of quadrupolar nuclei second-order broadening; multiple-quantum two-dimensional techniques partially separating quadrupolar interactions enhancement of spectral resolution; experiments with z-filter; full-echo experiments and other modifications (e.g. fast amplitude modulation FAM); influence of MAS speed, intensity of B0 and B1 magnetic fields on quality of the resulting 2D spectra. Correlation experiments involving quadrupolar nuclei (1H-27Al, 29Si-27Al). Applications on geopolymers and zeolites. 12. Technical aspects of NMR experiments in solid-state: Probehead design temperature ranges and temperature calibration; double-resonance probeheads optimization (wobb) is crucial precondition; triple-resonance probeheads exchangeable insert; setup of magic angle; homogeneity of B0 field - shimming; power levels of excitations and decoupling fields B1 minimum repetition delay (duty cycle); linear amplifiers; basic specifications delays, pulses, phases; rotor types limitations and advantages.
Literature
  • Melinda J. Duer, Solid-state NMR Spectroscopy: Principles and Applications. Blackwell Science, Oxford, 2002, ISBN 0-632-05351-8.
Teaching methods
Lectures
Assessment methods
oral exam
Language of instruction
Czech
Further comments (probably available only in Czech)
The course is taught once in two years.
Information on the per-term frequency of the course: od 2006/2007.
The course is taught: in blocks.
The course is also listed under the following terms Spring 2000, Autumn 2010 - only for the accreditation, Autumn 2005, Autumn 2006, Autumn 2008, Autumn 2009, Autumn 2010, Autumn 2011, Autumn 2011 - acreditation, Autumn 2012, Autumn 2015.
  • Enrolment Statistics (recent)
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