C5860 Applied NMR Spectroscopy

Faculty of Science
Autumn 2006
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
prof. RNDr. Miroslav Holík, CSc. (lecturer)
Guaranteed by
prof. RNDr. Miroslav Holík, CSc.
Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Mon 11:00–12:50 02004
Prerequisites
Passing out the lectures of Chemical Structure (C5020) and the seminar(C5030).
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 25 fields of study the course is directly associated with, display
Course objectives
Chemical shift: use of shift and relaxation reagents. Coupling constant: determination of its sign. Intensity of NMR signal in kinetic measurements; line shape analysis in equilibrium kinetics. Relaxation mechanisms: measurements of relaxation times; the nuclear Overhauser effect. Pulse techniques: spin echo, magnetization transfer. 2D-NMR experiments.
Syllabus
  • 1. Correlation of chemical shifts Components of screening constant, dependence of delta on electronegativity, on sigma's. Diamagnetic anisotropy, solvent shift, "edge-to face" and "face-to-face" interaction. Calculation of NMR spectra from increments and from electron densities. 2.Lanthanide shift reagents 1H NMR spectrum in the presence of a shift reagent. Bound chemical shift and shifting magnitude. Nonlinearity of induced chemical shifts with high concentration of LSR. Map of dipolar field (McConnell-Robertson equation). Increase of anisotropy by addition of LSR. Optical active shift reagents - diastereomeric complexes. Topomerisation and the rotation isomerie. Crystal structure of dipyridyl-LSR. 1:1 and 1:2 complexes - equilibrium constants. Complexation of LSR and salts of Ag, mixed shift reagent. LSR and quaternal salts. 3.Coupling constants Energetic levels for AX systém ( J=0, J>0 and J<0). Systems of the first and higher order. Technique INDOR and sign of coupling constants. Nonreducible components - total spin and multiplicity. A2B and A3B2 systems. Dependence of 2JHH and 4JHH on the bond angle. Karplusova dependence of 3JHH on dihedral angle. Coupling through space (JHH a JFF). 4.Dynamic NMR spectroscopie Temperature change of two singuletts and AB system. Magnetization and Bloch equations. Steady state. Separation of real and imaginary components of Mxy. Slow exchange, coalescence, fast exchange. Difference of chemical schifts at coalescence. Rate constant at coalescence: different aproximations. Gutowsky-Holm equation. Line shape analysis - exchange matrix for Bulvalene and migration of CHO in cyklopentadiene. Intermolecular exchange. 5.Relaxation Vector of magnetization and relaxation times T1 a T2. Energetic transitions at absorption and relaxation. Increase in intensity of 13C signals (NOE). Correlation time and spectral density of fluctual field. "Extreme narrowing limit - ENL". Dipol-dipol relaxation and other relaxation mechanisms. 6.Nuklear Overhauser effect (NOE) Steady-state NOE in rigid molecule. Cross-corelation, basic equation for rigid molecules. NOE for two spins; Bell-Sanders aproximation. NOE for three spins in "linear arrangement". 7.Measurement of relaxation times Tilting of magnetization vector (90 and 180 deg.). Methods for T1 and T2 measurement. Inversion recovery, progressive saturation and saturation recovery. Hahn and Carr-Purcell echo. Meiboom-Gill's correction. 8.Puls experiments Selektive inversion of population (SPI). Population on energie levels for INDOR and SPI. Selektive population transfer (SPT) for 13C and 15N. Pascal and Jakobsen triangles. Puls sequence INEPT, refocused INEPT, DEPT. Spin echo SEFT at AX, AX2 and AX3 groups. Schroedinger equation for AX system, shift operators, coherence. Multiquantum coherence, 13C-13C coupling (INADEQUATE ). 9.2D NMR - 1st part Periods of puls experiment. Changes after the first and the second FT. Graphical presentation of 2D spectra (stacked and contour plots). Homo J-resolved 2D NMR (J,delta-spectrum), hetero (H,C)-J-resolved 2D spektrum (spin-flip and gated decoupler). 3D J,J,delta-13C spectrum of CHD group. 10.2D NMR - 2nd part HH-COSY spectrum, long range COSY, SECSY. Puls sequence for HC-COSY. HHC-Relay experiment on o-nitroanilin. Puls sequence 3D-COSY (1H, 13C, 31P). Puls sequence NOESY. Heteronuklear 2D-NOE (HOESY), NOESY sequence with HS puls. CC-COSY (INADEQUATE) 2D sequence. EXSY spectra of N,N-dimethylacetamid. 11.Chemically induced dynamic nucler polarization (CIDNP) Radikal pair; singlet and triplet state. Kaptein's rules - sign of polarization. Multiplet effectu AE and EA. 12.Spin-latice relaxation in rotating frame Puls sequence for "spin-locking" experiment. Spectrum at different lock times.Use of T1(rho)- fast exchange, number of coordinated solvent molekules, nondirect measurement of 1J(14N-13C).
Literature
  • HOLÍK, Miroslav. Čtyři lekce z NMR spektroskopie. 1. vyd. Brno: Universita J.E. Purkyně, 1983, 113 s. info
  • SCHRAML, Jan. Dvourozměrná NMR spektroskopie. 1. vyd. Praha: Academia, 1987, 130 s. info
  • HÁJEK, Milan. Kvantitativní FT NMR spektroskopie v chemické praxi. 1. vyd. Praha: Academia, 1989, 164 s. ISBN 8020000968. URL info
  • GOLJER, Igor and Tibor LIPTAJ. Nové metódy FT NMR spektroskopie kvapalín. 1. vyd. Bratislava: VEDA vydavatel'stvo Slovenskej akadémie vied, 1986, 181 s. info
Assessment methods (in Czech)
Ústní zkouška buď v angličtině nebo češtině.
Language of instruction
Czech
Further Comments
The course can also be completed outside the examination period.
The course is taught annually.
The course is also listed under the following terms Autumn 2007 - for the purpose of the accreditation, Autumn 1999, Autumn 2010 - only for the accreditation, Autumn 2000, Autumn 2001, Autumn 2002, Autumn 2003, Autumn 2004, Autumn 2005, Autumn 2007, Autumn 2008, Autumn 2009, Autumn 2010, Autumn 2011, Autumn 2011 - acreditation.
  • Enrolment Statistics (Autumn 2006, recent)
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