Spin selective MQ-SQ correlation has been demonstrated by either selective pulses in homo-nuclear spin systems in isotropic and weakly orienting chiral media or by nonselective pulses in hetero-nuclear spin systems in strongly aligned media. As a consequence of the spin selective correlation, the coherence transfer pathway from MQ to SQ is spin state selective. This two dimensional approach enables the utilization of the passive couplings (remote couplings) to break a complex one dimensional spectrum into many sub spectra. Each sub spectrum contains fewer transitions and hence fewer couplings (active couplings). The role of the passive couplings is to displace the sub spectra and measurement of the displacements taking into account their relative tilt provides the magnitude of the passive couplings along with relative signs. Further possibility of a spin state selective MQ-SQ resolved experiment to determine very small remote couplings otherwise buried within linewidth in one dimensional spectrum has been demonstrated. The resolution of the multiple quantum spectrum in indirect dimension has also been exploited to separate the sub spectra. The technique renders the analysis of complex spectrum in isotropic system much simpler. The potentialities of the technique have also been demonstrated for discrimination of optical enantiomers and derivation of the residual dipolar couplings from very complicated spectrum. The second order spectrum in strongly aligned media restrict selective excitation, however in hetero-nuclear spin system the nonselective pulses on protons do not interact with the hetero-nuclear spins. Thus the weakly coupled part of a strongly coupled spectrum has been exploited for simplifying the second order spectrum and thereby its analysis. Thus several methodologies derived from spin selective correlation has been demonstrated.
Enantiopure spectrum has been recorded from a mixture of R and S enantiomers by a novel pulse scheme called Double Quantum Selective Refocusing Experiment. The dipolar coupled methyl protons in weakly orienting media are utilized. The selective excitation of double quantum coherence reduces the three spin system into a two spin system and remote couplings are refocused which otherwise leads to broadening. The sum of passive couplings being different for the enantiomers resolution in the DQ dimension is enhanced and thereby their discrimination.
Finally several decoupling schemes has been compared in the indirect dimension of HSQC experiment to resolve 13C satellite spectra otherwise buried within line width for increased confidence in determining hetero-nuclear framework information.
| Identifer | oai:union.ndltd.org:IISc/oai:etd.ncsi.iisc.ernet.in:2005/793 |
| Date | 05 1900 |
| Creators | Baishya, Bikash |
| Contributors | Suryaprakash, N |
| Source Sets | India Institute of Science |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
| Relation | G22331 |
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