<p> Two-dimensional C-H chemical shift correlation spectroscopy provides a large amount of information in a two dimensional matrix. Many variations of these experiments have been in an effort to enhance the information content of these experiments. Decoupling of multiplet signals is one method used to increase the sensitivity of an NMR experiment. Simple broadband decoupling in ω2 is done by irradiating the correlated channel during acquisition. Decoupling in ω1 must be done using less direct methods, one of which is to use bilinear rotation decoupling. The traditional description of the effect that a BIRD pulse has on the spin systems is based on a simple AX system which is at equilibrium at the beginning of the pulse, which does not apply in many real systems.</p> <p> This study uses the Superspin formalism to show in more detail the behaviour of more complex spin systems during the BIRD sequence, and the effect of varying parameters within the BIRD sequence. This treatment involved the derivation of complete spherical tensor descriptions of AX, AX2, and AX3 spin systems. This allowed the derivation of a mathematical description of an INEPT style pulse sequence, where the refocussing pulse in INEPT was replaced with the BIRD sequence. The derivation of the general evolution transformations of the spherical tensors in Liouville space also allowed the theoretical treatment to be done in a single basis, where earlier implementations of the Superspin formalism converted between a spherical tensor basis for the treatment of pulses and a Hamiltonian basis for the treatment of delays. This theoretical treatment allows the derivation of a functional form for the dependence of the carbon signal intensity on the variation of the interpulse delay in the BIRD sequence.</p> <p> This formalism was also used to analyze the occurrence of artifacts in two dimensional heteronuclear shift correlation spectra, due to strong coupling between methylene protons. These artifacts were studied in experiments that attempt broadband homonuclear decoupling in ω1 through the use of constant evolution time between the initial excitation pulse and polarization transfer. Two experiments were analyzed, the COLOC experiment and the HETRES experiment. The superspin formalism was used to deduce a functional form for the intensity of the artifact as a function of the strength of the coupling between the methylene protons.</p> / Thesis / Master of Science (MSc)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/19244 |
| Date | 04 1900 |
| Creators | Burton, Ian |
| Contributors | Bain, A. D., Chemistry |
| Source Sets | McMaster University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
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