<p>Nuclear Magnetic Resonance spectroscopy (NMR) is a powerful technique for rapid and efficient quantitation of compounds in chemical samples. NMR causes the nuclei in the molecules to resonate and various chemical arrangements appear as peaks in the Fourier spectrum of a free induction decay (FID). The spectral parameters elicited from the peaks serve as a fingerprint of the chemical components contained in the molecule. These fingerprints can be employed to understand the chemical structure. Signal acquired from a NMR spectrometer is ideally modelled as a superposition of multiple damped complex exponentials (cisoids) in Additive White Gaussian Noise (AWGN). The number as well as the spectral parameters of the cisoids need to be estimated for characterisation of the underlying chemicals. The estimation, however, suffers from numerous difficulties in practice. These include: unknown number of cisoids, large signal length, large dynamic range, large peak density, and numerous distortions caused by experimental artefacts. This thesis aims at the development of estimators that, in view of the above-mentioned practical features, are capable of rapid, high-resolution and apriori-information-free quantitation of NMR signals. Moreover, for the analytic evaluation of the performance of such estimators, the thesis aims to derive interpretable analytic results for the fundamental estimation theory tool for assessing the performance of an unbiased estimator: the Cramer Rao Lower Bound (CRLB). By such results, we mean those that analytically allow the determination, in terms of the CRLB, of the impact of the free model parameters on the estimator performance. For the CRLB, we report analytic expressions on the variance of unbiased parameter estimates of damping factors, frequencies and complex amplitudes of an arbitrary number of damped cisoids embedded in AWGN. In addition to the CRLB, analytic expressions for the determinant and the condition number of the associated Fisher Information Matrix (FIM) are also reported. Further results, in similar order, are reported for two special cases of the damped cisosid model: the Magnetic Resonance Relaxometry model and the amplitude-only model (employed in quantitative NMR - qNMR). Some auxiliary results for the above-mentioned models are also presented, i.e., on the multiplicity of the eigenvalues and the factorisation of the characteristic polynomial associated with their respective FIMs. These results have not been previously reported. The reported theoretical results successfully account for various physical and chemical phenomena observed in experimental NMR data, and quantify their impact on the accuracy of an unbiased estimator as a function of both model and experimental parameters, e.g., influence of prior knowledge, peak multiplicity, multiplet symmetry, solvent peak, carbon satellites, etc. For rapid, high-resolution and apriori-information-free quantitation of NMR signals, a sub-band Steiglitz-McBride algorithm is reported. The developed algorithm directly converts the time-domain FID data into a table of estimated amplitudes, phases, frequencies and damping factors, without requiring any previous knowledge or pre-processing. A 2D sub-band Steiglitz-McBride algorithm, for the quantitation of 2D NMR data in a similar manner, is also reported. The performance of the developed algorithms is validated by their application to experimental data, which manifests that they outperform the state-of-the-art in terms of speed, resolution and apriori-information-free operation.</p>
NMR refinement and peptide folding using the GROMACS software
