Weighted two-band target entropy minimization for the reconstruction of pure component mass spectra: Simulation studies and the application to real system

Master'sMASTER OF ENGINEERIN

Bayesian analysis of spectral mixture data using Markov Chain Monte Carlo Methods

This paper presents an original method for the analysis of multicomponent spectral data sets. The proposed algorithm is based on Bayesian estimation theory and Markov Chain Monte Carlo (MCMC) methods. Resolving spectral mixture analysis aims at recovering the unknown component spectra and at assessing the concentrations of the underlying species in the mixtures. In addition to non-negativity constraint, further assumptions are generally needed to get a unique resolution. The proposed statistical approach assumes mutually independent spectra and accounts for the non-negativity and the sparsity of both the pure component spectra and the concentration profiles. Gamma distribution priors are used to translate all these information in a probabilistic framework. The estimation is performed using MCMC methods which lead to an unsupervised algorithm, whose performances are assessed in a simulation study with a synthetic data set

Development of 2D- and 3D-BTEM for pattern recognition in higher-order spectroscopic and other data arrays

Ph.DDOCTOR OF PHILOSOPH

Development of multivariate curve resolution and associated system identification tools for IR emission, chiroptical, and far-infrared and far-raman spectroscopies

Ph.DDOCTOR OF PHILOSOPH

Bimetallic catalytic binuclear elimination reaction. Experimental, spectroscopic and kinetic elucidation

Ph.DDOCTOR OF PHILOSOPH

Topics in High-Dimensional Inference with Applications to Raman Spectroscopy.

Recent advances in technology have led to a demand for statistical techniques for high-dimensional data. This thesis explores dimension estimation and reduction, covariance estimation and regularization, and improving nearest neighbor graphs with some examples in the context of Raman spectroscopy. A new technique for estimating intrinsic dimension is proposed and used to estimate the number of pure components in a chemical mixture in Raman spectroscopy applications. We show how the new method improves over existing procedures, can be adapted via smoothing to deal with high noise levels, and has future applications in detecting mixture homogeneity. Next, we consider covariance estimation and regularization in high dimensions. Regularized covariance estimators in high dimensions depend on the ordering of variables or are completely invariant to variable permutations. We propose a new method, Isoband, which uses the unordered data to discover a suitable order for the variables and then apply methods which depend on variable ordering to improve covariance estimation for sparse covariance matrices. Our method has the additional advantage of being able to detect blocks within covariances and thus create additional sparsity and structure in the estimate. We show by simulations that when a suitable variable ordering exists, we do better by discovering it than by using a permutation- invariant method, and illustrate the new methodology on a real data example. The Isoband methodology relies on a nearest neighbor graph, and in the last chapter, we address improving robustness of nearest neighbor graphs, which have widespread statistical applications. In our application, the nearest neighbor graph is based on the variables rather than the observations. Two new methods are proposed which improve upon the basic nearest neighbor graphs by removing spurious edges by either bootstrapping the data or smoothing. Both methods are competitive compared to existing graph perturbation methods in the literature.Ph.D.StatisticsUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/60815/1/awagaman_1.pd