Hierarchical band-target entropy minimization curve resolution and Pearson VII curve-fitting analysis of cellular protein infrared imaging spectra.

A soft-modeling multivariate numerical approach that combines self-modeling curve resolution (SMCR) and mixed Lorentzian-Gaussian curve fitting was successfully implemented for the first time to elucidate spatially and spectroscopically resolved spectral information from infrared imaging data of oral mucosa cells. A novel variant form of the robust band-target entropy minimization (BTEM) SMCR technique, coined as hierarchical BTEM (hBTEM), was introduced to first cluster similar cellular infrared spectra using the unsupervised hierarchical leader-follower cluster analysis (LFCA) and subsequently apply BTEM to clustered subsets of data to reconstruct three protein secondary structure (PSS) pure component spectra-alpha-helix, beta-sheet, and ambiguous structures-that associate with spatially differentiated regions of the cell infrared image. The Pearson VII curve-fitting procedure, which approximates a mixed Lorentzian-Gaussian model for spectral band shape, was used to optimally curve fit the resolved amide I and II bands of various hBTEM reconstructed PSS pure component spectra. The optimized Pearson VII band-shape parameters and peak center positions serve as means to characterize amide bands of PSS spectra found in various cell locations and for approximating their actual amide I/II intensity ratios. The new hBTEM methodology can also be potentially applied to vibrational spectroscopic datasets with dynamic or spatial variations arising from chemical reactions, physical perturbations, pathological states, and the like.

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