A critical step in Raman spectroscopy is baseline correction. This procedure eliminates the background signals generated by residual Rayleigh scattering or fluorescence. Baseline correction procedures relying on asymmetric loss functions have been employed recently. They operate with a reduced penalty on positive spectral deviations that essentially push down the baseline estimates from invading Raman peak areas. However, their coupling with polynomial fitting may not be suitable over the whole spectral domain and can yield inconsistent baselines. Their requirement of the specification of a threshold and the non-convexity of the corresponding objective function further complicates the computation. Learning from their pros and cons, we have developed a novel baseline correction procedure called the iterative smoothing-splines with root error adjustment (ISREA) that has three distinct advantages. First, ISREA uses smoothing splines to estimate the baseline that are more flexible than polynomials and capable of capturing complicated trends over the whole spectral domain. Second, ISREA mimics the asymmetric square root loss and removes the need of a threshold. Finally, ISREA avoids the direct optimization of a non-convex loss function by iteratively updating prediction errors and refitting baselines. Through our extensive numerical experiments on a wide variety of spectra including simulated spectra, mineral spectra, and dialysate spectra, we show that ISREA is simple, fast, and can yield consistent and accurate baselines that preserve all the meaningful Raman peaks.

Motivated by a hemodialysis monitoring study, we propose a logistic model with a functional predictor, called the Sparse Functional Logistic Regression (SFLR), where the corresponding coefficient function is locally sparse, that is, it is completely zero on some subregions of its domain. The coefficient function, together with the intercept parameter, are estimated through a doubly-penalized likelihood approach with a B-splines expansion. One penalty is for controlling the roughness of the coefficient function estimate and the other penalty, in the form of the L 1 norm, enforces the local sparsity. A Newton-Raphson procedure is designed for the optimization of the penalized likelihood. Our simulations show that SFLR is capable of generating a smooth and reasonably good estimate of the coefficient function on the non-null region(s) while recognizing the null region(s). Application of the method to the Raman spectral data generated from the heomdialysis study pinpoint the wavenumber regions for identifying key chemicals contributing to the dialysis progress.

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