Preclassification of Broadband and Sparse Infrared Data by Multiplicative Signal Correction Approach.

Preclassification of raw infrared spectra has often been neglected in scientific literature. Separating spectra of low spectral quality, due to low signal-to-noise ratio, presence of artifacts, and low analyte presence, is crucial for accurate model development. Furthermore, it is very important for sparse data, where it becomes challenging to visually inspect spectra of different natures. Hence, a preclassification approach to separate infrared spectra for sparse data is needed. In this study, we propose a preclassification approach based on Multiplicative Signal Correction (MSC). The MSC approach was applied on human and the bovine knee cartilage broadband Fourier Transform Infrared (FTIR) spectra and on a sparse data subset comprising of only seven wavelengths. The goal of the preclassification was to separate spectra with analyte-rich signals (i.e., cartilage) from spectra with analyte-poor (and high-matrix) signals (i.e., water). The human datasets 1 and 2 contained 814 and 815 spectra, while the bovine dataset contained 396 spectra. A pure water spectrum was used as a reference spectrum in the MSC approach. A threshold for the root mean square error (RMSE) was used to separate cartilage from water spectra for broadband and the sparse spectral data. Additionally, standard noise-to-ratio and principle component analysis were applied on broadband spectra. The fully automated MSC preclassification approach, using water as reference spectrum, performed as well as the manual visual inspection. Moreover, it enabled not only separation of cartilage from water spectra in broadband spectral datasets, but also in sparse datasets where manual visual inspection cannot be applied.

Preprocessing Strategies for Sparse Infrared Spectroscopy: A Case Study on Cartilage Diagnostics.

The aim of the study was to optimize preprocessing of sparse infrared spectral data. The sparse data were obtained by reducing broadband Fourier transform infrared attenuated total reflectance spectra of bovine and human cartilage, as well as of simulated spectral data, comprising several thousand spectral variables into datasets comprising only seven spectral variables. Different preprocessing approaches were compared, including simple baseline correction and normalization procedures, and model-based preprocessing, such as multiplicative signal correction (MSC). The optimal preprocessing was selected based on the quality of classification models established by partial least squares discriminant analysis for discriminating healthy and damaged cartilage samples. The best results for the sparse data were obtained by preprocessing using a baseline offset correction at 1800 cm-1, followed by peak normalization at 850 cm-1 and preprocessing by MSC.

Direct infrared spectroscopy for the size-independent identification and quantification of respirable particles relative mass in mine dusts.

Due to the global need for energy and resources, many workers are involved in underground and surface mining operations where they can be exposed to potentially hazardous crystalline dust particles. Besides commonly known alpha quartz, a variety of other materials may be inhaled when a worker is exposed to airborne dust. To date, the challenge of rapid in-field monitoring, identification, differentiation, and quantification of those particles has not been solved satisfactorily, in part because conventional analytical techniques require laboratory environments, complex method handling, and tedious sample preparation procedures and are in part limited by the effects of particle size. Using a set of the three most abundant minerals in limestone mine dust (i.e., calcite, dolomite, and quartz) and real-world dust samples, we demonstrate that Fourier transform infrared (FTIR) spectroscopy in combination with appropriate multivariate data analysis strategies provides a versatile tool for the identification and quantification of the mineral composition in relative complex matrices. An innovative analytical method with the potential of in-field application for quantifying the relative mass of crystalline particles in mine dust has been developed using transmission and diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) within a unified multivariate model. This proof-of-principle study shows how direct on-site quantification of crystalline particles in ambient air may be accomplished based on a direct-on-filter measurement, after mine dust particles are collected directly onto PVC filters by the worker using body-mounted devices. Without any further sample preparation, these loaded filters may be analyzed via transmission infrared (IR) spectroscopy and/or DRIFTS, and the mineral content is immediately quantified via a partial least squares regression (PLSR) algorithm that enables the combining of the spectral data of both methods into a single robust model. Furthermore, it was also demonstrated that the size regime of dust particles may be classified into groups of hazardous and less hazardous size regimes. Thus, this technique may provide additional essential information for controlling air quality in surface and underground mining operations. Graphical Abstract.

Hydrogel-Embedded Model Photocatalytic System Investigated by Raman and IR Spectroscopy Assisted by Density Functional Theory Calculations and Two-Dimensional Correlation Analysis.

The presented study reports the synthesis and the vibrational spectroscopic characterization of different matrix-embedded model photocatalysts. The goal of the study is to investigate the interaction of a polymer matrix with photosensitizing dyes and metal complexes for potential future photocatalytic applications. The synthesis focuses on a new rhodamine B derivate and a Pt(II) terpyridine complex, which both contain a polymerizable methacrylate moiety and an acid labile acylhydrazone group. The methacrylate moieties are afterward utilized to synthesize functional model hydrogels mainly consisting of poly(ethylene glycol) methacrylate units. The pH-dependent and temperature-dependent behavior of the hydrogels is investigated by means of Raman and IR spectroscopy assisted by density functional theory calculations and two-dimensional correlation spectroscopy. The spectroscopic results reveal that the Pt(II) terpyridine complex can be released from the polymer matrix by cleaving the C═N bond in an acid environment. The same behavior could not be observed in the case of the rhodamine B dye although it features a comparable C═N bond. The temperature-dependent study shows that the water evaporation has a significant influence neither on the molecular structure of the hydrogel nor on the model photocatalytic moieties.