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This work provides new insight into the state of water in a series of aliphatic ketones. For our studies, we selected nine aliphatic ketones of different size and structure to examine the effect of various structural motifs on behavior of water in the mixtures. Our results reveal that conformational flexibility of aliphatic chains in the linear ketones allows for effective shielding of the carbonyl group, and this flexibility is the main reason for poor solubility of water. Hence, in the linear ketones molecules of water are involved mostly in ketone-water interactions, while the water-water interactions are rare. Higher solubility of water in the cyclic ketones allows for creation of clusters of water, where the molecules are in water-like environment. The temperature rise in wet cyclic ketones increases population of ketone-water interactions at the expense of the water-water ones, while in the linear ketones and 2,6-dimethylcyclohexanone at an elevated temperature there is an increase in the population of singly bonded water at the expense of the doubly bonded one. DFT calculations reveal that the substitution of cyclohexanone by a single methyl group does not affect the strength of the ketone-water interactions, while it has a significant impact on the solubility of water in the ketone. The most important conclusion from this study is that the accessibility of the carbonyl group is the most important factor determining the intermolecular interactions and solubility of water in aliphatic ketones., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

We investigated the anharmonicity and intermolecular interactions of N-methylformamide (NMF) and di-N,N-methylformamide (DMF) in the neat liquid phase with particular interest in the amide bands. The vibrational spectra, complex refractive index, and complex electric permittivity were determined in in the mid- (MIR) and near-infrared (NIR) regions (11,500-560 cm -1 ; 870-17857 nm). Dispersion analysis was based on the Classical Damped Harmonic Oscillator (CDHO) and simultaneous modelling of the real and imaginary components of the spectra. This data delivered insights into the vibrational energy dissipation and self-association in liquid amides. Identification of the MIR and NIR bands was based on anharmonic GVPT2//B3LYP/6-311++G(d,p) calculations. DMF and NMF follow distinct self-association, evidenced in the MIR fingerprint by the two components of the νCO, the analog of the Amide I band. These conclusions are supported by the structural information derived from the NIR spectra. Furthermore, the contribution of overtones and combination bands in the MIR spectra of amides was examined. The conclusions on molecular interactions and structural dynamics of NMF and DMF contribute to a deeper understanding of the effects of changes in the local environment of the amide group., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Quantum mechanical calculations are routinely used as a major support in mid-infrared (MIR) and Raman spectroscopy. In contrast, practical limitations for long time formed a barrier to developing a similar synergy between near-infrared (NIR) spectroscopy and computational chemistry. Recent advances in theoretical methods suitable for calculation of NIR spectra opened the pathway to modeling NIR spectra of various molecules. Accurate theoretical reproduction of NIR spectra of molecules reaching the size of long-chain fatty acids was accomplished so far. In silico NIR spectroscopy, where the spectra are calculated ab initio, provides substantial improvement in our understanding of the overtones and combination bands that overlap in staggering numbers and create complex lineshape typical for NIR spectra. This improves the comprehension of the spectral information enabling access to rich and detail molecular footprint, essential for fundamental research and useful in routine analysis by NIR spectroscopy and chemometrics. This review article summarizes the most recent accomplishments in the emerging field with examples of simulated NIR spectra of molecules reaching long-chain fatty acids and polymers. In addition to detailed NIR band assignments and new physical insights, simulated spectra enable innovative support in applications. Understanding of the difference in the performance observed between miniaturized NIR spectrometers and chemical interpretation of the chemometric models are noteworthy here. These new elements integrated into NIR spectroscopy framework enable a knowledge-based design of the analysis with comprehension of the processed chemical information., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Near-infrared (NIR) spectroscopy is a valued analytical tool in various applications involving polymers. However, complex nature of NIR spectra imposes difficulties in their direct interpretation. Here, anharmonic quantum chemical calculations are used to simulate NIR spectra of nine polymers; acrylonitrile butadiene styrene (ABS), ethylene-vinyl acetate (EVAC), polycarbonate (PC), polyethylene terephthalate (PET), polylactide or polylactic acid (PLA), polymethylmethacrylate (PMMA), polyoxymethylene (POM), polystyrene (PS) and polyvinylchloride (PVC). The generalized spectra-structure correlations are derived for these systems with focus given to the manifestation in NIR spectra of aromatic ring, C=O, C≡N and C-Cl functionalities. It is concluded that the nature of NIR polymer bands is only moderately sensitive to the remote chemical neighborhood. The majority of NIR absorption of polymers originates from binary combination bands, while the first overtones are meaningful only in ca. 6200-5500 cm -1 region. The contribution of the overtone bands is relatively higher for the polymers bearing aromatic rings because of higher intensity of C-H stretching overtones. Highly characteristic combination bands of the modes localized in aromatic ring (ring deformation and CH stretching) are relatively independent on the remaining structure of the polymer. The combination bands originating from C=O group are more sensitive to the chemical neighborhood in near proximity, forming a useful fingerprint for a specific polymer. In contrast, the vibrational bands of C≡N functionality are far less useful in NIR region than in infrared (IR) region. With aid of the calculated absorption bands, structural specificity of NIR spectroscopy of polymers can be markedly improved., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

The present review aims to draw a perspective on the vibrational spectroscopy combined with the tools of computational chemistry. This includes an overview of the accomplishments made so far, the assessment of the present development trends and the prospects for continuing these advances. State-of-the-art methods, current challenges and the expected future advances are evaluated from the point-of-view of the practical application in vibrational spectroscopy. A special attention is given to near-infrared (NIR) spectroscopy, which occupies a distinct position among the techniques of vibrational spectroscopy. As the result of intrinsically complex spectra, reliance on the anharmonicity as well as keen interest given to complex materials, NIR spectroscopy may particularly benefit from computational chemistry. The present key limitations hindering development of NIR spectroscopy are identified; these constitute primarily the limit in the treatable system size and the inability to effectively include chemical matrix effects. Given the expanding role of NIR spectroscopy in science and industry, lifting these limitations would directly enhance the general potential of this technique., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

Far-ultraviolet (FUV) spectroscopy in the region of 140-200 nm of condensed-phase has received keen interest as a new electronic spectroscopy. The introduction of the attenuated total reflection (ATR) technique to the FUV region has opened a new avenue for FUV spectroscopy of liquids and solids. ATR-FUV spectroscopy enables the study of electronic structures and transitions of most types of molecules. It also holds great promise for a variety of applications, i.e., from the application to basic sciences to practical applications. In this review, the characteristics and advantages of ATR-FUV spectroscopy in the condensed phase are described first; then, a brief historical overview is provided. Next, the ATR-FUV spectroscopy instrumentation is outlined. After these introductory parts, a variety of AFT-FUV spectroscopy applications are introduced, starting from applications to investigations of electronic structure and transitions of alkanes, graphenes, and polymers. Then, time-resolved ATR-FUV spectroscopy is discussed. The applications to materials research, such as the research on inorganic semiconductors and ionic liquids, follow. In the last part, the FUV spectroscopy perspective is emphasized., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The global demand for natural products grows rapidly, intensifying the request for the development of high-throughput, fast, non-invasive tools for quality control applicable on-site. Moisture content is one of the most important quality parameters of natural products. It determines their market suitability, stability and shelf life and should preferably be constantly monitored. Miniaturized near-infrared (NIR) spectroscopy is a powerful method for on-site analysis, potentially fulfilling this requirement. Here, a feasibility study for applicability and analytical performance of three miniaturized NIR spectrometers and two benchtop instruments was evaluated in that scenario. The case study involved 192 dried plant extracts composed of five different plants harvested in different countries at various times within two years. The reference analysis by Karl Fischer titration determined the water content in this sample set between 1.36% and 6.47%. For the spectroscopic analysis half of the samples were laced with a drying agent to comply with the industry standard. The performance of various calibration models for NIR analysis was evaluated on the basis of root-mean square error of prediction (RMSEP) determined for an independent test set. Partial least squares regression (PLSR), Gaussian process regression (GPR) and artificial neural network (ANN) models were constructed for the spectral sets from each instrument. GPR and ANN models performed superior for all samples measured by handheld spectrometers and for native ones analyzed by benchtop instruments. Moreover, the accuracy penalty when analyzing native samples was lower for GPR and ANN prediction as well. With GPR or ANN calibration, miniaturized spectrometers offered the prediction performance at the level of the benchtop instruments. Therefore, in this analytical application miniaturized spectrometers can be used on-site with no penalty to the performance vs. laboratory-based NIR analysis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Developing effective ways for controlling the quality of natural products that are sold in high volume worldwide is currently one of the most urgent goals of analytical chemistry. Black pepper (Piper nigrum) is a major spice that constitutes 34% of the global spice market. Black pepper is highly prone to quality variations, arising from alteration of the piperine content. Miniaturized NIR spectroscopy offers a high-throughput, cost-effective and laboratory independent technique for quality control of black pepper. Handheld NIR spectrometers differ in the implemented technology, with impact on their analytical performance and unit cost. In this work, the performance of three miniaturized NIR instruments in quantification of piperine in whole and milled seeds of black pepper was investigated. With HPLC method used as the reference analysis, partial least squares regression (PLSR) models were constructed for NIR spectra while the prediction accuracy with respect to the spectrometer used was monitored through root mean square error of prediction (RMSEP) determined for an independent test set validation. Prediction of piperine content in milled seeds was achieved with a RMSEP of 0.18% using the benchtop spectrometer Büchi NIRFlex N-500; while handheld instruments offered, respectively, 0.22% (microPHAZIR), 0.26% (MicroNIR 2200) and 0.42% (SCiO). In contrast, for the analysis of the whole pepper seeds, only the Büchi NIRFlex N-500 (RMSEP: 0.30%) and the Viavi MicroNIR 2200 (RMSEP: 0.37%) gained reliable results. The performance of Thermo Scientific microPHAZIR was satisfactory (RMSEP: 0.75%). The consumer-aimed spectrometer SCiO (Consumer Physics) was found adequate for milled samples, while the analysis of the whole seeds was unsuccessful. To gain better understanding of the features of PLSR models of piperine content in black pepper, quantum mechanical simulation of NIR absorption bands of piperine was performed. This step enabled elucidating the chemical information relevant to the calibration model, and interpreting the difference in the analytical performance of the compared spectrometers with statistical parameters of the calibration models below acceptable levels., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

We investigated caffeine and l-theanine, quality characteristics for camellia sinensis, in milled and ground black tea samples with near-infrared (NIR) spectroscopy giving a direct comparison between the performances of benchtop and handheld NIR spectrometers. The constructed partial least squares regression (PLSR) models for all spectrometers were validated by test-set-validation and according to the obtained root mean square errors of prediction (RMSEP). The performances of the spectrometers were as follows: The benchtop spectrometer NIRFlex N-500 (Büchi, Flawil, Switzerland) showed the best results for milled samples with a RMSEP of 0.14% for caffeine and 0.12% for l-theanine. For the ground samples, a RMSEP of 0.17% for caffeine and 0.12% for l-theanine was gained. While the handheld spectrometers MicroNIR 2200 (Viavi Solutions (former: JDS Uniphase Corporation), Milpitas, USA) and the microPHAZIR (Thermo Fisher Scientific, Waltham, USA) both provided good results for the prediction of caffeine in milled samples (RMSEP of 0.22% and 0.26%), only the microPHAZIR was able to satisfactorily determine the caffeine content in ground samples (RMSEP of 0.28%). The investigation of l-theanine with handheld spectrometers did not lead to convincing results, since R 2 was 0.75 for milled samples while ground samples could not be calculated. Decisive differences were concluded in how different NIR instruments capture the chemical information on caffeine vs. l-theanine. The handheld spectrometers manifested limited applicability to l-theanine. Deeper insight was obtained through the detailed NIR band assignments of caffeine and l-theanine derived from quantum mechanical simulation. Narrow working spectral region of handhelds omits the characteristic absorption bands of l-theanine. Therefore, information on l-theanine content measured by the evaluated miniaturized spectrometers is insufficient to enable its effective quantification. In contrast, the most characteristic NIR absorption of caffeine matches the working spectral regions of the handheld NIR spectrometers, hence their performance is comparable with the benchtop device., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Infrared (IR; or mid-infrared, MIR; 4000-400 cm -1 ; 2500-25,000 nm) spectroscopy has become one of the most powerful and versatile tools at the disposal of modern bioscience. Because of its high molecular specificity, applicability to wide variety of samples, rapid measurement and non-invasivity, IR spectroscopy forms a potent approach to elucidate qualitative and quantitative information from various kinds of biological material. For these reasons, it became an established bioanalytical technique with diverse applications. This work aims to be a comprehensive and critical review of the recent accomplishments in the field of biomolecular and bioanalytical IR spectroscopy. That progress is presented on a wider background, with fundamental characteristics, the basic principles of the technique outlined, and its scientific capability directly compared with other methods being used in similar fields (e.g. near-infrared, Raman, fluorescence). The article aims to present a complete examination of the topic, as it touches the background phenomena, instrumentation, spectra processing and data analytical methods, spectra interpretation and related information. To suit this goal, the article includes a tutorial information essential to obtain a thorough perspective of bio-related applications of the reviewed methodologies. The importance of the fundamental factors to the final performance and applicability of IR spectroscopy in various areas of bioscience is explained. This information is interpreted in critical way, with aim to gain deep understanding why IR spectroscopy finds extraordinarily intensive use in this remarkably diverse and dynamic field of research and utility. The major focus is placed on the diversity of the applications in which IR biospectroscopy has been established so far and those onto which it is expanding nowadays. This includes qualitative and quantitative analytical spectroscopy, spectral imaging, medical diagnosis, monitoring of biophysical processes, and studies of physicochemical properties and dynamics of biomolecules. The application potential of IR spectroscopy in light of the current accomplishments and the future prospects is critically evaluated and its significance in the progress of bioscience is comprehensively presented., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Vibrational coupling between carbohydrates and the hydration shell is unveiled as the underlying mechanism that improves wavenumber-selectively the carbohydrate discrimination performance by near-infrared (NIR) spectroscopy. The investigation is based on measurement of six carbohydrates (fructose, glucose, mannose, ribose, xylose and sorbitol) in aqueous solution in different concentration levels (5 mg/L, ~0.03 mmol/dm -3 and 20 mg/L, ~0.1 mmol/dm -3 ). The results of multivariate classification are interpreted by quantum mechanical NIR spectra simulations. The simulation unveils that the phenomenon is vibration-selective and thus wavenumber-selective, and leads to an enhancement of the qualitative information contained in the specific spectral regions. The location of these regions and the related performance correspond fully to the appearance and magnitude of the unveiled cooperative vibration effect., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

We investigated near-infrared (7500-4000 cm -1 ) spectra of n-hexanol, cyclohexanol and phenol in CCl 4 (0.2 M) by using anharmonic quantum calculations. These molecules represent three major kinds of alcohols; linear and cyclic aliphatic, and aromatic ones. Vibrational second-order perturbation theory (VPT2) was employed to calculate the first overtones and binary combination modes and to reproduce the experimental NIR spectra. The level of conformational flexibility of these three alcohols varies from one stable conformer of phenol through four conformers of cyclohexanol to few hundreds conformers in the case of n-hexanol. To take into account the most relevant conformational population of n-hexanol, a systematic conformational search was performed. Accurate reproduction of the experimental NIR spectra was achieved and detailed spectra-structure correlations were obtained for these three alcohols. VPT2 approach provides less reliable description of highly anharmonic modes, i.e. OH stretching. In the present work this limitation was manifested in erroneous results yielded by VPT2 for 2νOH mode of cyclohexanol. To study the anharmonicity of this mode we solved the corresponding time-independent Schrödinger equation based on a dense-grid probing of the relevant vibrational potential. These results allowed for significant improvement of the agreement between the calculated and experimental 2νOH band of cyclohexanol. Various important biomolecules include similar structural units to the systems investigated here. A detailed knowledge on spectral properties of these three types of alcohols is therefore essential for advancing our understanding of NIR spectroscopy of biomolecules., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The applicability of two elimination techniques for interferences occurring in measurements with cells of short pathlength using Fourier transform near-infrared (FT-NIR) spectroscopy was evaluated. Due to the growing interest in the field of vibrational spectroscopy in aqueous biological fluids (e.g. glucose in blood), aqueous solutions of d-(+)-glucose were prepared and split into a calibration set and an independent validation set. All samples were measured with two FT-NIR spectrometers at various spectral resolutions. Moving average smoothing (MAS) and fast Fourier transform filter (FFT filter) were applied to the interference affected FT-NIR spectra in order to eliminate the interference pattern. After data pre-treatment, partial least squares regression (PLSR) models using different NIR regions were constructed using untreated (interference affected) spectra and spectra treated with MAS and FFT filter. The prediction of the independent validation set revealed information about the performance of the utilized interference elimination techniques, as well as the different NIR regions. The results showed that the combination band of water at approx. 5200 cm -1 is of great importance since its performance was superior to the one of the so-called first overtone of water at approx. 6800 cm -1 . Furthermore, this work demonstrated that MAS and FFT filter are fast and easy-to-use techniques for the elimination of interference fringes in FT-NIR transmittance spectroscopy., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Quantum chemical reproduction of entire NIR spectra is a new trend, enabled by contemporary advances in the anharmonic approaches. At the same time, recent increase of the importance of NIR spectroscopy of biological samples raises high demand for gaining deeper understanding of NIR spectra of biomolecules, i.e. fatty acids. In this work we investigate saturated and unsaturated medium-chain fatty acids, hexanoic acid and sorbic acid, in the near-infrared region. By employing fully anharmonic density functional theory (DFT) calculations we reproduce the experimental NIR spectra of these systems, including the highly specific spectral features corresponding to the dimerization of fatty acids. Broad range of concentration levels from 5·10 -4 M in CCl 4 to pure samples are investigated. The major role of cyclic dimers can be evidenced for the vast majority of these samples. A highly specific NIR feature of fatty acids, the elevation of spectral baseline around 6500-4000cm -1 , is being explained by the contributions of combination bands resulting from the vibrations of hydrogen-bonded OH groups in the cyclic dimers. Based on the high agreement between the calculated and experimental NIR spectra, a detailed NIR band assignments are proposed for hexanoic acid and sorbic acid. Subsequently, the correlations between the structure and NIR spectra are elucidated, emphasizing the regions in which clear and universal traces of specific bands corresponding to saturated and unsaturated alkyl chains can be established, thus demonstrating the wavenumber regions highly valuable for structural identifications., (Copyright © 2017 Elsevier B.V. All rights reserved.)