The request for novel hyphenated instruments and techniques, capable of affording exhaustive information and results, is a focus continuously watched out. In this context, the present work aimed at the development of an integrated system combining gas chromatographic (GC) separation with mass spectrometry (MS) and (solid deposition) Fourier transform infrared spectroscopy (FTIR) detection. An external transfer line was designed in the lab for the parallel coupling of the two detectors, in such a way to obtain complementary analytical information consisting of an MS spectrum, an IR spectrum and linear retention indices (LRI), within a single analysis. The instrument performance was demonstrated for the analysis of a commercial mixture consisting of 139 hydrocarbons, comprising linear, branched, unsaturated and aromatic compounds. A 100-m poly(dimethylsiloxane) column was employed for the separation, and the outlet flow was split 95:5 between the IR and MS detectors using two uncoated capillaries. The IR spectra were acquired from solid deposits on a zinc selenide disc (-90 °C), over a spot (detector area) of about 0.1 mm2, in the range of 4000-700 cm-1 and at a resolution of 4 cm-1. Final identification of the separated compounds by a library search was achieved by excluding incorrect results, sequentially using a three-filter approach (85% similarity against reference MS and IR library spectra and ±10 LRI unit tolerance). Based on these preliminary results, the GC-MS/sd-FTIR system is a promising tool for the characterization of complex matrix constituents, for which identification is cumbersome, by using only one detection technique.

Food safety became one of the most critical issues owing to the large expansion of international trading and emission of various pollutants in air, water and soil. Fungal contamination of food and feed has attracted most of the attention in the last decade because of the emerging analytical tools that facilitate the detection and discrimination of fungal species in imported foodstuff, seeds, grains, plants, meats …etc. In this work, we give an insight on the application of integrated attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy and artificial-intelligence algorithms to the determination and discrimination of fungal species/strains which potentially infect plants, seeds and grains. The proposed method is based on a microcontroller which allows the PC to analyze a large number of samples via serial connection with an UART module. Penicillium chrysogenum, Aspergillus niger, Aspergillus fumigatus, Aspergillus solani, Aspergillus flavus and two different strains of Fusarium oxysporum were used as model microorganisms. The use of artificial-intelligence algorithms herein provides the advantage of automation enabling high throughput screening of large numbers of food samples in less than 5 s. In addition, the classification accuracy is enhanced by applying these machine-learning classification techniques. Principle component analysis (PCA) was used in order to extract the spectral discriminative features from the recorded fungal FTIR spectra. Three intelligent methods of classification; namely, artificial neural network (ANN), support-vector machine (SVM) and k-nearest neighbor (KNN), were used in this study in order to prove that integration of spectroscopic measurements with varying machine-learning methods give a simple analytical tool for detection and classification of foodborne pathogens. All the utilized classifiers gave an accuracy of 100 % and were able to discriminate different species and/or strains of the investigated fungi in few milliseconds.

Since both top and bottom illuminations are widely used in infrared transmission measurements, in this paper, we study the effects of different illuminations on the signatures in infrared microspectroscopy. By simulating a series of dielectric samples, we show that their extinction efficiency, Q ext $$ {Q}_{\\mathrm{ext}} $$ , remains unchanged when the direction of the incident plane wave is reversed, even though the field distributions both inside and outside of the sample may be dramatically different. We find features in Q ext $$ {Q}_{\\mathrm{ext}} $$ that are correlated with whispering gallery modes for one beam direction and correspond to completely different field distributions for the opposite beam direction. In addition, by linking the optical theorem and the reciprocity relation of far-field scattered field, we rigorously prove the invariance of Q ext $$ {Q}_{\\mathrm{ext}} $$ for arbitrary dielectric targets under opposite plane-wave illuminations. Furthermore, we show the difference in the apparent absorbance spectrum for opposite beam directions when considering numerical apertures.

The increasing global demand for cement significantly impacts greenhouse gas emissions and resource consumption, necessitating sustainable alternatives. This study investigates fresh geopolymer (GP) pastes incorporating 20 wt.% of five industrial wastes-suction dust, red mud from alumina production, electro-filter dust, and extraction sludges from food supplement production and from partially stabilized industrial waste-as potential replacements for traditional cement. Consistent synthesis methods are used to prepare the geopolymers, which are characterized for their physicochemical, mechanical, and biological properties. Ionic conductivity and pH measurements together with integrity tests, thermogravimetry analysis (TGA), and leaching analysis are used to confirm the stability of the synthesized geopolymers. Fourier-transform Infrared (FT-IR) spectroscopy is used to follow geopolymerization occurrences. Results for ionic conductivity, pH, and integrity revealed that the synthesized GPs were macroscopically stable. TGA revealed that the main mass losses were ascribable to water dehydration and to water entrapped in the geopolymer networks. Only the GP filled with the powder of the red mud coming from alumina production experienced a mass loss of 23% due to a partial waste degradation. FT-IR showed a red shift in the main Si-O-(Si or Al) absorption band, indicating successful geopolymer network formations. Additionally, most of the GPs filled with the wastes exhibited higher compressive strength (37.8-58.5 MPa) compared to the control (22 MPa). Only the GP filled with the partially stabilized industrial waste had a lower mechanical strength as its structure was highly porous because of gas formation during geopolymerization reactions. Despite the high compressive strength (58.5 MPa) of the GP filled with suction dust waste, the concentration of Sb leached was 25 ppm, which limits its use. Eventually, all samples also demonstrated effective antimicrobial activity against Escherichia coli and Staphylococcus aureus due to the alkaline environment and the presence of metal cations able to react with the bacterial membranes. The findings revealed the possibility of recycling these wastes within several application fields.

Reactions of bis(benzene)chromium (Bz2Cr) and ozone (O3) were studied using low-temperature argon matrix-isolation infrared spectroscopy with supporting DFT calculations. When Bz2Cr and O3 were co-deposited, they reacted upon matrix deposition to produce two new prominent peaks in the infrared spectrum at 431 cm-1 and 792 cm-1. These peaks increased upon annealing the matrix to 35 K and decreased upon UV irradiation at λ = 254 nm. The oxygen-18 and mixed oxygen-16,18 isotopic shift pattern of the peak at 792 cm-1 is consistent with the antisymmetric stretch of a symmetric ozonide species. DFT calculations of many possible ozonide products of this reaction were made. The formation of a hydrogen ozonide (H2O3) best fits the original peaks and the oxygen-18 isotope shift pattern. Energy considerations lead to the conclusion that the chromium-containing product of this reaction is the coupled product benzene-chromium-biphenyl-chromium-benzene (BzCrBPCrBz). 2Bz2Cr+O3→H2O3+BzCrBPCrBz, ∆Ecalc=-52.13kcal/mol.

In contrast to the traditional analysis of molecules using local mode behavior, where the degree of locality is given through a function in terms of Morse potential parameters, new criteria for locality/normality (LN) suitable for application to any molecular system are proposed. The approach is based on analysis of the connection between the algebraic normal and local mode representations. It is shown that both descriptions are equivalent as long as the polyad (total number of quanta) in the local representation is not conserved. The constraint of a local polyad conservation naturally provides a criterion for assigning an LN degree in quantitative form, without an analogue in configuration space. The correlation between the different parameters reveals the physical properties of molecules. A clear connection between the LN degree (based on the fundamentals) and spectroscopic properties is also presented, suggesting a promising approach for identifying mixtures of isotopologues.

Coffee bean oxidation is associated with enzymatic and non-enzymatic browning, the degradation of desirable aromatic compounds, the development of undesirable flavors, increased susceptibility to microbial spoilage, and volatile compound losses. This study investigated natural dry process (DP) and honey process (HP) green coffee beans stored in GrainPro® bags for 0, 5, 10, and 20 days under accelerated storage conditions at 30 °C, 40 °C, and 50 °C with relative humidity of 50%. A kinetic model was used to estimate the shelf life of the green coffee beans. DP recorded durability of 45.67, 29.9, and 24.92 days at 30 °C, 40 °C, and 50 °C, respectively, with HP 60.34, 38.07, and 19.22 days. Partial least squares (PLS) analysis was performed to build the models in order to predict the shelf life of coffee based on peroxide (PV) and thiobarbituric acid reactive substances (TBARS) values. In terms of prediction with leave-one-out cross-validation (LOOCV), PLS provided a higher accuracy for TBARS (R2 = 0.801), while PV was lower (R2 = 0.469). However, the auto-prediction showed good agreement among the observed and predicted values in both PV (R2 = 0.802) and TBARS (R2 = 0.932). Based on the variable importance of projection (VIP) scores, the ATR-FTIR peaks as 3000-2825, 2154-2150, 1780-1712, 1487-2483, 1186-1126, 1107-1097, and 1012-949 cm-1 were identified to be the most related to PV and TBARS on green coffee beans shelf life. ATR-FITR showed potential as a fast and accurate technique to evaluate the oxidation reaction that related to the loss of coffee quality during storage.

Classical potassium binders are used in the treatment of hyperkalemia and are widely associated with gastrointestinal side effects, with crystal colonic injury being rare but potentially fatal. In this report, we describe the case of an 82-year-old male with hyperkalemia and calcium polystyrene sulfonate crystal-associated colonic necrosis. Traditionally, this diagnosis has relied on the examination of crystal morphology and polarization through microscopy. Our study enhances crystal identification by incorporating an analysis of the physical characteristics of the crystals using infrared spectroscopy. This is the first description, to our knowledge, of the calcium polystyrene sulfonate infrared spectrum.

Hypophosphatasia (HPP) is a rare genetic condition associated with poor bone mineralization, low serum alkaline phosphatase, high urinary pyrophosphate excretion, and nephrocalcinosis. Nephrocalcinosis is thought to develop due to the increased filtered loads associated with hypercalcemia and hyperphosphatemia, but the composition of these calcifications is incompletely understood. We report the first ever magnesium pyrophosphate (MgPPi) urinary stone, which prompted the new diagnosis of HPP in a 12-year-old boy. Stone analysis labs should include infrared spectra of PPi salts in their reference libraries to facilitate identification of these rare but clinically important stones.

As a prototype adsorption reaction of gas Brønsted acid on oxides, we study the adsorption of formic acid on anatase. We perform infrared spectroscopy measurements of adsorbed HCOOH and HCOOD on TiO2 nanopowders, from 13 K up to room temperature in an ultra-high vacuum chamber. We assign the IR signals via computed spectra from nuclear quantum dynamics simulations using our divide-and-conquer semiclassical ab initio molecular dynamics method. The acid proton forms an extraordinarily short and strong hydrogen bond with the surface oxygen. The strength of this hydrogen bond, that compares to H bonds in ice at high pressures, is at the root of a substantial redshift with respect to the typical free OH stretching frequency, which eludes its straightforward detection.