Novel insights on the Pd speciation in Pd/SSZ-13 and on the role of H2O in the Pd reduction by CO.

Pd speciation induced by the combined effect of CO and water on Pd/SSZ-13 samples prepared by both impregnation and ion exchange was examined by FT-IR spectroscopy of CO adsorbed at room temperature and at liquid nitrogen temperature on anhydrous and hydrated samples. Starting from the literature findings related to the CO reducing effect on Pd cations, the present work gives precise spectroscopic evidences on how water is necessary in this process not only for compensating with H+ the zeolite exchange sites set free by Pd reduction, but also for mobilizing isolated Pd2+/Pd+ cations and making possible the reduction reactions. The aggregation of some Pd+ sites, just formed by the reduction and mobilized by the hydration, gives rise to the formation of Pd2O particles. Also, Pd0(100) sites are observed with CO on hydrated sample, formed by the aggregation and reduction of isolated Pd cations. Moreover, Pd0(111) sites are formed on the surface of PdOx particles during CO outgassing. The observation of the combined effect of water and CO allowed to define assignments of IR bands related to carbonyls of Pd in different oxidation states and coordination degrees.

Study of chemical reactivity and molecular interactions of the hydrochlorothiazide-4-aminobenzoic acid cocrystal using spectroscopic and quantum chemical approaches.

In this study, the molecular, electronic, and chemical properties of the drug hydrochlorothiazide (HCTZ) are determined after cocrystallization with 4-aminobenzoic acid (4-ABA). Analysis has been performed to understand how those variations lead to alteration of physical properties and chemical reactivity in the cocrystal HCTZ-4ABA. IR and Raman characterizations were performed along with quantum chemical calculations. A theoretical investigation of hydrogen bonding interactions in HCTZ-4ABA has been conducted using two functionals: B3LYP and wB97X-D. The results obtained by B3LYP and wB97X-D are compared which leads to the conclusion that B3LYP is the best applied function (density functional theory) to obtain suitable results for spectroscopy. The chemical reactivity descriptors are used to understand various aspects of pharmaceutical properties. Natural bond orbital (NBO) analysis and quantum theory of atoms (QTAIM) are used to analyze nature and strength of hydrogen bonding in HCTZ-4ABA. QTAIM analyzed moderate role of hydrogen bonding interactions in HCTZ-4ABA. The calculated HOMO-LUMO energy gap shows that HCTZ-4ABA is chemically more active than HCTZ drug. These chemical parameters suggest that HCTZ-4ABA is chemically more reactive and softer than HCTZ. The results of this study suggest that cocrystals can be a good alternative for enhancing physicochemical properties of a drug without altering its therapeutic properties.

Grape pomace and pecan shell fortified bread: The effect of dietary fiber-phenolic compounds interaction on the in vitro accessibility of phenolic compounds and in vitro glycemic index.

Grape pomace (GP) and pecan shell (PS) are two by-products rich in phenolic compounds (PC), and dietary fiber (DF) that may be considered for the development of functional baked foods. In this study, four formulations with different GP:PS ratios (F1(8%:5%), F2(5%:5%), F3(5%:2%), F4(0%:5%), and control bread (CB)) were elaborated and characterized (physiochemical and phytochemical content). Also, their inner structure (SEM), changes in their FTIR functional group's vibrations, and the bioaccessibility of PC and sugars, including an in vitro glycemic index, were analyzed. Results showed that all GP:PS formulations had higher mineral, protein, DF (total, soluble, and insoluble), and PC content than CB. Additionally, PC and non-starch polysaccharides affected gluten and starch absorbance and pores distribution. In vitro digestion model showed a reduction in the glycemic index for all formulations, compared to CB. These findings highlight the possible health benefits of by-products and their interactions in baked goods.

Guanosine hydrogels in focus: A comprehensive analysis through mid-infrared spectroscopy.

Guanosine nucleosides and nucleotides have the peculiar ability to self-assemble in water to form supramolecular complex architectures from G-quartets to G-quadruplexes. G-quadruplexes exhibit in turn a large liquid crystalline lyotropic polymorphism, but they eventually cross-link or entangle to form a densely connected 3D network (a molecular hydrogel), able to entrap very large amount of water (up to the 99% v/v). This high water content of the hydrogels enables tunable softness, deformability, self-healing, and quasi-liquid properties, making them ideal candidates for different biotechnological and biomedical applications. In order to fully exploit their possible applications, Attenuated Total Reflection-Fourier Transform InfraRed (ATR-FTIR) spectroscopy was used to unravel the vibrational characteristics of supramolecular guanosine structures. First, the characteristic vibrations of the known quadruplex structure of guanosine 5'-monophosphate, potassium salt (GMP/K), were investigated: the identified peaks reflected both the chemical composition of the sample and the formation of quartets, octamers, and quadruplexes. Second, the role of K+ and Na+ cations in promoting the quadruplex formation was assessed: infrared spectra confirmed that both cations induce the formation of G-quadruplexes and that GMP/K is more stable in the G-quadruplex organization. Finally, ATR-FTIR spectroscopy was used to investigate binary mixtures of guanosine (Gua) and GMP/K or GMP/Na, both systems forming G-hydrogels. The same G-quadruplex-based structure was found in both mixtures, but the proportion of Gua and GMP affected some features, like sugar puckering, guanine vibrations, and base stacking, reflecting the known side-to-side aggregation and bundle formation occurring in these binary systems.

Observation on Switching Properties of WO3-Based H2 Sensor Regulated by Temperature and Gas Concentration.

Transition metal oxide semiconductors have great potential for use in H2 sensors, but in recent years, the strange phenomena about gas-sensitive performance associated with their special properties have been more widely discussed in research. In some cases, the resistance of transition metal oxide gas sensors will emerge with some changes contrary to their intrinsic semiconductor characteristics, especially in gas sensor research of WO3. Based on the hydrothermal synthesis of WO3, our work focuses on the abnormal change of tungsten oxide resistance to different gases at low temperature (80-200 °C) and high temperature (above 200 °C). Through in situ FT-IR and in situ XPS, combined with density functional theory calculations, a new reasonable explanation of WO3 is proposed for the abnormal resistance change caused by temperature and the strange response due to gas concentration. The occurrence of these findings can be attributed to the synergistic effect resulting from the presence of two contributing factors. One of them is attributed to the alteration in the surface valence state of WO3 induced by gas, resulting in the reduction of W6+. The other one is due to the reaction between gas and adsorbed oxygen on the surface of WO3. This work presents a novel and rational concept for addressing the reaction mechanism between gas and transition metal oxide semiconductors, thereby paving the way for the development of highly efficient gas sensors based on transition metal oxide semiconductors.

Photocatalytic Nanocomposite Based on Titanate Nanotubes Decorated with Plasmonic Nanoparticles for Enhanced Broad-Spectrum Antibacterial Activity.

Infections resulting from microorganisms pose an ongoing global public health challenge, necessitating the constant development of novel antimicrobial approaches. Utilizing photocatalytic materials to generate reactive oxygen species (ROS) presents an appealing strategy for combating microbial threats. In alignment with this perspective, sodium titanate nanotubes were prepared by scalable hydrothermal method using TiO2 and NaOH. Ag, Au, and Ag/Au-modified titanate nanotubes (TNTs) were prepared by a cost-effective and simple ion-exchange method. All samples were characterized by XRD, FT-IR, HRTEM, and DLS techniques. HRTEM images indicated that the tubular structure was preserved in all TNTs even after the replacement of Na+ with Ag+ and/or Au3+ ions. The antibacterial activity in dark and sunlight conditions was evaluated using different bacterial strains, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The results showed that while a low bacterial count (∼log 5 cells per well) was used for inoculation, the TNTs exhibited no antibacterial activity against the three bacterial strains, regardless of whether they were tested under light or dark conditions. However, the plasmonic nanoparticle-decorated TNTs showed remarkable activity in the dark. Additionally, Ag/Au-TNTs demonstrated significantly higher activity in the dark compared with either Ag-TNTs or Au-TNTs alone. Notably, under dark conditions, the Au/Ag-TNTs achieved log reductions of up to 4.5 for P. aeruginosa, 5 for S. aureus, and 3.7 for E. coli. However, when exposed to sunlight, Au/Ag-TNTs resulted in a complete reduction (log reduction ∼9) for P. aeruginosa and E. coli. The combination of two plasmonic nanoparticles (Ag/Au) decorated on the surface of TNTs showed synergetic bactericidal activity under both dark and light conditions. Ag/Au-TNTs could be explored to design surfaces that are responsive to visible light and exhibit antimicrobial properties.

Analysis and discrimination of adhesive species using ATR-FTIR combined with Raman, and HS-GC-IMS together with multivariate statistical analysis.

Identifying the species and origin of adhesives in criminal investigations aids in narrowing inquiry scope and supporting case detection. This study introduces two advanced combined analytical techniques for distinguishing adhesive species, including attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) combined with Raman spectroscopy, and headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) together with multivariate statistical analysis. ATR-FTIR categorized seven adhesives into three groups based on the base materials, with further differentiation achieved via Raman spectra. Analysis of volatile components identified 79 volatile organic compounds (VOCs), with esters being the most concentrated. The fingerprint profile clearly illustrated the characteristic fingerprint sequence and unique marker compounds of each adhesive, effectively enabling their differentiation. Multivariate statistical analysis methods, including principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), heatmap, and hierarchical cluster analysis (HCA), were utilized to visually interpret the classification of adhesives. This integrated analytical approach provides a comprehensive analysis of adhesive compositions, facilitating the diversification and precision of adhesive species identification, and broadening the scope for detecting and analyzing trace evidence in forensic science.

Monitoring molecular events during photo-driven ubiquinone pool reduction in PufX+ and PufX- membranes from Rhobobacter capsulatus by time-resolved FTIR difference spectroscopy.

The PufX protein is found in the photosynthetic membranes of several purple bacteria and is involved in ubiquinol-ubiquinone exchange at the QB site of the reaction center. We have studied quinone pool reduction in chromatophores from PufX+ and PufX- strains of Rhodobacter capsulatus by time-resolved FTIR difference spectroscopy under and after continuous illumination. To our knowledge, it is the first time that quinone pool reduction has been directly followed in real time in Rba. capsulatus membranes. Thanks to the availability in the literature of IR marker bands for protein conformational changes, ubiquinone consumption, ubiquinol production, Q---QH2 quinhydrone complex formation, as well as for RC-bound QA- and QB- semiquinone species, it is possible to follow all the molecular events associated with light-induced quinone pool reduction. In Rba. capsulatus PufX + chromatophores, these events resemble the ones found in Rba. sphaeroides wild-type membranes. In PufX- chromatophores the situation is different. Spectra recorded during 22.7 s of illumination showed a much smaller amount of photoreduced quinol, consistent with previous observations that PufX is required for efficient QH2/Q exchange at the QB site of the RC. Q consumption and QH2 formation are rapidly associated with QA- formation, showing that the structure of the RC-LH1 complex in PufX- membranes does not provide efficient access to the QB site of the RC to a large fraction of the quinone pool, evidently because the LH1 ring increases in size to impair access to the RC. The presence of a positive band at 1560 cm-1 suggests also the transient formation, in a fraction of chromatophores or of RC-LH1 complexes, of a Q---QH2 quinhydrone complex. Experiments carried out after 2-flash and 10-flash sequences make it possible to estimate that the size of the quinone pool with access to the QB site in PufX- membranes is ≥ 5 ubiquinone molecules per RC. The results are discussed in the framework of the current knowledge of protein organization and quinone pool reduction in bacterial photosynthetic membranes.

Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) Spectroscopy Analysis of Saliva as a Diagnostic Specimen for Rapid Classification of Oral Squamous Cell Carcinoma Using Chemometrics Methods.

BACKGROUND & AIM: Recent advancements in analytical techniques have highlighted the potential of Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) spectroscopy as a quick, cost-effective, non-invasive, and efficient tool for cancer diagnosis. This study aims to evaluate the effectiveness of ATR-FTIR spectroscopy in combination with supervised machine learning classification models for diagnosing OSCC using saliva samples. METHODS & MATERIALS: Eighty unstimulated whole saliva samples from OSCC patients and healthy controls were collected. The ATR-FTIR spectroscopy was performed and spectral data were used to classify healthy and OSCC groups. The data were analyzed using machine learning classification methods such as Partial Least Squares-Discriminant Analysis (PLS-DA) and Support Vector Machine Classification (SVM-C). The classification performance of the models was evaluated by computing sensitivity, specificity, precision, and accuracy. RESULTS: The samples were classified into two classes based on their spectral data. The obtained results demonstrate a high level of accuracy in the prediction sets of the PLS-DA and SVM-C models, with accuracy values of 0.960 and 0.962, respectively. The OSCC group sensitivity values for both PLS-DA and SVM-C models was 1.00, respectively. CONCLUSION: The study indicates that ATR-FTIR spectroscopy, combined with chemometrics, is a potential method for the non-invasive diagnosis of OSCC using saliva samples. This method achieved high accuracy and the findings of this study suggest that ATR-FTIR spectroscopy could be further developed for clinical applications in OSCC diagnosis.

Growth, characterization and cognition of 2-cyanopyridinium perchlorate single crystals for nonlinear optical applications.

The fascinating electronic applications attracted researchers to explore the field of nonlinear optical (NLO) materials. The slow evaporation of solvent technique (SEST) was employed to grow the 2-cyanopyridinium perchlorate (2-CPPC) NLO single crystals. The cell parameters of the grown 2-CPPC crystal are confirmed by the single crystal X-ray diffraction (SCXRD) study. The powder X-ray diffraction studies confirm the crystallinity of 2-CPPC crystals, and the peaks were indexed. The computation for the geometry optimization, HOMO-LUMO energy gap, global reactivity parameters, natural bond orbital (NBO) analysis, polarizability, and hyperpolarizability of the 2-CPPC molecule was done using B3LYP (6-311G basis set) functional of DFT method. The experimental FTIR and UV-Vis results of the 2-CPPC compound were compared with the simulated results. The second harmonic generation (SHG) study for the 2-CPPC crystal was employed using Kurtz-Perry powder technique. Single beam Z-scan technique using He-Ne laser is used to study the third-order NLO properties.

Untargeted Metabolomics Analysis Using FTIR and LC-HRMS for Differentiating Sonchus arvensis Plant Parts and Evaluating Their Biological Activity.

The composition and concentration of compounds in medicinal plants vary based on several factors, including the specific part of the plant being used. These variations in composition and concentration lead to differences in biological activity levels. In this study, we aimed to assess the phytochemical profile of Sonchus arvensis and to investigate the biological activity of different plant parts (roots, stems, and leaves) using a metabolomics approach. We analyzed the plant extracts for total phenolic and flavonoid levels, antioxidant activity, and xanthine oxidase inhibition. We also conducted metabolite profiling using Fourier-transform infrared spectroscopy and liquid chromatography-high resolution mass spectrometry. A total of 17 metabolites were identified (13 in leaves, 10 in stems, and 9 in roots). Principal component analysis effectively differentiated S. arvensis extracts based on differences in plant parts. These findings indicate that the quantity and diversity of metabolites present in the roots, stems, and leaves influence the biological activity of S. arvensis.

Synthesis, characterization, and crystal structure of hexa-kis-(1-methyl-1H-imidazole-κN 3)zinc(II) dinitrate.

The synthesis of the title compound, [Zn(C4H6N2)6](NO3)2, is described. This complex consists of a central zinc metal ion surrounded by six 1-methyl-imidazole ligands, charge balanced by two nitrate anions. The complex crystallizes in the space group P. In the crystal, the nitrate ions are situated within the cavities created by the [Zn(N-Melm)6]2+ cations, serving as counter-ions. The three oxygen atoms of the nitrate ion engage in weak C-H⋯O inter-actions. In addition to single-crystal X-ray diffraction analysis, the complex was characterized using elemental analysis, 1H NMR, 13C NMR, and FTIR spectroscopy.

Unveiling the impact of organically activated biochar on physiological, biochemical, and yield attributes of maize under varied field moisture conditions.

Water deficiency in semiarid regions is a limiting factor that affects crop quality and yield. In Punjab, Pakistan, a 27% decline in maize yield was detected over the past two decades just because of water scarcity. Currently, no studies have reported the effects of organically activated biochar (AB) on crop productivity under natural field conditions. For this purpose, a field experiment in a split-split-plot design was conducted with three amendment levels (0, 2, and 4 tonnes ac-1), and three maize hybrids (DK-9108, DK-6321, and Sarhaab) under 100%, 70%, and 50% irrigation water (IW) of crop evapotranspiration (ETc). The AB significantly improved the soil's physical and chemical properties, and maximum improvement was recorded in 4 tonnes ac-1 AB amendment in organic matter (16.6%), total organic carbon (17%), phosphorus (11.43%), and available potassium (29.27%). The 4 tonnes ac-1AB amendment in soil had a significant impact on total chlorophyll content (0.3-1-fold in DK-6321), carotenoid content (3.9-4.4-fold in Sarhaab), and relative water content (30% and 21% in Sarhaab) under 50% irrigation water (IW) of ETc at V14th and R3 stages, respectively. Moreover, a significant decline in stress markers (proline content and sugar content) was detected at both growth stages in all maize hybrids in AB amended soil. The analysis of plant metabolites indicated increased intensities of phenolics, alkyl esters, and carbohydrates by 2.5-7%, 17-80%, and 40-43% in DK-6321 under 50% IW in 2-4 tonnes ac-1 AB amended soil, respectively. The highest improvement in growth and yield attributes among maize hybrids was detected in the order DK-6321¿DK-9108¿Sarhaab in 2-4 tonnes ac-1AB amended soil under 70% and 50% IW of ETc, respectively. Hence, this research might help to develop an effective soil amendment to restore degraded soils and improve maize growth under arid climatic conditions.

Valorization of treated wastewater from the soaking of baby alpaca skin fur.

Baby alpaca fur industry generates considerable wastewater during the soaking process, which contains high levels of total suspended solids (TSSs), proteins, and salts, among other components. The valorization of wastewater after precipitation, coagulation-flocculation, and aeration treatments was evaluated for use in irrigation water, fertigation, groundwater recharge, concrete construction, and disposal. The precipitation treatment sludge and the coagulation-flocculation treatment were evaluated as a protein source, soil quality improvement, and disposal. The treatment system included evaluations of nine pH levels, seven coagulant doses, and seven aeration times. The contents of TSSs, chemical oxygen demand (COD), total Kjeldalh nitrogen (TKN), ammonia nitrogen (N-NH3), and oils and fats (O&G), among other parameters, were determined in the treated and untreated wastewater. Before entering the treatment system, the physicochemical characterization of the wastewater showed a high concentration of parameters related to organic matter and dust, such as O&G, five-day biological oxygen demand (BOD5), COD, TSSs, TKN, and N-NH3. The optimal removal parameters were pH 12 for the chemical precipitation of proteins, a dose of 480 mg/L FeCl3 as a coagulant for TSSs removal, and 150 min of aeration; removal efficiencies of 99.02 %, 77.49 %, 79.93 %, and 64.62 % for TSSs, Cod, TKN, and N-NH3, respectively, were obtained. The wastewater after treatment can be used for groundwater recharge and concrete construction, and the wastewater with 2 % dilution can be used for irrigation water and fertigation. The sludge after precipitation is rich in protein and can be used as a protein source or soil quality improver.

Toxic Effects of 4-Bromodiphenyl Ether (BDE-3) on Antioxidant Enzymes, Cell Viability, Histology and Biomolecules in Zebrafish Embryo-Larvae.

Polybrominated diphenyl ethers (PBDEs) are a class of flame retardants that are being used widely in industrial and consumers products such as plastics, electronics, furniture, textiles and so forth. They can undergo debromination process to form less brominated diphenyl ethers, which are bioaccumulative, more volatile and more toxic in nature. The current study was conducted to reveal the biochemical, apoptotic, histopathological, ultrastructural and biomolecular (ATR-FTIR) toxicity of 4-bromodiphenyl ether (BDE-3) in zebrafish larvae. After the 96-h LC50 determination, the zebrafish embryos were exposed to sublethal concentrations of BDE-3, that is, 0.79 and 1.59 mg/L. The MDA content was found to be significantly increased in BDE-3 exposed larvae whereas the FRAP activity was found to be decreased. The catalase (CAT), glutathione-S-transferase (GST) and acetylcholinesterase (AChE) activity were observed to be significantly increased, and a decreased superoxide dismutase (SOD) activity was reported after the BDE-3 exposure in zebrafish larvae. The cell viability was reported to be decreased in zebrafish larvae after BDE-3 exposure. Histopathological and ultrastructural alterations were also observed in the BDE-3 exposed zebrafish larvae. The changes in the biomolecules such as DNA and protein were also revealed via ATR-FTIR analysis. The present investigation will help to understand the toxic nature of less brominated diphenyl ethers and could be utilised to assess environmental risk.

Electronic structure, global reactivity descriptors and nonlinear optical properties of glycine interacted with ZnO, MgO and CaO for bacterial detection.

Modern laboratory medicine relies on analytical instruments for bacterial detection, focusing on biosensors and optical sensors for early disease diagnosis and treatment. Thus, Density Functional Theory (DFT) was utilized to study the reactivity of glycine interacted with metal oxides (ZnO, MgO, and CaO) for bacterial detection. Total dipole moment (TDM), frontier molecular orbitals (FMOs), FTIR spectroscopic data, electronic transition states, chemical reactivity descriptors, nonlinear optical (NLO) characteristics, and molecular electrostatic potential (MESP) were all investigated at the B3LYP/6-31G(d, p) level using DFT and Time-Dependent DFT (TD-DFT). The Coulomb-attenuating approach (CAM-B3LYP) was utilized to obtain theoretical electronic absorption spectra with the 6-31G(d, p) basis set to be more accurate than alternative quantum chemical calculation approaches, showing good agreement with the experimental data. The TDM and FMO investigation showed that glycine/CaO model has the highest TDM (10.129Debye) and lowest band gap (1.643 eV). The DFT computed IR and the experimental FTIR are consistent. The calculated UV-vis spectra showed a red shift with an increase in polarity following an increase in the absorption wavelength due to the interaction with ZnO, MgO, and CaO. Among the five solvents of water, methanol, ethanol, DMSO and acetone, the water and DMSO enhances the UV-Vis absorption. Glycine/CaO model showed high linear polarizability (14.629 × 10-24esu) and first hyperpolarizability (23.117 × 10-30esu), indicating its potential for nonlinear optical applications. The results showed that all model molecules, particularly glycine/CaO, contribute significantly to the development of materials with potential NLO features for sensor and optoelectronic applications. Additionally, MESP confirmed the increased electronegativity of the studied structures. Additionally, glycine/ZnO nanocomposite was synthesized and characterized using IR and UV-visible spectroscopy to determine their structural and spectroscopic features. It was discovered that there was good agreement between the DFT computed findings and the related experimental data. The antibacterial activity of glycine/ZnO nanocomposites against Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa were studied in terms of concentration and time. The results showed that increasing the concentration of glycine/ZnO nanocomposite significantly enhanced its antibacterial efficacy by lowering optical density. Notably, Pseudomonas aeruginosa exhibited lower susceptibility to the nanocomposite compared to S. aureus, requiring higher concentrations for effective bactericidal action. In summary, this study contributes novel insights into the dual functionality of glycine-metal oxide complexes, with significant implications as optical biosensor for microbial detection.

Semi-quantitative chemometric models for characterization of mixtures of sugars using infrared spectral data.

Sugars (saccharides) are sweet-tasting carbohydrates that are abundant in foods and play very important roles in living organisms, particularly as sources and stores of energy, and as structural elements in cellular membranes. They are desirable therapeutic targets, as they participate in multiple metabolic processes as fundamental elements. However, the physicochemical characterization of sugars is a challenging task, mostly due to the structural similarity shared by the large diversity of compounds of this family. The need for fast, accurate enough, and cost-effective analytical methods for these substances is of extreme relevance, in particular because of the recently increasing importance of carbohydrates in Medicine and food industry. With this in view, this work focused on the development of chemometric models for semi-quantitative analysis of samples of different types of sugars (glucose, galactose, mannitol, sorbose and fructose) using infrared spectra as data, as an example of application of a novel approach, where the Principal Component Analysis (PCA) score plots are used to estimate the composition (weight-%) of the mixtures of the sugars. In these plots, polygonal geometric shapes emerge in the vectorial space of the most significant principal components, that allow grouping different types of samples on the vertices, edges, faces and interior of the polygons according to the composition of the samples. This approach was applied successfully to mixtures of up to 5 sugars and shown to appropriately extract the compositional information from the hyper-redundant complex spectral data. Thought the method has been applied here to a specific problem, it shall be considered as a general procedure for the semi-quantitative analysis of other types of mixtures and applicable to other types of data reflecting their composition. In fact, the methodology appears as an efficient tool to solve three main general problems: (i) use hyper-redundant (in variables) data, as spectral information, directly and with minimum pre-treatment, to evaluate semi-quantitatively the composition of mixtures; (ii) do this for systems which produce data that can be considered rather similar; and (iii) do it for a number of substances present in the mixtures that might be greater than that usually considered in chemistry, which in general is limited to 3 components. In addition, this work also demonstrates that, similarly to the developed analysis based on the PCA score plots, the Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) chemometric method can also be used successfully for the qualitative (when used without any previous knowledge of the components present in the samples) or semi-quantitative (when the pure components spectral profiles are provided as references) analyses of mixtures of (at least) up to 5 distinct sugars.

Molecular profiling of blood plasma-derived extracellular vesicles derived from Duchenne muscular dystrophy patients through integration of FTIR spectroscopy and machine learning reveals disease signatures.

PURPOSE: To identify and monitor the FTIR spectral signatures of plasma extracellular vesicles (EVs) from Duchenne Muscular Dystrophy (DMD) patients at different stages with Healthy controls using machine learning models. MATERIALS AND METHODS: Whole blood samples were collected from the DMD (n = 30) and Healthy controls (n = 12). EVs were extracted by the Total Exosome Isolation (TEI) Method and resuspended in 1XPBS. We characterize the morphology, size, particle count, and surface markers (CD9, Alix, and Flotillin) by HR-TEM, NTA, and Western Blot analysis. The mid-IR spectra were recorded from (4000-400 cm-1) by Bruker ALPHA II FTIR spectrometer model, which was equipped with an attenuated total reflection (ATR) module. Machine learning algorithms like Principal Component Analysis (PCA) and Random Forest (RF) for dimensionality reduction and classifying the two study groups based on the FTIR spectra. The model performance was evaluated by a confusion matrix and the sensitivity, specificity, and Receiver Operating Characteristic Curve (ROC) was calculated respectively. RESULTS: Alterations in Amide I & II (1700-1470 cm-1) and lipid (3000-2800 cm-1) regions in FTIR spectra of DMD compared with healthy controls. The PCA-RF model classified correctly the two study groups in the range of 4000-400 cm-1 with a sensitivity of 20 %, specificity of 87.50 %, accuracy of 71.43 %, precision of 33.33 %, and 5-fold cross-validation accuracy of 82 %. We analyzed the ten different spectral regions which showed statistically significant at P < 0.01 except the Ester Acyl Chain region. CONCLUSION: Our proof-of-concept study demonstrated distinct infrared (IR) spectral signatures in plasma EVs derived from DMD. Consistent alterations in protein and lipid configurations were identified using a PCA-RF model, even with a small clinical dataset. This minimally invasive liquid biopsy method, combined with automated analysis, warrants further investigation for its potential in early diagnosis and monitoring of disease progression in DMD patients within clinical settings.

Beach wracks microbiome and its putative function in plastic polluted Mediterranean marine ecosystem.

The coasts of the world's oceans and seas accumulate various types of floating debris, commonly known as beach wracks, including organic seaweeds, seagrass, and ubiquitous anthropogenic waste, mainly plastic. Beach wrack microbiome (MB), surviving in the form of a biofilm, ensures decomposition and remineralization of wracks, but can also serve as a vector of potential pathogens in the environment. Through the interdisciplinary approach and comprehensive sampling design that includes geological analysis of the sediment, plastic debris composition analysis (ATR-FTIR) and application of 16S rRNA gene metabarcoding of beach wrack MBs, this study aims to describe MB in relation to beach exposure, sediment type and plastic pollution. Major contributors in beach wrack MB were Proteobacteria, Bacteroidetes, Actinobacteria, Planctomycetes, Verrucomicrobia and Firmicutes and there was significant dissimilarity between sample groups with Vibrio, Cobetia and Planococcus shaping the Exposed beach sample group and Cyclobacteriaceae and Flavobacterium shaping the Sheltered beach sample group. Our results suggest plastisphere MB is mostly shaped by beach exposure, type of seagrass, sediment type and probably beach naturalness with heavy influence of seawater MB and shows no significant dissimilarity between MBs from a variety of microplastics (MP). Putative functional analysis of MB detected plastic degradation and potential human pathogen bacteria in both beach wrack and seawater MB. The research provides the next crucial step in beach wrack MP accumulation research, MB composition and functional investigation with focus on beach exposure as an important variable.

New phase transition of p-cresol studied by DSC analysis and FT-IR spectroscopy.

We have investigated polymorphism in p-cresol using the FT-IR spectroscopy and differential scanning calorimetry. The present results show that in addition to the well-known two crystalline phases of p-cresol, which melts at 307.6 and 309.2 K, we discovered the existence of a new crystalline phase, which melts at 302.9 K. For the first time we have received the FT-IR spectra of three polymorphs and their temperature dependencies in the region 300-12 K. Comparison between the FT-IR spectra of three polymorphs shows that they are completely different.