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This study investigates the combined effects of nanoscale surface roughness and electron-phonon interaction on the vibrational modes of cadmium telluride (CdTe) using resonant Raman spectroscopy. Raman spectra simulations aided in identifying the active phonon modes and their dependence on roughness. Our results reveal that increasing surface roughness leads to an asymmetric line shape in the first-order longitudinal optical (1LO) phonon mode, attributed to an increase in the electron-phonon interaction. This asymmetry broadens the entire Raman spectrum. Conversely, the overtone (second-order longitudinal optical [2LO]) mode exhibits a symmetrical line shape that intensifies with roughness. Additionally, we identify and discuss the contributions of surface optical phonon mode and multiphonon modes to the Raman spectra, highlighting their dependence on roughness. This work offers a deeper understanding of how surface roughness and electron-phonon scattering influence the line shape of CdTe resonant Raman spectra, providing valuable insights into its vibrational properties.

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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.

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Fish are excellent bioindicators and can reveal the presence of plastic in the environment. Diagnosing the composition and abundance of polymers in the fish diet makes it possible to evaluate their point sources and possible trophic transfers. We aimed to use the gastrointestinal contents of Poecilia reticulata in subtropical urban streams to detect the occurrence, shape, color, size, and chemical composition of polymers. For this, the diet of 240 individuals was analyzed using the volumetric method, and the microplastics (MPs; < 5 mm) recorded were characterized using Raman spectroscopy. Individuals predominantly consumed organic detritus and aquatic macroinvertebrates, with higher proportions of Diptera. A total of 111 plastic particles (< 0.5 to 12 mm) were recorded, and a subset of 14.4% was subjected to a micro-Raman spectrometer (830 nm excitation). The occurrence of polyethylene terephthalate (PET) and polypropylene (PP) with phthalocyanine dye was recorded. Some fragments could not be identified by Raman, but they contained indigo blue dye. Poecilia reticulata had a predominantly detritivorous diet with a record of plastic consumption, reflecting environmental pollution. Our results demonstrate that individuals of P. reticulata have ingested MPs in urban streams. This reinforces the need for future studies on the relationship between the presence of MPs in fish and the level of pollution in streams, comparisons with species of different feeding habits, and the potentially harmful effects on the entire biota.

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The presence of microplastics in freshwater systems can have harmful effects on the food chain. Zooplankton, especially suspension and filter feeders, can ingest microplastics, which can cause adverse effects and transfer them to higher trophic levels. Here, we analyze the presence, abundance, and distribution of microplastics in surface water, zooplankton, and fish in two tropical lakes in central Mexico. We collected water samples in triplicate at three sites in each lake and 120 fish of the genus Chirostoma. From each water sample, 300 rotifers and 150 microcrustaceans were randomly isolated and processed independently. Of the particles found in the water, zooplankton, and fish from both lakes, the fragments were the predominant ones. The total abundance of microplastics in the water column of both lakes varied between 1.2 and 17.0 items L-1. In zooplankton, fragments were found predominantly with up to 0.1 items ind-1, while in fish, up to 4.5 items ind-1 was recorded. Our results confirm the presence of microplastics in different compartments of the food webs of freshwater bodies, water column, zooplankton, and fish. Further work is required on the possible effects of these stressors at the different trophic levels.

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The World Health Organization categorizes air pollution as the presence of one or more contaminants in the atmosphere such as smoke, dust, and particulate matter like microplastics, which are considered a priority pollutant. However, only a few studies have been developed on atmospheric pollution, and knowledge about MPs in the atmosphere is still limited. Spider webs have been tested and used as a passive sampling approach to study anthropogenic pollution. Despite this, studies on microplastic contamination using spiderwebs as samplers are scarce. Thus, this study uses spider webs as passive indicators to investigate air quality regarding microplastic contamination in an urbanized area. Therefore, 30 sampling points were selected, and webs of Nephilingis cruentata were collected. The spider webs were dipped in KOH 10 %. After digestion, the solution was washed and sieved through a 90 µm geological sieve. The remaining material was transferred to a Petri dish with filter paper, quantified, and identified by type and color. The chemical composition of the polymers was determined using Raman spectroscopy. 3138 microplastics were identified (2973 filaments and 165 fragments). The most frequent colors were blue and black. Raman spectroscopy revealed five types of polymers: Isotactic Polypropylene, Polyethylene Terephthalate, Polyurethane, Polyamide, and Direct Polyethylene.

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Bacteriocins are antimicrobial compounds that have awakened interest across several industries due to their effectiveness. However, their large-scale production often becomes unfeasible on an industrial scale, primarily because of high process costs. Addressing this challenge, this work analyzes the potential of using low-cost whey permeate powder, without any supplementation, to produce bacteriocin-like inhibitory substances (BLIS) through the fermentation of Latilactobacillus sakei. For this purpose, different concentrations of whey permeate powder (55.15 gL-1, 41.3 gL-1 and 27.5 gL-1) were used. The ability of L. sakei to produce BLIS was evaluated, as well as the potential of crude cell-free supernatant to act as a preservative. Raman spectroscopy and surface-enhanced Raman scattering (SERS) provided detailed insights into the composition and changes occurring during fermentation. SERS, in particular, enhanced peak definition significantly, allowing for the identification of key components, such as lactose, proteins, and phenylalanine, which are crucial in understanding the fermentation process and BLIS characteristics. The results revealed that the concentration of 55.15 gL-1 of whey permeate powder, in flasks without agitation and a culture temperature of 32.5 °C, presented the highest biological activity of BLIS, reaching 99% of inhibition of Escherichia coli and Staphylococcus aureus with minimum inhibitory concentration of 36-45%, respectively. BLIS production began within 60 h of cultivation and was associated with class II bacteriocins. The results demonstrate a promising approach for producing BLIS in an economical and environmentally sustainable manner, with potential implications for various industries.

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This study aimed to identify differences in the composition of whole blood of patients with chronic kidney disease (CKD), before and after a hemodialysis session (HDS), and possible differences in blood composition between stages and between genders using Raman spectroscopy and principal component analysis (PCA). Whole blood samples were collected from 40 patients (20 women and 20 men), before and after a HDS. Raman spectra were obtained and the spectra were evaluated by PCA and partial least squares (PLS) regression. Mean spectra and difference spectrum between the groups were calculated: stages Before and After HDS, and gender Women and Men, which had their most intense peaks identified. Stage: mean spectra and difference spectrum indicated positive peaks that could be assigned to red blood cells, hemoglobin and deoxi-hemoglobin in the group Before HDS. There was no statistically significant difference by PCA. Gender: mean spectra and difference spectrum Before HDS indicated positive peaks that could be assigned to red blood cells, hemoglobin and deoxi-hemoglobin with greater intensity in the group Women, and negative peaks to white blood cells and serum, with greater intensity in the group Men. There was statistically significant difference by PCA, which also identified the peaks assigned to white blood cells, serum and porphyrin for Women and red blood cells and amino acids (tryptophan) for Men. PLS model was able to classify the spectra of the gender with 83.7% accuracy considering the classification per patient. The Raman technique highlighted gender differences in pacients with CKD.

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BACKGROUND: Amelogenesis imperfecta is a hereditary disorder affecting dental enamel. Among its phenotypes, hypocalcified AI is characterized by mineral deficiency, leading to tissue wear and, consequently, dental sensitivity. Excessive fluoride intake (through drinking water, fluoride supplements, toothpaste, or by ingesting products such as pesticides or insecticides) can lead to a condition known as dental fluorosis, which manifests as stains and teeth discoloration affecting their structure. Our recent studies have shown that extracts from Colombian native plants, Ilex guayusa and Piper marginatum, deposit mineral ions such as phosphate and orthophosphate into the dental enamel structure; however, it is unknown whether these extracts produce toxic effects on the dental pulp. OBJECTIVE: To assess cytotoxicity effects on human dental pulp stem cells (hDPSCs) exposed to extracts isolated from I. guayusa and P. marginatum and, hence, their safety for clinical use. METHODS: Raman spectroscopy, fluorescence microscopy, and flow cytometry techniques were employed. For Raman spectroscopy, hDPSCs were seeded onto nanobiochips designed to provide surface-enhanced Raman spectroscopy (SERS effect), which enhances their Raman signal by several orders of magnitude. After eight days in culture, I. guayusa and P. marginatum extracts at different concentrations (10, 50, and 100 ppm) were added. Raman measurements were performed at 0, 12, and 24 h following extract application. Fluorescence microscopy was conducted using an OLIMPUS fv1000 microscope, a live-dead assay was performed using a kit employing a BD FACS Canto TM II flow cytometer, and data analysis was determined using a FlowJo program. RESULTS: The Raman spectroscopy results showed spectra consistent with viable cells. These findings were corroborated using fluorescence microscopy and flow cytometry techniques, confirming high cellular viability. CONCLUSIONS: The analyzed extracts exhibited low cytotoxicity, suggesting that they could be safely applied on enamel for remineralization purposes. The use of nanobiochips for SERS effect improved the cell viability assessment.

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This work aimed to set inline Raman spectroscopy models to monitor biochemically (viable cell density, cell viability, glucose, lactate, glutamine, glutamate, and ammonium) all upstream stages of a virus-like particle-making process. Linear (Partial least squares, PLS; Principal components regression, PCR) and nonlinear (Artificial neural networks, ANN; supported vector machine, SVM) modeling approaches were assessed. The nonlinear models, ANN and SVM, were the more suitable models with the lowest absolute errors. The mean absolute error of the best models within the assessed parameter ranges for viable cell density (0.01-8.83 × 106 cells/mL), cell viability (1.3-100.0 %), glucose (5.22-10.93 g/L), lactate (18.6-152.7 mg/L), glutamine (158-1761 mg/L), glutamate (807.6-2159.7 mg/L), and ammonium (62.8-117.8 mg/L) were 1.55 ± 1.37 × 106 cells/mL (ANN), 5.01 ± 4.93 % (ANN), 0.27 ± 0.22 g/L (SVM), 4.7 ± 2.6 mg/L (SVM), 51 ± 49 mg/L (ANN), 57 ± 39 mg/L (SVM) and 2.0 ± 1.8 mg/L (ANN), respectively. The errors achieved, and best-fitted models were like those for the same bioprocess using offline data and others, which utilized inline spectra for mammalian cell lines as a host.

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Nanoporous gold electrodes are of great interest in electroanalytical chemistry, because of their unusual activity and large surface area. The electrochemical activity can be further improved by coating with molecular catalysts such as the tetraruthenated cobalt-tetrapyridylporphyrazines investigated in this work. The plasmonic enhancement of the scattered light at the nanoholes and borders modifies the electrode's optical characteristics, improving the transmission through the surface-enhanced Raman scattering (SERS) effect. When monitored by hyperspectral dark-field and confocal Raman microscopy, this effect allows probing of the porphyrazine species at the plasmonic nanholes, improving the understanding of the chemically modified gold electrodes.

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The significance of accurate determination of ethanol content in hydrogel formulations was accentuated during COVID-19 pandemic coinciding with the heightened demand for sanitizing agents. The present article proposes three robust methodologies for this purpose: Fourier Transform Infrared Spectroscopy (FTIR), Raman spectroscopy, and Densitometry with matrix effect correction by Near-Infrared Spectroscopy (NIR). All three methods demonstrated outstanding linearity (R2 ≥ 0.99) and minimal errors (< 1.7%), offering simplicity and operational efficiency. FTIR and Raman, being non-destructive and requiring minimal preparation, enable practical on-site analysis capabilities, underscoring the potential of the spectroscopic methods to expedite health investigations and inspections, empowering on-site ethanol determination, and relieving the burden on official laboratories. Additionally, the densitometry with NIR-based approach showcased superior accuracy and precision compared to spectroscopic methods, meeting validation criteria while offering operational advantages over the costly official distillation-based method. Therefore, it stands as a reliable and reproducible technique for comprehensive health and criminal compliance assessments, making it a compelling alternative for both industry and official laboratories.

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This study summarizes the concentration in dry weight (dw) of several metal(oid)s (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn), as well as the abundance and characteristics of microplastics (MP) in wet weight (ww) of the soft tissues of clam Corbicula fluminea from Chubut River (Patagonia, Argentina). The contents of essential elements were in the following decreasing order: Zn > Mn > Cu > Ni; meanwhile, non-essential elements Cd, Cr and Pb were below the detection limit (<0.5 µg/g dw). A high mean concentration of As (6.1 ± 0.3 µg/g dw) was found, surpassing the maximum allowable limit established by the Argentine Food Code for bivalve molluscs. The number of MP ranged from 0.07 to 1.27 items/ind. and from 0.2 to 2.9 items/g ww. Fibers were the most common shape, mainly transparent. The size of MP ranged from 42 to 1917 µm, accounting for 62 % of MP between 50 and 450 µm. The dominant polymer was PET based on the results of Raman spectroscopy. Based on the widespread distribution of MP in the environment and the wide range of effects on organisms, it is necessary to develop long-term monitoring programs for MP contamination in different environmental matrices. Understanding the bioaccumulation of MP in bivalves is crucial to assess the potential risk to human health through consumption and to the ecosystem. We propose that the widespread Asian clam could serve as a useful biomonitor for MP and As pollution in freshwater and estuarine environments such as the Chubut River.

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Objective: To evaluate the influence of opacity and the layering technique on the fluorescence of different composite resins. Materials and Methods: Two opacities (enamel and dentin) and the layering technique (enamel + dentin) of the composite resins: Filtek® Z350 and Palfique LX5 were evaluated in vitro. Composite resin discs were fabricated using a preformed matrix of 10 mm diameter and 0.5 mm thick for the single opacity groups and 10 mm thick for the layering technique groups, using 2 layers of 0.5 mm thickness of each opacity (n = 5). Specimens were analyzed using the Raman spectroscopy method. Data were analyzed using the Kruskall-wallis and Mann-Whitney U tests. Results: When evaluating the intensity of fluorescence, no statistically significant difference was found when comparing the layering technique and enamel opacity (p2> 0.05) and an increase in the dentin opacity value for both brands of composite resin. Regarding wavelength, no statistically significant difference was found when comparing the layering technique with enamel opacity and dentin opacity for both Filtek® Z350 and Palfique LX5® composite resins (p2 > 0.05). Conclusions: The fluorescence intensity of the layering technique is similar to enamel opacity for both composite resins. Likewise, the wavelength of the layering technique is similar to the enamel opacity and dentin opacity for both brands.

Objetive: Evaluar la influencia de la opacidad y de la técnica de estratificación en la fluorescencia de diferentes resinas compuestas. Materiales y Métodos: Se evaluó in vitro 2 opacidades (Esmalte y Dentina) y la técnica de estratificación (Esmalte + Dentina) de las resinas compuestas: Filtek® Z350 y Palfique LX5. Se fabricaron discos de resina compuesta, utilizando una matriz preformada de 10 mm de diámetro y 0,5 mm de grosor para los grupos de opacidad única y 10 mm de grosor para los grupos de técnica estratificada, utilizando 2 capas de 0,5 mm de cada opacidad (n = 5). Los especímenes se analizaron mediante el método de Espectroscopía Raman. Los datos se analizaron utilizando la prueba de Kruskall-wallis y Prueba U de Mann Whitney. Resultado: Al evaluar la intensidad de fluorescencia no se encontró diferencia estadísticamente significativa entre los pares: Técnica estratificada versus Opacidad Esmalte para ambas marcas de resina compuesta Filtek® Z350 y para Palfique LX5® (p2 > 0,05). Para longitud de onda no se encontró diferencia estadísticamente significativa entre los pares: Técnica estratificada versus Opacidad Esmalte y Técnica estratificada VS Opacidad Dentina para ambas resinas compuesta Filtek® Z350 y Palfique LX5® (p2> 0,05). Conclusión: La intensidad de fluorescencia de la técnica estratificada es similar a la opacidad Esmalte para ambas resinas compuestas. De igual manera la longitud de onda de la técnica estratificada es similar a la opacidad Esmalte y opacidad Dentina para ambas marcas.

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Azospirillum brasilense is a non-photosynthetic α-Proteobacteria, belongs to the family of Rhodospirillaceae and produces carotenoids to protect itself from photooxidative stress. In this study, we have used Resonance Raman Spectra to show similarity of bacterioruberins of Halobacterium salinarum to that of A. brasilense Cd. To navigate the role of genes involved in carotenoid biosynthesis, we used mutational analysis to inactivate putative genes predicted to be involved in carotenoid biosynthesis in A. brasilense Cd. We have shown that HpnCED enzymes are involved in the biosynthesis of squalene (C30), which is required for the synthesis of carotenoids in A. brasilense Cd. We also found that CrtI and CrtP desaturases were involved in the transformation of colorless squalene into the pink-pigmented carotenoids. This study elucidates role of some genes which constitute very pivotal role in biosynthetic pathway of carotenoid in A. brasilense Cd.

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We present a Raman spectroscopy study of the vibrational properties of free-base meso-tetra(4-pyridyl) porphyrin polycrystals under various temperature and hydrostatic pressure conditions. The combination of experimental results and Density Functional Theory (DFT) calculations allows us to assign most of the observed Raman bands. The modifications in the Raman spectra when excited with 488 nm and 532 nm laser lights indicate that a resonance effect in the Qy band is taking place. The pressure-dependent results show that the resonance conditions change with increasing pressure, probably due to the shift of the electronic transitions. The temperature-dependent results show that the relative intensities of the Raman modes change at low temperatures, while no frequency shifts are observed. The experimental and theoretical analysis presented here suggest that these molecules are well represented by the C2v point symmetry group.

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Chemical oxidizers and redox enzymes have traditionally been used to enhance the quality of baked goods. However, consumers now seek natural and clean-label ingredients, avoiding those with chemical-sounding names. Honey, a natural source of glucose oxidase (GOX), represents a promising alternative to purified enzymes for baking purposes. This study aimed to evaluate the effect of honey on the molecular structure and microstructure of gluten proteins in sourdough fermented by different lactic acid bacteria (LAB) strains. Four wheat-rye (1:1) sourdoughs were prepared, each supplemented with honey and inoculated with a different LAB strain. Additionally, two uninoculated doughs, one with honey (honey dough) and the other without (control dough), were prepared under identical conditions. Electronic paramagnetic resonance spectroscopy revealed the presence of hydrogen peroxide in honey solutions, indicating its role as an active source of GOX. Raman spectroscopy showed that honey addition altered the molecular structure of gluten by increasing the proportion of random coils at the expense of α-helix structures. This change is likely attributed to the competition between honey sugars and gluten proteins for water molecules in this system. Moreover, honey led to a decrease in the free sulfhydryl content of gluten compared to the control dough, suggesting an increase in disulfide crosslinking points. These enhanced protein-protein interactions were observed in scanning electron microscopy micrographs as a coarse gluten network composed of interconnected strands and fibrils. All LAB strains exhibited optimal acidification (pH < 4.3) in honey-supplemented sourdoughs, promoting the hydrolysis of gluten proteins into smaller fragments. Overall, honey-supplemented sourdoughs showed a gradual increase in the ß-sheet content while decreasing the proportion of random coils over time. This trend suggests that the polypeptide fragments interacted through interchain hydrogen bonds, leading to a more ordered structure, which likely contributes to providing dough with good baking aptitude.

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The oxidative stability of biodiesel is defined by its relative resistance to the action of oxygen at room temperature. Its determination is an essential reference to the quality of biofuel and a significant parameter to be determined. This parameter concerns the quality of the biodiesel to be supplied to the consumer, and its determination is fundamental to maintaining the engine's proper functioning. Raman spectroscopy allows the rapid obtaining of structural information regarding biodiesel quality and, when aided by multivariate analysis methods, allows a quantitative determination of specific properties. This work uses Raman spectroscopy, Multivariate Curve Resolution with Alternative Least Squares (MCR-ALS) method, and Evolving Factor Analysis (EFA) to study biodiesel's oxidation kinetics. Also, the vibrational modes C = C, CH2, and CH3 were identified as the main structural groups involved in this process, corroborating previous studies. The MCR-ALS & EFA combination allowed modeling of the degradation kinetics following an A â†’ B â†’ C mechanism, where A corresponds to the biodiesel (starting material), B is related to the hydroperoxide mixture, and C is the final product. The results also suggested that this process follows a first-order reaction, with kinetic constant values of k1 = 0.0056 min-1 and k2 = 0.0031 min-1.

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Lithium-oxygen batteries show promising energy storage potential with high theoretical energy density; however, further investigation of chemical reactions is required. In this study, experimental Raman and theoretical analyzes are performed for a Li-O2 battery with LiClO4/dimethyl sulfoxide (DMSO) electrolyte and carbon cathode to understand the role of intermediate species in the reactional mechanism of the cell using a high donor number solvent. Operando Raman results reveal reversible changes in the DMSO bands, in addition to the formation and decomposition of Li2O2. On discharge, a decrease in DMSO polarizability is observed and bands of DMSO-Li+-anion interactions are evidenced and supported by ab initio density functional theory (DFT) calculations. Molecular dynamics (MD) force field simulations and operando Raman show that DMSO interacts with LiO2(sol), highlighting the stability of the electrolyte compared to the interaction with reactive O 2 - ${\rm O}_2^{-}$ . On charging, the presence of Li+ indicates the formation of a lithium-deficient phase, followed by the release of Li+ and oxygen. Therefore, this study contributes to understanding the discharge/charge chemistry of a Li-O2 cell, employing a common carbon cathode and DMSO electrolyte. The combination of a simple characterization technique in operando mode and theoretical studies provides essential information on the mechanism of Li-O2 system.

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The interaction of L-Phe with the membrane components, i.e., lipids and proteins, has been discussed in the current literature due to the interest to understand the effect of single amino acids in relation to the formation of amyloid aggregates. In the present work, it is shown that L-Phe interacts with 9:1 DMPC (1,2-dimyristoyl-sn-glycero-3 phosphocholine)/DPPC (1,2-dipalmitoyl-sn-glycero-3 phosphocholine) mixtures but not in the 1:9 one. An important observation is that the interaction disappears when DPPC is replaced by diether PC (2-di-O-hexadecyl-sn-glycero-3-phosphocholine) a lipid lacking carbonyl groups (CO). This denotes that CO groups may interact specifically with L-Phe in accordance with the appearance of a new peak observed by Infrared spectroscopy (FTIR-ATR). The interaction of L-Phe affects the compressibility pattern of the 9:1 DMPC/DPPC mixture which is congruent with the changes observed by Raman spectra. The specific interaction of L-Phe with CO, propagates to phosphate and choline groups in this particular mixture as analyzed by FTIR-ATR spectroscopy and is absent when DMPC is dopped with diether PC.

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In this work, we used Raman spectroscopy to identify compounds present at different maturation stages of the exocarp of scarlet eggplant and two banana cultivars, 'prata' and 'nanica'. Raman spectral analyses of both fruits showed bands attributed to phenolic acids, flavonoids, carotenoids, and fatty acids. During the scarlet eggplant's maturation process, Raman spectral profile changes are mainly observed in the carotenoid content rather than flavonoids. Furthermore, it is suggested that naringenin chalcone together with ß-carotene determines the orange-red color of the ripe stage. Variations in chemical composition among the maturation stages of bananas were observed predominantly in 'prata' when compared to 'nanica'. In contrast to scarlet eggplant changes in the spectral profile were more evident in the content of the flavonoid/phenolic acids. The in situ analysis was demonstrated to be useful as a guide in selecting bioactive compounds on demand from low-cost horticultural waste.