Determination of bioequivalence between generic and reference drugs using laser-induced breakdown spectroscopy.

BACKGROUND: In vitro bioequivalence studies are strictly limited to the comparison of dissolution performance to a reference drug. These studies are performed without considering the chemical similarity between the generic and reference drug formulations. This work has focused on developing a groundbreaking method based on the laser-induced breakdown spectroscopy (LIBS) technique for the in vitro bioequivalence determination of immediate-release solid oral dosage form generic drugs and as an alternative method for establishing the biowaiver of in vivo generic drug studies. RESULTS: The novel LIBS-based methodology to determine in vitro bioequivalence is fast, easy to perform, and can be carried out without the requirement of tedious and complicated sample pre-treatment, nor expensive instrumentals and reagents, almost directly on the drug samples. Furthermore, the proposed methodology demonstrated that it is enough to identify the spectrochemical similarity of the formulation between generic drugs to a reference drug through the chemometric study of their LIBS spectra, based on the determination of the differentiation and similarity factors, f1 and f2, respectively, used in the pharmaceutical industry in this purpose. After analysing their LIBS spectra, the generic drugs selected for this work have all been shown to be in vitro bioequivalent, given their f1 values of less than 15 and f2 values greater than 50, according to the technical regulations on which the American and European medicines agencies are based for the approval of registration for generic immediate-release solid oral dosage form drugs. This has been evidenced even for drugs from Class III and Class IV of the biopharmaceutical classification system, whose active principle nominal concentration is very low as 0.1 and 0.25 mg/tablet, respectively. SIGNIFICANCE: for the first time the LIBS technique has been successfully used in an advanced application for the pharmaceutical industry. The proposed method constitutes a reliable and specialized methodology for the establishment of formulation similarity between two drugs, without the requirement of separate identification of each of their components, which is a new and potential tool to determine the in vitro bioequivalence for generic immediate-release solid oral dosage form drugs.

An overview on the Brazilian Coffea canephora scenario and the current chemometrics-based spectroscopic research.

This review explores the historical, botanical, sensory, and quality aspects of Coffea canephora, with a focus on Brazil's rise as a producer of specialty canephora coffees in the Amazon region, Espírito Santo, and Bahia. Brazil has gained global recognition through the first geographical indications for canephora: Matas de Rondônia for robusta amazônico coffee and Espírito Santo for conilon coffee. Despite this, comprehensive insights into how variety, terroir, environmental conditions, and cultivation practices influence the chemical and sensory attributes of Brazilian canephora remain underdeveloped compared to well-studied arabica coffee. Producers and researchers are working to elevate canephora coffees to higher market levels, despite technological, production, and perception challenges stemming from its historical reputation for poor quality. Ensuring the sustainability of Amazonian canephora coffee without deforestation is particularly challenging due to the need to verify practices across numerous small-scale farms. There is also a critical need for standardized production and tasting protocols for Brazilian canephora, leveraging local expertise and professional cuppers to ensure consistent quality and reliable sustainability claims. Significant opportunities exist in valuing the production chain of geographically unique canephora coffees, which could increase specialty exports, enhance economic prospects for local farmers, and support Amazon preservation. Recognizing and marketing these coffees as premium products with unique flavor profiles can boost their global appeal. Another challenge lies in establishing new specialty standards for soluble coffee from specialty canephora to meet consumer demands for convenience without compromising taste or ethical standards. In such a scenario, several analytical methods have been suggested to identify high-quality variants, combating their stigmatization. The potential of spectroscopy techniques and chemometrics-based data science is highlighted in confirming coffee quality, authenticity, traceability, and geographical origin, enhancing model interpretation and predictive accuracy through synergistic and complementary information. Non-targeted spectroscopic analyses, providing comprehensive spectral fingerprints, are contrasted with targeted analyses. Overall, this review offers valuable insights for the coffee scientific community, exporters, importers, roasters, and consumers in recognizing the potential of Brazilian canephora coffees.

Influence of different opacities and layering technique of nanotechnology composite resins regarding the wavelength and fluorescence intensity: in vitro study / Influencia de diferentes opacidades y la técnica de estratificación de resinas compuestas de nanotecnología en la longitud de onda e intensidad de fluorescencia: estudio in vitro

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.

Microwave-induced combustion for further determination of potentially toxic elements in honey by ICP-MS.

Microwave-induced combustion (MIC) was proposed in this study for honey decomposition aiming for As, Cd, Hg, and Pb determination by inductively coupled plasma mass spectrometry (ICP-MS). Sample mass (up to 1.0 g), absorbing solution (0.5 to 14.4 mol L-1 HNO3, and H2O), heating program, and combustion aids were evaluated. The Eurachem guidelines were used for method validation. The proposed method enabled combustion of a high sample mass (0.8 g of honey, with 0.4 g of microcrystalline cellulose and 100 µL of 6 mol L-1 NH4NO3) using 6 mL of an absorbing solution consisting of 1 mol L-1 HNO3, which resulted in low residual carbon in solution (< 25 mg L-1). Honey samples from different geographical origins were analyzed. Results showed no significant difference in comparison to other two microwave decomposition methods, based on microwave-assisted wet digestion with single reaction chamber (MAWD-SRC) and microwave-assisted wet digestion (MAWD). Standard addition experiments resulted in recoveries higher than 98%. The limits of detection ranged from 1.10 (As) to 4.60 ng g-1 (Pb). In addition to using only diluted reagents and resulting in digests virtually free of interferences, the proposed method was faster (< 30 min) than most of those presented in the literature.

Low cost sample preparation method using ultrasound for the determination of environmentally critical elements in seaweed.

In this study, ultrasound (US) was evaluated for As, Cd, Pb, Mn, Sr and V extraction from seaweed samples. The following parameters of ultrasound-assisted extraction (UAE) using an US bath were: frequency (25 to 130 kHz), amplitude (30 to 100%), temperature (30 to 80 °C), sample mass (50 to 200 mg), extractant concentration (1 to 3 mol L-1 of HNO3) and treatment time (5 to 30 min). Acoustic density and power density distribution were calculated using the calorimetric method and mapping of the acoustic pressure distribution was also evaluated. The optimized UAE conditions were 200 mg of sample in 10 mL of 2 mol L-1 HNO3 and 30 min of sonication in a 25 kHz US bath (37.2 ± 4.0 W L-1) at 70% of amplitude and 70 °C. Analytes were quantified using inductively coupled plasma mass spectrometry and results were compared with values obtained using "silent" conditions (magnetic or mechanical stirring at 500 rpm, and without stirring), and a reference method based on microwave-assisted wet digestion (MAWD). The UAE method demonstrated the best extraction efficiency (higher than 95%) for all analytes, especially for As, Cd and V, with lower standard deviations (up to 5%) and lower blank values in comparison with the silent conditions. The proposed UAE method was more advantageous than the reference method, being faster, simpler, safer, more environmentally friendly, and with higher detectability (lower limits of quantification, from 0.0033 to 1.34 µg g-1). In addition, negligible blank values were obtained for UAE and no interference were observed in the determination step. Furthermore, the optimized UAE method was applied for Antarctic seaweed samples and comparison with results obtained by MAWD was satisfactory. In this sense, UAE is demonstrated to be a suitable option for sample preparation of seaweed samples and further determination of environmentally critical elements avoiding the use of concentrated reagents as in the MAWD reference method.

An overview of preconcentration techniques combined with inductively coupled plasma mass spectrometry for trace element determination in biological studies.

In the last decades, the determination of trace elements in biological materials has emerged as an important area of study because of its relevance to human health and the environment. Inductively coupled plasma mass spectrometry (ICP-MS) has proven to be a powerful tool for trace element analysis, owing to its high sensitivity and ability to determine several elements in a single measurement. However, given the complex nature of biological matrices and the presence of elements, most of them at ultratrace levels, it becomes crucial to complement ICP-MS with preconcentration techniques to increase the sensitivity and selectivity of analytical methods. This article presents an exhaustive overview of liquid- and solid-phase preconcentration techniques used in combination with ICP-MS for trace element determination in different biological samples from 2000 to the present. An in-depth discussion of the advances on the application of state-of-the-art solvents and materials in trace element extraction and preconcentration is presented. Special attention is given to different strategies for elemental speciation analysis, employing both chromatographic and non-chromatographic techniques. The role of automation in these methodologies is also described. Finally, future trends and challenges related to this topic are discussed.

A new ultrasound-assisted microextraction for elemental impurities determination in tablets by ICP-MS according to USP chapters 232 and 233.

Along with the United States Pharmacopeia (USP) chapters 232 and 233 regarding elemental impurities in pharmaceutical products, new challenges have been imposed in terms of sample preparation procedures prior to inductively coupled plasma mass spectrometry analysis, considering the matrix complexities. As so, a new microextraction procedure assisted by ultrasound using a cup-horn sonoreactor, minimal reactants, and sample was proposed and validated according to USP. The procedure was optimized with samples of milled tablets and 3 different acid mixtures (HNO3, 3HNO3:1HCl, and 9HNO3:1HF) and it was compared with microwave-assisted acid digestion. In the validation step, recoveries ranging from 85 to 120 % and RSD below 10 % were obtained for 22 analytes (except Ag and Pt) with satisfactory linearity and good sensitivity. The method was then applied for 37 samples of antidepressants, which presented trace levels of As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Pd, Sn, and V.

A one-class classification approach for authentication of specialty coffees by inductively coupled plasma mass spectroscopy (ICP-MS).

Due to the lucrative nature of specialty coffees, there have been instances of adulteration where low-cost materials are mixed in to increase the overall volume, resulting in illegal profit. A widely used and recommended approach to detect possible adulteration is the application of one-class classifiers (OCC), which only require information about the target class to build the models. Thus, this work aimed to identify adulterations in specialty coffees with low-quality coffee using multielement analysis determined by ICP-MS and to evaluate the performance of one-class classifiers (dd-SIMCA, OCRF, and OCPLS). Therefore, authentic specialty coffee samples were adulterated with low-quality coffee in 25 % to 75 % (w/w) proportions. Samples were subjected to acid decomposition for analysis by ICP-MS. OCPLS method presented the best performance to detect adulterations with low-quality coffee in specialty coffees, showing higher specificity (SPE = 100 %) and reliability rate (RLR = 94.3 %).

Direct Determination of Ca, K, and Mg in Soy Leaf Samples Using Laser-Induced Breakdown Spectroscopy.

This study was dedicated to developing analytical methods for determining macronutrients (Ca, K, and Mg) in soy leaf samples with and without petioles. The study's primary purpose was to present Laser-induced breakdown spectroscopy (LIBS) as a viable alternative for directly analyzing leaf samples using chemometric tools to interpret the data obtained. The instrumental condition chosen for LIBS was 70 mJ of laser pulse energy, 1.0 µs of delay time, and 100 µm of spot size, which was applied to 896 samples: 305 of soy without petioles and 591 of soy with petioles. The reference values of the analytes for the proposition of calibration models were obtained using inductively coupled plasma optical emission spectroscopy (ICP-OES) technique. Twelve normalization modes and two calibration strategies were tested to minimize signal variations and sample matrix microheterogeneity. The following were studied: multivariate calibration using partial least squares and univariate calibration using the area and height of several selected emission lines. The notable normalization mode for most models was the Euclidean norm. No analyte showed promising results for univariate calibrations. Micronutrients, P and S, were also tested, and no multivariate models presented satisfactory results. The models obtained for Ca, K, and Mg showed good results. The standard error of calibration ranged from 2.3 g/kg for Ca in soy leaves without petioles with two latent variables to 5.0 g/kg for K in soy leaves with petioles with two latent variables.

Plasticizer concentration effect on films and coatings based on poly(vinyl alcohol) and cationic starch blends.

Films based on poly(vinyl alcohol) (PVA) and cationic starch (CS) were combined with different percentages of sorbitol (S; 15.0, 22.5, and 30.0% w v-1) to assess the effect of plasticizer on the films. Spectroscopic analyses confirmed the interaction between them. However, micrographs indicated the formation of sorbitol crystals on the surface of the films, especially at higher sorbitol concentrations. The blends presented low water vapor transmission rate values, reaching (7.703 ± 0.000) g h-1 m-2 (PVA75CS25S15), and low solubility values for the films containing higher CS amounts. The lack of statistical differences in most parameters suggests that no significant gain comes from increasing the amount of sorbitol at percentages higher than 15%. As a coating, the blend PVA75CS25S15 successfully decreased the loss of moisture content in acerolas by 1.15 times (compared to the control), confirming the suitability of this matrix as a fruit coating.

Poly-ε-caprolactone based nanoparticles for delivery of genistein in melanoma treatment

We developed poly-ε-caprolactone (PCL)-based nanoparticles containing D-α-tocopherol polyethylene glycol-1000 succinate (TPGS) or Poloxamer 407 as stabilizers to efficiently encapsulate genistein (GN). Two formulations, referred to as PNTPGS and PNPol, were prepared using nanoprecipitation. They were characterized by size and PDI distribution, zeta potential, nanoparticle tracking analysis (NTA), GN association (AE%), infrared spectroscopy (FT-IR), and differential scanning calorimetry (DSC). PNTPGS-GN exhibited a particle size of 141.2 nm, a PDI of 0.189, a zeta potential of -32.9 mV, and an AE% of 77.95%. PNPol-GN had a size of 146.3 nm, a better PDI than PNTPGS-GN (0.150), a less negative zeta potential (-21.0 mV), and an AE% of 68.73%. Thermal and spectrometric analyses indicated that no new compounds were formed, and there was no incompatibility detected in the formulations. Cellular studies revealed that Poloxamer 407 conferred less toxicity to PCL nanoparticles. However, the percentage of uptake decreased compared to the use of TPGS, which exhibited almost 80% cellular uptake. This study contributes to the investigation of stabilizers capable of conferring stability to PCL nanoparticles efficiently encapsulating GN. Thus, the PCL nanoparticle proposed here is an innovative nanomedicine for melanoma therapy and represents a strong candidate for specific pre-clinical and in vivo studie

ICP-OES analysis of total As and Cd in Columbian Oryza sativa L. rice.

Arsenic (As) and cadmium (Cd) are considered toxic elements, even at trace levels. Their accurate quantification in crops can be complex at low levels and due to interference with other elements. The aim of this work was to develop and validate an analytical method for As and Cd quantification in rice stem and grains from the production systems "Irrigated Rice Ecosystems" (IRE) and "Rainfed Rice Ecosystems" (RRE) in Colombia. Mineralisation was carried out by acid digestion using an open system with a heating plate. Metal detection was performed by inductively coupled plasma optical emission spectrometry (ICP-OES). Method adjustment, calibration, and validation were performed in accordance with AOAC standards, considering sensitivity, precision, accuracy, and selectivity parameters. The obtained method was applied to quantify levels in 259 rice stem and 443 grain samples from IRE and RRE.

Contenido de arsénico, conocimiento y actitud en el consumo del agua de pozo familiar / Arsenic content, knowledge and attitude in family well water consumption / Conteúdo de arsênico, conhecimento e atitude em relação ao consumo doméstico de água de poço

La contaminación por arsénico del agua de consumo humano, es un problema de salud pública, porque produce diversas enfermedades cancerígenas y de piel. Objetivo. Determinar niveles de arsénico en el agua de pozos, y evaluar el grado de conocimiento y actitud sobre el consumo del agua familiar. Materiales y métodos. Se utilizaron 96 muestras del agua de pozos del distrito de Juliaca. Las cuales se analizaron en laboratorio de Unidad de Servicios de Análisis Químicos de la Facultad de Química - Universidad Nacional Mayor de San Marcos-Lima, mediante la técnica Espectrofotometría de Absorción Atómica con Horno de Grafito. Los datos de arsénico fueron procesados estadísticamente mediante el diseño completamente al azar. Asimismo, la descripción del conocimiento y actitud del consumo de agua familiar se realizó aplicando la técnica de la encuesta y el instrumento fue un cuestionario de 11 ítems para la variable conocimiento y 7 para la variable actitud, con respuestas de alto, medio y bajo para conocimiento y buena, regular y mala calificadas con escala de Likert. Resultados. La concentración promedio fue 0.031 mg de As/L de agua y entre zonas hubo semejanza (p>0.05). En el grado de conocimiento sobre contaminación con arsénico en el agua de consumo humano respondieron el 40.81 % con calificación alta y el 59.19% están entre medio y bajo; en actitud, la calificación buena obtuvo menos del 50 % de encuestados y el resto están entre regular y mala. Conclusiones. El contenido arsenical en el agua de pozos supera los límites máximos permisibles según Organización Mundial de Salud y más del 50% se exponen al agua contaminada.

Arsenic contamination of drinking water is a public health problem, because it causes various carcinogenic and skin diseases. Objective. To determine arsenic levels in well water, and to evaluate the degree of knowledge and attitude about family water consumption. Materials and methods. Ninety-six samples of well water from the district of Juliaca were used. These were analyzed in the laboratory of the Chemical Analysis Services Unit of the Faculty of Chemistry - Universidad Nacional Mayor de San Marcos-Lima, using the technique Atomic Absorption Spectrophotometry with Graphite Furnace. The arsenic data were statistically processed using a completely randomized design. Likewise, the description of the knowledge and attitude of family water consumption was carried out by applying the survey technique and the instrument was a questionnaire of 11 items for the knowledge variable and 7 for the attitude variable, with answers of high, medium and low for knowledge and good, regular and bad rated with a Likert scale. Results. The average concentration was 0.031 mg As/L water and there was similarity between zones (p>0.05). In the degree of knowledge about arsenic contamination in drinking water, 40.81% responded with high qualification and 59.19% were between medium and low; in attitude, the good qualification obtained less than 50% of respondents and the rest were between regular and bad. Conclusions. The arsenic content in well water exceeds the maximum permissible limits according to the World Health Organization and more than 50% are exposed to contaminated water.

A contaminação da água potável por arsênico é um problema de saúde pública, pois causa várias doenças de pele e carcinogênicas. Objetivo. Determinar os níveis de arsênico na água de poço e avaliar o grau de conhecimento e atitude em relação ao consumo doméstico de água. Materiais e métodos. Foram utilizadas 96 amostras de água de poço do distrito de Juliaca. Elas foram analisadas no laboratório da Unidade de Serviços de Análises Químicas da Faculdade de Química da Universidade Nacional Mayor de San Marcos-Lima, usando a técnica de Espectrofotometria de Absorção Atômica com Forno de Grafite. Os dados sobre arsênico foram processados estatisticamente usando um desenho completamente aleatório. Da mesma forma, a descrição do conhecimento e da atitude do consumo familiar de água foi realizada aplicando a técnica de pesquisa e o instrumento foi um questionário de 11 itens para a variável conhecimento e 7 para a variável atitude, com respostas de alto, médio e baixo para o conhecimento e classificado como bom, regular e ruim em uma escala Likert. Resultados. A concentração média foi de 0,031 mg As/L de água e houve similaridade entre as zonas (p>0,05). Quanto ao grau de conhecimento sobre a contaminação por arsênico na água potável, 40,81% responderam com uma pontuação alta e 59,19% ficaram entre médio e baixo; quanto à atitude, a pontuação boa foi obtida por menos de 50% dos entrevistados e o restante ficou entre regular e ruim. Conclusões. O teor de arsênico na água de poço excede os limites máximos permitidos de acordo com a Organização Mundial da Saúde e mais de 50% estão expostos à água contaminada.

Analysis of pH, calcium ion release, and energy dispersive spectroscopy of a bioceramic root canal dressing.

This study compared the pH and calcium ion release of calcium silicate- (Bio-C Temp) and calcium hydroxide-based (Ultracal XS) medications. Intracanal remnants of both medications were also evaluated using SEM-EDS after the removal protocol. Thirty-five bovine teeth were prepared. Fifteen were filled with Bio-C Temp and 15 with Ultracal XS. Five remained without intracanal medication (control group). Five samples from each experimental time (i.e.. 24, 72, and 168 hours) were used to measure pH and calcium ions release using a digital pH meter and microplate reader, respectively. Afterward, the peaks of the chemical elements composing both medications were analyzed in SEM-EDS. One-way ANOVA and Tukey's post hoc test analyzed the pH and calcium ion release data. Student's t-test compared the medications in each experimental time. SEM-EDS described the percentage of chemical elements in the samples. Bio-C Temp and Ultracal XS showed a significant pH increase from 24 to 168 hours (p<0.05). Ultracal XS showed a higher pH value at 24 hours than Bio-C Temp (p<0.05) but were similar at 72 and 168h (p > 0.05). Calcium ion release did not depend on the experimental period (p > 0.05). Bio-C Temp showed lower calcium ions release than Ultracal XS at 24 hours (p<0.05). SEM-EDS analyses showed the remains of both medications, but the concentration of Si, Al, and W ions was present only in the calcium silicate-based medication. Bio-C Temp presented alkaline pH and a satisfactory calcium ion release over the time. The remaining of both medications were present after the protocols for paste removal.

(Ro)vibrational Spectroscopic Constants, Lifetime and QTAIM Evaluation of Fullerene Dimers Stability.

The iconic caged shape of fullerenes gives rise to a series of unique chemical and physical properties; hence a deeper understanding of the attractive and repulsive forces between two buckyballs can bring detrimental information about the structural stability of such complexes, providing significant data applicable for several studies. The potential energy curves for the interaction of multiple van der Waals buckyball complexes with increasing mass were theoretically obtained within the DFT framework at ωB97xD/6-31G(d) compound model. These potential energy curves were employed to estimate the spectroscopic constants and the lifetime of the fullerene complexes with the Discrete Variable Representation and with the Dunham approaches. It was revealed that both methods are compatible in determining the rovibrational structure of the dimers and that they are genuinely stable, i.e., long-lived complexes. To further inquire into the nature of such interaction, Bader's QTAIM approach was applied. QTAIM descriptors indicate that the interactions of these closed-shell systems are dominated by weak van der Waals forces. This non-covalent interaction character was confirmed by the RDG analysis scheme. Indirectly, QTAIM also allowed us to confirm the stability of the non-covalent bonded fullerene dimers. Our lifetime calculations have shown that the studied dimers are stable for more than 1 ps, which increases accordingly with the number of carbon atoms.

Spectroscopic Insights of an Emissive Complex between 4'-N,N-Diethylaminoflavonol in Octa-Acid Deep-Cavity Cavitand and Rhodamine 6G.

Excited-state chemistry relies on the communication between molecules, making it a crucial aspect of the field. One important question that arises is whether intermolecular communication and its rate can be modified when a molecule is confined. To explore the interaction in such systems, we investigated the ground and excited states of 4'-N,N-diethylaminoflavonol (DEA3HF) in an octa acid-based (OA) confined medium and in ethanolic solution, both in the presence of Rhodamine 6G (R6G). Despite the observed spectral overlap between the flavonol emission and the R6G absorption, as well as the fluorescence quenching of the flavonol in the presence of R6G, the almost constant fluorescence lifetime at different amounts of R6G discards the presence of FRET in the studied systems. Steady-state and time-resolved fluorescence indicate the formation of an emissive complex between the proton transfer dye encapsulated within water-soluble supramolecular host octa acid (DEA3HF@(OA)2) and R6G. A similar result was observed between DEA3HF:R6G in ethanolic solution. The respective Stern-Volmer plots corroborate with these observations, suggesting a static quenching mechanism for both systems.

Reduction of metmyoglobin by inorganic disulfide species.

The mechanism of the metal centered reduction of metmyoglobin (MbFeIII) by inorganic disulfide species has been studied by combined spectroscopic and kinetic analyses, under argon atmosphere. The process is kinetically characterized by biexponential time traces, for variable ratios of excess disulfide to protein, in the pH interval 6.6-8.0. Using UV-vis and resonance Raman spectroscopies, we observed that MbFeIII is converted into a low spin hexacoordinated ferric complex, tentatively assigned as MbFeIII(HSS-)/MbFeIII(SS2-), in an initial fast step. The complex is slowly converted into a pentacoordinated ferrous form, assigned as MbFeII according to the resonance Raman records. The reduction is a pH-dependent process, but independent of the initial disulfide concentration, suggesting the unimolecular decomposition of the intermediate complex following a reductive homolysis. We estimated the rate of the fast formation of the complex at pH 7.4 (kon = 3.7 × 103 M-1 s-1), and a pKa2 = 7.5 for the equilibrium MbFeIII(HSS-)/MbFeIII(SS2-). Also, we estimated the rate for the slow reduction at the same pH (kred = 10-2 s-1). A reaction mechanism compliant with the experimental results is proposed. This mechanistic study provides a differential kinetic signature for the reactions of disulfide compared to sulfide species on metmyoglobin, which may be considered in other hemeprotein systems.

Argentination: A Silver Bullet for Cannabinoid Separation by Differential Mobility Spectrometry.

As the legality of cannabis continues to evolve globally, there is a growing demand for methods that can accurately quantitate cannabinoids found in commercial products. However, the isobaric nature of many cannabinoids, along with variations in extraction methods and product formulations, makes cannabinoid quantitation by mass spectrometry (MS) challenging. Here, we demonstrate that differential mobility spectrometry (DMS) and tandem-MS can distinguish a set of seven cannabinoids, five of which are isobaric: Δ9-tetrahydrocannabinol (Δ9-THC), Δ8-THC, exo-THC, cannabidiol, cannabichromene, cannabinol, and cannabigerol. Analytes were detected as argentinated species ([M + Ag]+), which, when subjected to collision-induced dissociation, led to the unexpected discovery that argentination promotes distinct fragmentation patterns for each cannabinoid. The unique fragment ions formed were rationalized by discerning fragmentation mechanisms that follow each cannabinoid's MS3 behavior. The differing fragmentation behaviors between species suggest that argentination can distinguish cannabinoids by tandem-MS, although not quantitatively as some cannabinoids produce small amounts of a fragment ion that is isobaric with the major fragment generated by another cannabinoid. By adding DMS to the tandem-MS workflow, it becomes possible to resolve each cannabinoid in a pure N2 environment by deconvoluting the contribution of each cannabinoid to a specific fragmentation channel. To this end, we used DMS in conjunction with a multiple reaction monitoring workflow to assess cannabinoid levels in two cannabis extracts. Our methodology exhibited excellent accuracy, limits of detection (10-20 ppb depending on the cannabinoid), and linearity during quantitation by standard addition (R2 > 0.99).

Canine visceral leishmaniasis diagnosis by UV spectroscopy of blood serum and machine learning algorithms.

Visceral leishmaniasis (VL) is a zoonotic disease caused by the protozoan Leishmania infantum, and dogs are considered the main urban hosts for future disease transmission. The first and most effective control against the spread of disease relies on identifying infected animals, followed by their treatment or sacrifice, to reduce the protozoan reservoirs. Despite the availability of various diagnostic tests for VL in dogs the development of a quick and accurate diagnosis is essential from a public health and ethical point of view. Here we analyze the use of UV-Vis spectroscopy as an alternative diagnostic method for VL diagnosis by using the antigen-antibody interaction in canine blood serum and machine learning algorithms. The main UV spectra in the 220 to 280 nm range exhibit nine electronic absorption bands, but no significative difference could be identified between the positive and negative group spectra. Finally, UV pre-proceed spectra by SNV (standard normal variate) were submitted to principal component analysis followed by Linear SVM algorithm, the prediction model was tested in a leave-one-out cross-validation and external validation test reaching an overall accuracy of 75%.

Trace Elements in Soy-Based Beverages: A Comprehensive Study of Total Content and In Vitro Bioaccessibility.

Soy-based beverages are one of the most consumed plant-based beverages, which have been used as a substitute for dairy products. Soy is a source of several nutrients (vitamins, minerals, and phenolic compounds, etc.) and its consumption is usually associated with several benefits, such as the prevention of cardiovascular diseases, cancer, and osteoporosis. However, non-essential trace elements can be found in these beverages. Thus, a comprehensive study concerning trace elements Al, As, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, Sb, Se, Sn, Sr, and Zn in soy-based beverages was proposed. In vitro digestion allowed to simulate the gastrointestinal juice (bioaccessibility) and the Caco-2 cells culture model was applied for the bioavailability assay. Trace elements measures were performed by inductively coupled plasma optical emission spectrometry (ICP OES). Multivariate analysis classified soy-based beverages according to their soy source (isolate protein, hydrosoluble extract, and beans); Al, Cu, Fe, Mn, Sr, Se, and Zn bioaccessible fractions corresponded to approximately 40%-80% of their total content, and soy-based beverages were found to be a good Fe, Se, and Zn source. However, our results showed risk exposure assessment from daily consumption of one glass of soy-based beverage can contribute to 3.5% and 0.9% of Al Provisional Tolerable Weekly Intake (PTWI) for children and adults, respectively.