A Theoretical Study on the Mechanisms Involved in Catalytic Dehydrogenation and Dehydration of Isopropanol on SrTiO3.

The dehydrogenation and dehydration of isopropanol on the SrO and TiO2 terminated surfaces, of the SrTiO3 perovskite, is addressed by periodic DFT calculations in order to shed light on the involved mechanisms. The results show that the dehydrogenation occurs through a mechanism involving the dissociative adsorption of the alcohol on the SrO terminated surface, followed the nucleophilic attack of a hydride species on the previously adsorbed hydrogen atom to form molecular hydrogen and the corresponding carbonyl compound. The dehydration instead occurs by the molecular adsorption of the alcohol on the TiO2 terminated surface, followed by various possible E1 elimination pathways leading to the formation of the corresponding alkene and a water molecule. The article reports a thorough study on the involved mechanisms, including identification of the transition states and intermediates along the reaction paths, and evaluation of the respective activation barriers, as well. Thus, this article provides significant insights about the mechanisms of dehydrogenation and dehydration of isopropanol on the SrTiO3 , not reported earlier in literature. The calculated barrier energies are in good agreement with experimental values.

Selective Recovery of Polyphenols from Discarded Blueberries (Vaccinium corymbosum L.) Using Hot Pressurized Liquid Extraction Combined with Isopropanol as an Environmentally Friendly Solvent.

The use of water-ethanol mixtures in hot pressurized liquid extraction (HPLE) to recover phenolic compounds from agro-industrial waste has been successfully investigated. However, the unresolved challenge of reducing solvent costs associated with the process hinders the scaling of this eco-friendly technology. This study evaluated the use of isopropanol as an alternative, lower-cost solvent for recovering polyphenols from discarded blueberries through the HPLE process. HPLE was carried out using water-isopropanol mixtures (0, 15 and 30%) at 70, 100, and 130 °C. The total polyphenol content (TPC), antioxidant capacity (DPPH and ORAC), glucose and fructose contents, and polyphenol profile of the extracts were determined. HPLE extracts obtained using high isopropanol concentrations (30%) and high temperatures (130 °C) presented the highest TPC (13.57 mg GAE/gdw) and antioxidant capacity (IC50: 9.97 mg/mL, ORAC: 246.47 µmol ET/gdw). Moreover, the use of 30% water-isopropanol resulted in higher yields of polyphenols and removal of reducing sugars compared to atmospheric extraction with water-acetone (60%). The polyphenolic profiles of the extracts showed that flavanols and phenolic acids were more soluble at high concentrations of isopropanol (30%). Contrarily, flavonols and stilbenes were better recovered with 15% isopropanol and pure water. Therefore, isopropanol could be a promising solvent for the selective recovery of different bioactive compounds from discarded blueberries and other agro-industrial residues.

Influence of seasonality on the physicochemical properties of Moringa oleifera Lam. Seed oil and their oleochemical potential.

The effect of abiotic factors, such as weather and climate can alter the properties of vegetable oils. In this work, the effects of the refining process and pre-drying of Moringa oleifera Lam. seeds collected in the dry and rainy seasons (seasonality) were evaluated on the characteristics of the extracted oils. The refined and crude dry season oils had lower acidity and moisture content than the dry and raw rainy season oils. Oleic acid (C18:1) showed the highest concentration in the different Moringa oils studied. The results suggest that dry season oils are more suitable for application as feedstocks in the cosmetic, food, medicinal and pharmaceutical industries. Furthermore, refining proved to be efficient in removing free fatty acids and in lightening the oil.

INVESTIGACIÓN DE LA CALIDAD DE SANITIZANTES PARA MANOS SECUESTRADOS POR LA JUSTICIA EN EL MARCO DE LA PANDEMIA DE COVID-19 / Research on the quality of hand sanitizers seized by the Department of Justice in the context of COVID-19 pandemic

En el marco de la pandemia de COVID-19, las agencias reguladoras del mundo, junto a la Organización Mundial de la Salud, recomendaron el uso de sanitizantes de manos para disminuir la transmisión viral. El repentino incremento del uso de estos productos por parte de la población derivó, entre otras cosas, en la aparición de vías de comercialización no autorizadas. Como consecuencia, y por intervención de la justicia, el Laboratorio Nacional de Control del Instituto Nacional de Medicamentos recibió numerosas muestras a fin de conocer la composición cuali-cuantitativa dado que, por la apariencia de los envases y rótulos, denotaban ilegitimidad. Para ello, se llevaron a cabo diversos análisis físico-químicos por picnometría, cromatografía gaseosa y espectrofotometría de infrarrojo medio. Los resultados indicaron que, si bien las muestras analizadas contenían etanol y/o isopropanol, en la mayoría de los casos su concentración no se hallaba en los valores recomendados y casi todos los envases no cumplían con la normativa vigente de rotulado

In the context of COVID-19 pandemic, the use of hand sanitizers was recommended to reduce viral transmission by the global regulatory agencies together with the World Health Organization. The sudden increase in the use of these products by the population led, among other things, to the emergence of unauthorized marketing channels. As a result, and due to judicial intervention, numerous samples were received by the National Control Laboratory of the National Institute of Medicines in order to determine the qualitative-quantitative composition, since the appearance of the containers and labels denoted illegitimacy. To that end, various physicochemical analyses were carried out by pycnometry, gas chromatography and mid-infrared spectrophotometry. Although the analyzed samples contained ethanol and/or isopropanol, the results showed that in most cases the concentration was not within the recommended values and almost all the containers did not comply with the current labeling regulations.

Simultaneous green extraction of fat and bioactive compounds of cocoa shell and protein fraction functionalities evaluation.

This work aimed to verify the feasibility of using alcoholic solvents under atmospheric pressure for the simultaneous extraction of fat and bioactive compounds from cocoa shell (CS), a byproduct of the cocoa industry, as well as to determine the influence of processing on the characteristics of defatted solids (DS). To this end, CS fat (CSF) extraction kinetics using ethanol or isopropanol as solvents were determined at 75 and 90 °C. Relative extraction yields of flavanols and alkaloids were determined, and protein functionalities such as the nitrogen solubility index were evaluated. CSF extraction yields from 36 to 70% were obtained with the highest figures related to absolute solvents. Conversely, hydrated alcohols were suitable to extract bioactive compounds, especially alkaloids, with extraction yields up to 73%. The best values of DS functionalities were obtained with the use of isopropanol, with a foaming capacity of (34 ± 2)% and stability of (57 ± 3)%; regarding emulsifying capability, the highest value was (126 ± 2) m2/g with a stability of (53 ± 4) min. CSF with a fatty acid composition similar to that of cocoa butter and DS with interesting protein functionalities were achieved, indicating that CS can be applied in food systems.

Extraction of carotenoid-rich palm pressed fiber oil using mixtures of hydrocarbons and short chain alcohols.

Solvent extraction is the most efficient method for recovering residual oil from palm pressed fiber (PPFO), which may contain up to eight times the carotenoid content of that found in crude palm oil. The objective of the present study is the use of binary mixtures of hydrocarbons (HC), hexane (Hex), cyclohexane (CHex) or heptane (Hep), and alcohols (ALC), ethanol (Eth) or isopropanol (IPA), in order to promote the highest recovery of a carotenoid-rich PPFO, in which the compositions of the mixtures are defined based on the calculation of solute-solvent distance (Ra) considering ß-carotene as the solute. The extraction experiments were conducted in batch, at 60 ± 2 °C, or in a fixed-bed packed column, at 55 ± 3 °C. Hex and Hep:IPA provided 80% of batch PPFO extraction yield, while in column, the highest yields were obtained with Eth and Hex:IPA (66%). The total carotenoid content obtained was the same independent of the solvent and extraction configuration (from 1790 ± 230 up to 2539 ± 78 mg ß-carotene/kg PPFO). In terms of the carotenoid profile, ß-carotene was mostly extracted by Hex, Hex:Eth stood out in the extraction of α-carotene, and Eth extracted the highest content of lycopene. It is possible to infer that mixtures of HC and ALC with compositions defined based on Hansen Solubility Parameters (HSPs) demonstrated good ability to extract carotenoid-rich PPFO, maintaining their relatively stable fatty acids composition and free acidity, showing that partial substitution of HC by ALC is technically possible.

Liver steatosis in hypothalamic obese rats improves after duodeno-jejunal bypass by reduction in de novo lipogenesis pathway.

AIMS: Hypothalamic obesity is a severe condition without any effective therapy. Bariatric operations appear as an alternative treatment, but the effects of this procedure are controversial. We, herein, investigated the effects of duodeno-jejunal bypass (DJB) surgery upon the lipid profile and expression of genes and proteins, involved in the regulation of hepatic lipid metabolism, in hypothalamic obese (HyO) rats. METHODS: During the first 5days of life, male newborn Wistar rats received subcutaneous injections of monosodium glutamate [4g/kg body weight, HyO group] or saline (control, CTL group). At 90days of life, HyO rats were randomly submitted to DJB (HyO DJB) or Sham-operations (HyO Sham group). Six months after DJB, adiposity, hepatic steatosis and lipid metabolism were verified. KEY FINDINGS: HyO Sham rats were obese, hyperinsulinemic, insulin resistant and dyslipidemic. These rats had higher liver contents of trygliceride (TG) and presented disorganization of the hepatocyte structures, in association with higher hepatic contents of acetyl-CoA carboxylase (ACC), fatty acid synthase (FASN), and stearoyl-CoA desaturase-1 mRNAs and protein. DJB surgery normalized insulinemia, insulin resistance, and dyslipidemia in HyO rats. TG content in the liver and the hepatic microscopic structures were also normalized in HyO DJB rats, while the expressions of ACC and FASN proteins were decreased in the liver of these rodents. SIGNIFICANCE: The DJB-induced amelioration in hepatic steatosis manifested as a late effect in HyO rats, and was partly associated with a downregulation in hepatic de novo lipogenesis processes, indicating that DJB protects against liver steatosis in hypothalamic obesity.

Effect of the type and level of hydration of alcoholic solvents on the simultaneous extraction of oil and chlorogenic acids from sunflower seed press cake.

BACKGROUND: The present study aimed to evaluate the replacement of hexane by alcoholic solvents in oil extraction from sunflower seed press cake. The use of ethanol and isopropanol has important advantages, including low toxicity and good operational safety. Thus, in the present study, solid-liquid extractions were performed in a single stage from 60 to 90 °C and in consecutive extractions in three stages at 90 °C. RESULTS: Solvent hydration negatively affected the extraction of oil but favored the extraction of chlorogenic acids (CAs), especially when ethanol was used. Regarding oxidative stability, the oils extracted using ethanol presented long induction times, which could be related to the high levels of not only CAs and tocopherols, but also phospholipids. CONCLUSION: Alcoholic solvents can be used for extraction to produce sunflower seed oil containing minor compounds that give it greater oxidative stability. In addition, the results obtained using hydrous ethanol showed that this solvent can yield defatted sunflower seed meal with a low content of CAs, enabling future use of the protein fraction. © 2017 Society of Chemical Industry.

Análise comparativa dos cimentos MTA cinza e branco associados ao álcool isopropílico / Comparative analysis of gray and white MTA associated with isopropyl alcohol

O objetivo deste estudo ex vivo foi investigar e comparar os efeitos antibacterianos, a citotoxicidade, a adaptação marginal e a capacidade seladora do agregado trióxido mineral (MTA), branco e cinza (Angelus, Londrina, Brasil), quando combinados com água destilada ou álcool isopropílico. Os efeitos antibacterianos de ambas as formulações foram avaliados através do teste de difusão em agar utilizando Staphylococcus aureus (ATCC25923) e Pseudomonas aeruginosa (ATCC27853) para a seleção da concentração de escolha. A geração das espécies reativas do oxigênio (ERO) foi analisada, primeiramente, utilizando cepas de Escherichia coli proficiente (AB1157) e triplo mutante (BW535), deficiente nos mecanismos de reparo. A geração de ERO também foi analisada através da degradação plasmidial (método de eletroforese) e com a utilização da sonda DCF. A geração das espécies reativas do nitrogênio (ERN) foi avaliada através da sonda DAF. A citotoxicidade dos eluatos dos cimentos foi avaliada pelo MTT, com células L929. A adaptação marginal foi feita através da microscopia eletrônica de varredura (MEV). A capacidade seladora foi realizada através de ensaios de infiltração bacteriana. Os resultados mostraram que a incorporação do isopropanol ao MTA aumentou os halos de inibição no modelo Gram-positivo (S. aureus-ATCC25923) (P <0.05). A adição de isopropanol 70% aos cimentos de MTA branco e cinza aumentou a atividade antimicrobiana para E. coli selvagem (AB1157) e triplo mutante (BW535) (P <0.0001). Não ocorreu a total degradação do DNA plasmidial para as amostras de MTA branco e cinza manipuladas com isopropanol 70%. As amostras de MTA branco e cinza manipuladas de acordo com o fabricante geraram significativamente mais espécies reativas do oxigênio (sonda DCF) (P <0.0001 e P =0.0002) e do nitrogênio (sonda DAF) (P =0.0002 e P =0.0003) do que as manipuladas com isopropanol 70%. Os cimentos manipulados com água destilada foram mais citotóxicos do que a associação com solução de isopropanol 70% (P <0.05). A análise ao MEV mostrou melhor adaptação ao preparo nas amostras com o isopropanol 70%, entretanto o ensaio de infiltração bacteriana ex vivo com Enterococcus faecalis (ATCC29212), não mostrou diferença estatística para as amostras manipuladas com isopropanol ou com água (P >0.05). Podemos concluir que a manipulação com isopropanol melhorou a atividade antimicrobiana do MTA tornando-o menos citotóxico, sem alterar a capacidade seladora.

The aim of this study was to investigate and compare the antibacterial effects, cytotoxicity, marginal adaptation and sealing ability of mineral trioxide aggregate (MTA), white and gray (Angelus, Londrina, Brasil), when combined with distilled water or isopropyl alcohol. The antibacterial effects of both formulations were evaluated by agar diffusion method using Staphylococcus aureus (ATCC25923) and Pseudomonas aeruginosa (ATCC27853) for selecting the suitable concentration of isopropyl alcohol. The antimicrobial mechanism by the generation of reactive oxygen species (ROS) was first analyzed using Escherichia coli strains: proficient (AB1157) and triple mutant (BW535), deficient in the repair mechanisms. The ROS generation was also analyzed by degradation of DNA plasmid (electrophoresis method) and with the DCF probe. The generation of reactive nitrogen species (RNS) was assessed by DAF probe. The cytotoxicity of the eluates was assessed by MTT test, with L929 cells. The marginal adaptation was evaluated by scanning electron microscopy (SEM). The sealing ability was performed using bacterial leakage assay. The results showed that the incorporation of isopropanol to MTA increased the inhibitory haloes in Gram-positive model (S. aureus-ATCC25923) (P <0.05). Adding 70% isopropanol to white and gray MTA cements increased antimicrobial activity against both E. coli wild (AB1157) and triple-mutant (BW535) strains (P <0.0001). The DNA plasmid was not completely degraded for the samples of white and gray MTA manipulated with 70% isopropanol. The white and gray MTA samples, handled according to the manufacturer, generated significantly more ROS (DCF probe) (P <0.0001 e P =0.0002) and RNS (DAF probe) (P =0.0002 e P =0.0003) than that manipulated with 70% isopropanol. The cements handled with distilled water were more cytotoxic than when associated with isopropanol solution 70% (P <0.05). The SEM analysis showed better adaptation to the cavity prepares when the samples were filled with MTA with 70% isopropanol, however the ex vivo bacterial infiltration test with Enterococcus faecalis (ATCC29212), was not statistically different from samples manipulated with isopropanol or water (P >0.05). We can conclude that the manipulation with isopropanol improved the antimicrobial activity of the MTA rendering less citotoxicity, without altering the sealing ability.

Etanol e isopropanol: genotoxicidad y teratogénesis evaluada aplicando el modelo de Drosophila melanogaster / Ethanol and isopropanol: genotoxicity and teratogenicity evaluated using Drosophila melanogaster as a model system

El etanol y el isopropanol son, de los alcoholes alifáticos de cadena corta, los más frecuentemente asociados a la actividad humana tanto a nivel industrial como en el entorno doméstico. En este trabajo se presentan los principales hallazgos reportados en la literatura para ensayos de genotoxicidad y teratogénesis en modelos experimentales de distinto nivel de complejidad, con especial énfasis en Drosophila melanogaster. El metabolismo de estos alcoholes es semejante en Drosophila y en humanos por lo cual la mosca es un buen modelo in vivo para la evaluación de sus potenciales efectos tóxicos, genotóxicos y teratogénicos.

Ethanol and isopropanol are two of the short chain aliphatic alcohols more frequently associated to the human environment, both in the industrial and domestic conditions. The aim of this work was to present the main findings reported in the literature about their genotoxicity and teratogenicity in experimental models of different level of complexity, with special emphasis in Drosophila melanogaster. Taking into account that the metabolism of both alcohols in Drosophila and humans is similar, the fly is a good model for the evaluation of their potentially toxic, genotoxic and teratogenic effects.

Extração de óleo de farelo de arroz utilizando solventes alcoólicos: avaliação de alterações na fração proteica e na composição do óleo / Rice bran oil extraction using alcoholic solvents: evaluation of changes in protein fraction and oil composition

Um dos principais setores do sistema agroindustrial brasileiro é composto pelo processamento de oleaginosas. Sua importância não se deve apenas ao seu produto principal, o óleo, mas também à fração desengordurada, composta por proteínas. Tradicionalmente, hexano é o solvente empregado na extração de óleos vegetais e, por esta razão, os objetivos principais deste trabalho foram estudar a viabilidade de substituição deste solvente por solventes alcoólicos na extração do óleo de farelo de arroz e, neste sentido, avaliar o impacto desta mudança nas características do óleo e da fração proteica. Foram realizados experimentos de extração sólido-líquido na condição de equilíbrio com a finalidade de avaliar a influência das variáveis de processo, tipo de solvente (etanol ou isopropanol), teor de água no solvente (0, 6 ou 12%) e temperatura (50 a 80 °C), na extração do óleo de farelo de arroz. Através dos experimentos de extração foi possível caracterizar os extratos obtidos e o farelo desengordurado em termos de rendimento de extração de compostos lipídicos, proteicos e minoritários, além da caracterização da fração proteica presente no rafinado, em termos de solubilidade e análise térmica. De maneira geral, os resultados mostraram influência da água no solvente no sentido da supressão da extração de óleo e, por outro lado, observou-se que o aumento da temperatura favoreceu o processo de extração lipídica. No caso do conteúdo proteico presente no extrato, observou-se que a hidratação do solvente e a temperatura favoreceram a extração de proteínas. A elevação da temperatura de processo favoreceu também, a extração de γ-orizanol, porém o aumento da água no solvente diminuiu a extração deste composto minoritário. A água também exerceu forte influência na quantidade de acilgliceróis e ácidos graxos livres transferidos para o extrato, porém, para o teor de fosfolipídeos, essa influência foi menor. As condições de processo não afetaram significativamente a composição do óleo, que se mostrou típica de óleo de farelo de arroz. Com relação à fração proteica, a solubilidade e propriedades térmicas, que definem o grau de desnaturação proteica, sofreram forte influência do grau de hidratação do solvente e da temperatura de processo, uma vez que à medida que a quantidade de água no solvente e a temperatura foram aumentados, notou-se uma diminuição no índice de solubilidade de nitrogênio. A partir dos resultados obtidos pode-se inferir que a extração de óleo de farelo de arroz com solventes alternativos, etanol e isopropanol, é possível, porém, as condições de processo devem ser muito bem avaliadas de maneira que este seja viável e os produtos oriundos, tanto o óleo de farelo de arroz quanto a fração proteica, possuam qualidade adequada para serem destinados à fins alimentícios.

One of the main areas of the Brazilian agroindustrial system is composed by the processing of oilseeds. Its importance is not only due to its main product, the oil, but also to the defatted fraction, composed of proteins. The hexane is the solvent traditionally used in vegetable oils extraction and, for that matter, the main objectives of this paper were to study the feasibility of substitution of t his solvent for alcoholic solvents on the rice bran oil extraction and also evaluate the impact of this change on the oil characteristics and the protein fraction. Some solid-liquid extraction experiments on balance condition were made to evaluate the variables on the process, such as the solvent type (ethanol or isopropanol), solvent water content (0, 6 or 12%) and temperature (50 to 80 °C) in the rice bran oil extraction. This way, the results show water influence on the solvent suppressing the oil extraction, and, on the other hand, the temperature increase benefits the process. Through extraction experiments, it was possible to characterize the obtained extracts and the defatted bran in terms of lipid, protein and minorities compound extraction, besides the characterization of the protein fraction present on the raffinated in terms of solubility and thermal analysis. In general, the results showed the water solvent influence in order to suppress the oil extraction and, on the other hand, it has been observed that the temperature increase benefited the lipid extraction process. Related to the protein content present in the extract, it was observed that the solvent hydration and temperature benefited the protein extraction. The temperature increase on the process also benefited the the γ-oryzanol extraction, however, the water solvent increase decreased the extraction of this minority compound. The water also has a strong influence on the amount of acylglycerol and free fatty acid transferred to the extract, however, for the phospholipids content, there is a decreasing influence. The process conditions did not have a significant affection on the oil composition, which is typical on rice bran oil. Regarding the protein fraction, solubility and thermal properties, which define the protein denaturing degree, there was a strong influence of the solvent hydration degree and the processing temperature, once the amount of water in the solvent and temperature are increased, it was noticed the decrease on the nitrogen solubility index. Based on the results it is possible to infer that the rice bran oil extraction with alternative solvents, ethanol and isopropanol, is possible, however, the process conditions must be well evaluated in order to be viable and the originated products, as well the rice bran oil as the protein fraction, have the proper quality for food purposes.