Abstract in English:Over the last few years, researchers have started to explore a particular class of compounds defined as ionic liquids (ILs) in attempts to use their unique characteristics. Since ILs have a very low vapor pressure, these fascinating compounds hold great potential as high performance chemicals for several applications in the (bio)pharmaceutical industry. In general, and unlike common organic solvents with comparable polarities, ILs are quite compatible with enzymes (enhancing their structural and chemical stability) and other proteins, since they can promote higher selectivities, faster reaction rates and greater enzyme stabilities in biocatalytic reactions providing, at the same time, a path for the structural and functional stabilization of protein entities. ILs appear to enhance the delivery of macromolecules, particularly protein entities, and their interactions with ILs will be tackled in detail in this review paper.
Abstract in English:Regarding all the green aspects of sustainable chemical transformations, eco-friendly processes along with economic development, environmental protection as well as natural resources preservation are mandatory. The use of unconventional media for organic transformations has been part of the quest for new eco-friendly process. As new alternative media for volatile organic solvents, deep eutectic solvents (DES) can be defined as the eutectic mixtures formed of two or more phase-immiscible components, which furnish a new homogeneous liquid phase with lower freezing point than those observed for individual counterparts. They found applications in several different fields, such as solvent/catalyst for organic transformations, biotransformations, and polymerization reactions, metal and biomass processing applications, and separation technologies. This review describes the recent studies on the use of deep eutectic mixtures as solvent and/or catalyst for multicomponent reactions in the synthesis of complex organic compounds.
Abstract in English:The investigations of the antibacterial actions, observed in ternary associations involving silver nanoparticles (AgNPs), chitosan and the antibiotics azithromycin (AZ), levofloxacin (LE) or tetracycline (TE), against Gram-negative and Gram-positive bacterial strains, were performed by in vitro antimicrobial susceptibility testing and checkerboard assays. The pH impact in the culture medium was carefully discarded, but preserving the best conditions for solubilizing chitosan. The synergistic antibacterial effects were observed in the most combinations of AgNPs, chitosan and antibiotic, leading to a reduction from 37 to 97% in the minimum inhibitory concentration of the drugs. The mechanisms for the enhanced antimicrobial effects were proposed based on the investigations of the adsorptions of the drugs on the silver surfaces through surface-enhanced Raman scattering (SERS) spectroscopy.
Abstract in English:During biodiesel storage, chemical reactions may occur, producing sludges. The aim of this study was to characterize the chemical and microbial composition of the sludge found in a biodiesel storage tank. The material was collected in a biodiesel production plant. The sludge chemical characterization was performed by Fourier transform infrared (FTIR) spectroscopy, flame atomic absorption spectroscopy (FAAS), gas chromatography (GC), and the microbial investigation used culture-dependent techniques. The deteriogenic potential of the native microbial community was evaluated using the sludge as a microbial inoculum in a 60 day experiment. The microbial growth, biodiesel degradation, pH alterations, and the detection of esters in the aqueous phase were evaluated. The chemical analysis indicated the sludge composition as fatty acids esters and metallic ions; sterols glycosides were not detected. Seven bacteria and five fungi species were obtained from the sludge. The microbial growth analysis indicated that the native community does not have high biodiesel deteriogenic capacity.
Abstract in English:4-Nonylphenol, a degradation product of ethoxylated alkylphenols, due to its harmful effects on the environment, has been banned in European Union countries, alongside their precursors. The guide on quality of drinking water from the United States Environmental Protection Agency (US EPA) recommends a maximum concentration of 28 µg L-1 for fresh water. In Brazil, there is no clear legislation containing values of maximum concentration of 4-nonylphenol. Due to this lack of regulation, a continuous monitoring is necessary for this pollutant in environmental samples. The occurrence of 4-nonylphenol (4-NP) in the surface waters of Guandu River in the state of Rio de Janeiro, Brazil, was studied by using solid-phase extraction and reversed phase liquid chromatography separation with UV detection. The analytical method satisfies these requirements, being able to detect and quantify 4-NP in a desired concentration range. Of the 19 samples analyzed, 4-nonylphenol was detected in 12, quantified in 2, showing concentration levels of 1.73 and 2.32 µg L-1 in Santa Cruz and Paracambi, respectively. This is the main hydrographic basin in the state of Rio de Janeiro, where water is collected for treatment and later distributed to most cities in the metropolitan region, including Rio de Janeiro City, and these results are therefore alarming.
Abstract in English:Immunosensors based on impedance spectroscopy for diagnosing hepatitis C are reported where the sensing units were made with the antigenic peptide PPLLESWKDPDYVPPWHG (NS5A-1) derived from the NS5A protein of the hepatitis C virus (HCV) immobilized in layer-by-layer (LbL) films with silk fibroin (SF) and deposited on gold interdigitated electrodes. The electrical response of the sensing units varied upon immersion into solutions containing the antibody anti-HCV owing to the biomolecular recognition of NS5A-1. This was associated with morphological changes on the LbL films caused by adsorption of NS5A-1 and inferred from atomic force microscopy images. Buffer solutions with different anti-HCV concentrations down to 2 ng mL-1 could be clearly distinguished by analyzing the impedance spectroscopy data with a multidimensional projection technique. The specificity toward anti-HCV antibodies was confirmed in control experiments where no significant changes in the electrical response were measured by exposing the sensing units to solutions containing an anti-human immunodeficiency virus (HIV) antibody. The high sensitivity and selectivity of the units made with LbL films demonstrate the feasibility of measuring electrical impedance as an immunosensing strategy to detect hepatitis C.
Abstract in English:Some simple reactions using commercially available chemicals were used in the preparation of new biologically remarkable quinoxaline 1,4-dioxide derivatives. Several steps performed on 4-chloro-2-nitroaniline resulted in a quinoxaline 1,4-dioxide derivative, which reacted with dimethylformamide dimethylacetal (DMF-DMA) to produce an enamine. Transamination of this enamine with anilines gave the fused 1,2-dihydropyrido[3,4-b]quinoxaline 5,10-dioxide derivatives via an addition-elimination mechanism. Basic condensation reaction of quinoxaline active methyl afforded unexpected decarboxylated arylidene derivatives by using different aromatic aldehydes. Bridged oxadiazol-2-yl derivatives were obtained from the reaction of a hydrazide derivative with carbon disulfide and p-nitrobenzoic acid respectively. Whereas, acidic condensation of that hydrazide with aromatic aldehydes afforded the arylidene hydrazides.
Abstract in English:In the present research effort, production of a crude anthocyanin extract from the fruits of jussara (Euterpe edulis Martius) was pursued. The physico-chemical characteristics of the crude anthocyanin extracts were evaluated via Fourier transform infrared spectrophotometry, X-ray diffraction, X-ray fluorescence, computed tomography via X-ray transmission, UV-Vis spectrophotometric scannings, differential scanning calorimetry, antimicrobial activity, anthocyanin quantification, total phenolic content, thin layer chromatography for sugars and pigments, free radical 2,2-diphenyl-1-picryl-hydrazil (DPPH) scavenging activity and antioxidant activity via the molybdenum phosphate complex. The results gathered suggest that the crude anthocyanin extracts had both obvious antioxidant activity and radical scavenging effects with the DPPH assay, and light antibacterial activity against Staphylococcus aureus, further suggesting that this crude pigment extract might be a valuable addition for either food or pharmaceutical applications.
Abstract in English:A great diversity of fruits is used in the food industry to obtain different products such as juices, sauces and foods. However, the food industry produces high amounts of residues. Passion fruit and guava are worldwide known fruits and very used by the food industry and generate tons of seed as residue. This work aims to study the extraction of oils from passion fruit and guava juice industries residues, their characterization and potential application as raw materials to obtain biodiesel and bio-oil. The passion fruit and guava seed oils content were 25 and 9%, respectively. In both oils, polyunsaturated fatty acids are predominant. Biodiesel obtained by esterification/transesterification of both seed oils match most of the parameters specified for biodiesel in Brazil. Bio-oils obtained by thermal cracking of the seed oils were mainly composed by hydrocarbons similar to those observed in petroleum diesel.
Abstract in English:The present work presents the development of a sensitive and selective amperometric sensor for the determination of hydrazine (HZ) in pharmaceutical formulations using a glassy carbon electrode (GCE) modified with a composite based on Co(Salophen), reduced graphene oxide (rGO) and deoxyribonucleic acid (DNA). The rGO/Co(Salophen)/DNA composite was characterized by using Fourier-transform infrared spectroscopy (FTIR), cyclic voltammetry, and amperometry. The proposed platform presented a well-defined voltammetric profile with a redox couple around 0.32 V vs. Ag/AgCl which showed excellent catalytic activity towards HZ oxidation. The peak current of HZ electrochemical oxidation on the proposed electrochemical platform have changed linearly with the HZ concentration in the range from 2 to 364 µmol L-1. The proposed platform presented sensitivity, limit of detection, and limit of quantification of 0.056 µA L µmol-1, 0.54 µmol L-1, and 1.64 µmol L-1 to HZ, respectively. The relative standard deviation for eight determinations using a solution of 50 µmol L-1 HZ was 0.85%. The proposed sensor was successfully applied for the determination of HZ in pharmaceutical formulations, and the recovery tests showed a good accuracy with recovery percentage between 99 and 101%.
Abstract in English:A binary solvent dispersive liquid-liquid microextraction (BS-DLLME) technique was developed for simultaneous determination of diuron, teflubenzuron, atrazine, and two of its metabolites (desisopropylatrazine and desethylatrazine) in natural waters. The extraction was investigated using a three components mixture design to determine the best ratio between the extractors (dichloromethane and chloroform) and the disperser solvent (acetonitrile). According to the analysis of variance, empirical response surfaces were obtained for each analyte, correlating the absolute recovery and the mixture composition. The analysis of the overlapping surfaces allowed the detection of the best condition for the analytes extraction: 481 µL of chloroform, 56.6 µL of dichloromethane, 906 µL of acetonitrile, 5.00 mL of the aqueous sample, and 10% (m/v) of sodium chloride. The proposed method was validated and successfully applied in the analysis of surface waters, presenting suitable linearity (r > 0.9990), low limits of detection (0.015 to 0.36 µg L-1) and quantification (0.049 to 1.2 µg L-1), and relative recoveries between 84.8 and 106.1%.
Abstract in English:An investigation was conducted to standardize conditions for laccase and lipase activity required to maximize trichothecene degradation. The analytical methods were suitable and validated in model solutions for detection of five analytes (T-2 toxin, deoxynivalenol, nivalenol, 3-acetyldeoxynivalenol and 15-acetyldeoxynivalenol), the methods were then applied in the degradation tests of these trichothecenes. The method of salting-out assisted liquid-liquid extraction (SALLE), using three different NaCl concentration levels, obtained recoveries in the range of 47.4-103.4% at pH 5.0 and 36.6-106.8% at pH 7.0, with an intra-day relative standard deviation under 15% for the majority of the compounds. Quantification limits remained in the region of 0.07 µg mL-1 for 15-acetyldeoxynivalenol and 0.3 µg mL-1 for nivalenol. Finally, the suitable analytical methods were applied in a study of trichothecene degradation by enzymatic action, resulting in a reduction of 12.3% for T-2 toxin, 68.4% for deoxynivalenol, 50.2% for 3-acetyldeoxynivalenol and 45.4% for 15-acetyldeoxynivalenol.
Abstract in English:The accumulation of antibiotics in wastewater has led to the development and spreading of antibiotic resistance in the environment. Amoxicillin (Amox), a beta-lactamic antibiotic, is one of the most frequently consumed antibiotics in the world. We have applied two metal-organic frameworks (MOFs) containing zinc(II) as platforms to degrade Amox. We have predicted the adsorption of this antibiotic via molecular docking calculations which have been further corroborated by means of Fourier transform infrared and UV-Vis spectroscopies, thermogravimetric analysis, X-ray diffraction and scanning microscopy measurements. We have subsequently performed mass spectrometry analysis of Amox@zeolitic imidazolate framework-8 (ZIF-8) and Amox@Zn(1,4-benzenedicarboxylate) (ZnBDC) to demonstrate the degradation of Amox upon contact with the Zn-containing frameworks. We propose a possible pathway for the degradation of Amox involving the cleavage of the four-membered β-lactam ring. These Zn-containing frameworks provide a biocompatible platform for the degradation in solution of Amox, which should also be suitable to degrade other β-lactam antibiotics.
Abstract in English:A solid-phase extraction (SPE) method based on conductive polypyrrole (PPy) nanofibers which were fabricated by electrospinning and in situ polymerization was developed. PPy nanofibers-mediated SPE followed by high performance liquid chromatography (HPLC) was used for the determination of three synthetic estrogens, namely diethylstilbestrol (DES), dienestrol (DIS), or hexestrol (HS) in milk sample. Extraction conditions including extraction nanofibers, donor solution pH and salt concentration were optimized. The target compounds were extracted from a 0.5 mL aqueous sample at pH 5.0 through PPy fibers, and then were eluted with 0.1 mL methanol. After extraction, the eluant was directly injected into an HPLC system for detection. Under the optimized extraction conditions, a large enrichment factor was achieved for three estrogens. The limit of detection (LOD) at a signal to noise ratio (S/N) of 3 ranged from 0.02 to 0.05 µg mL-1 for the estrogens in milk sample.
Abstract in English:Pd nanoparticle catalyst loading 4.7 wt.% was prepared by the deposition-precipitation method and characterized by X-ray diffraction and transmission electron microscopy (TEM). The crystallite size estimated from the integral width of the highest intensity line using the Scherrer equation was 2.3 nm. Images obtained from TEM showed an equal distribution of the particles size between 0-2 and 2-4 nm, and also a good dispersion of the nanoparticles on the catalyst support. The catalytic activity of this nanocatalyst was studied for racemization reactions of (S)-(-)-1-phenylethylamine. After that, the catalyst was used in the chemoenzymatic dynamic kinetic resolution (DKR) of some primary amines. Expressive yields and optical purities were obtained.
Abstract in English:This paper describes the use of a multiple-injection capillary electrophoresis method as a fast strategy to determine the antinitrosating capacity of nine commercial teas through nitrite quantification. The method consists of the injection of the sample followed by the injection of the control solution, employing a fused-silica capillary of 32.0 cm total length (23.5 cm effective length, 50 µm internal diameter) with background electrolyte composed of 4.0 g L-1 β-alanine and 1.5 g L-1 perchloric acid (pH 3.79) and sodium thiocyanate was used as the internal standard. Before the injections the tea samples were maintained by 1 h of incubation, at 37 °C, with sodium nitrite in perchloric acid medium (pH 2.3). In order to avoid nitrite oxidation and nitrate formation, ultra-pure nearly oxygen-free water was used to prepare the solutions. Black tea, green tea and white tea, obtained from Camellia sinensis, showed greater antinitrosating capacity (96, 93 and 89%, respectively).
Abstract in English:Crude oils containing large quantities of waxes, and in situations where sudden temperature drops occur, a crystalline network can be formed, generating flow difficulties in production, transfer and offloading lines. Despite the scientific and economic importance of this phenomenon, correlations between the behavior of petroleum in relation to its pour point are scarce in the literature. In this work, nine crude oil samples were characterized regarding density, water content, wax fraction (one- and two-dimensional chromatography), pour point, yield stress and wax appearance temperature. The results showed that the storage conditions and oil characteristics had a strong influence on the pour point. Yield stress was influenced by initial temperature of the sample, cooling rate and shear rate during cooling. Finally, the content of aromatic compounds in oil with low concentration of n-alkanes can contribute to increase the pour point.
Abstract in English:The influence of temperature on devulcanization of waste sidewall rubber via supercritical ethanol was investigated. The effect of parameters on devulcanizing process was analyzed by a full factorial experimental design. The devulcanized products at different temperatures were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry and derivative thermogravimetry (TG-DTG) and Fourier transform infrared (FTIR) spectrophotometry. In addition, the kinetics analysis for the devulcanizing process via supercritical ethanol was established. It was found that the reaction temperature was the only significant parameter. When the temperature rose above 240 ºC, the reaction rate increased dramatically. A special phenomenon was observed that the devulcanizing reaction rate of natural rubber (NR) was faster than that of butadiene rubber (BR) in supercritical ethanol. Moreover, when the reaction temperature reached 270 ºC, the use of the devulcanizing reagent did not significantly affect the sol fraction. The analysis of experimental results indicated that supercritical ethanol beyond the critical temperature could strongly promote the devulcanizing reaction, maintaining polymer structure of products as the most intact state.
Abstract in English:A method based on QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction and gas chromatography-mass spectrometry (GC-MS) detection was described for the pesticides dichlorvos, disulfoton, ethoprophos, parathion methyl, fenchlorphos, chlorpyrifos, azinphos methyl and prothiofos in sapodilla. For all compounds studies, it was observed a strong matrix effect showing the need to use matrix matched calibration strategy. Method was validated, and good linearity (R > 0.99) was obtained for all pesticides studied with limits of detection (LODs) and quantification (LOQs) ranging from 0.01 to 0.06 mg kg-1 and 0.03 to 0.2 mg kg-1, respectively. Recovery studies were performed at different levels (0.08, 0.10, 0.14, 0.20, 0.35 and 1.17 mg kg-1) and showed good results (between 70 and 120% with relative standard deviation (RSD) < 20%). A statistical test was applied to the coefficients of the analytical curves obtained in the sapodilla matrix. Analyses of commercial samples showed chlorpyrifos were detected in about 70 and 33% for fruit and pulps samples, respectively. It should be noted that chlorpyrifos is not permitted in sapodilla crops by ANVISA and EC guidelines.
Abstract in English:In this study, it was developed a method for Ca, Mg, Mn, Fe and Zn determination in palm oil samples by flame atomic absorption spectrometry (FAAS) after ultrasound-assisted emulsification and extraction induced by emulsion breaking (EIEB). Optimization of the method was carried out by a constrained mixture design. The developed method has presented limits of detection (LOD) between 0.012 and 0.057 mg L-1, limits of quantification (LOQ) between 0.039 and 0.19 mg L-1 and precision was expressed as repeatability (%RSD, n = 10) between 1.8 and 3.2% for the five studied metals. Method accuracy was assessed by the application of recovery tests (87 to 113%) and by comparison of concentration values with the dry ashing method, showing good agreement with the standard method. The developed methodology allows operational simplicity, multi-sample treatment, and low cost when compared with some methods based on decomposition. It was applied in palm oil samples collected in the Bahia State (Brazil). The concentrations (in mg L-1) found in the samples were: 3.93-13.9 Ca, 0.37-2.26 Mg, > LOQ-0.32 Mn, 1.77-8.57 Fe and 0.38-2.54 Zn.
Abstract in English:In this study, a new thiosemicarbazone ligand, namely acetylpyrazine N(4)butylthiosemicarbazone (APBT), was synthesized and characterized using 1H and 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies. Quantum chemical calculations were performed using density functional theory at the B3LYP/6-311++G(d,p) basis set level. The optimized molecular geometry of APBT is discussed based on X-ray structural reports from the literature. The assignment of the vibrational frequencies was done based on a potential energy distribution analysis using the vibrational energy distribution analysis (VEDA) 4 software. The energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) was evaluated to study the reactivity and stability of the compound. Global chemical reactivity and local reactivity descriptors of reactants and the product (APBT) were calculated to study the reaction mechanism. The region of interaction during the reaction to form APBT was determined using molecular electrostatic potential analysis. Finally, a preliminary study of the title compound as a cyclin-dependent kinase (CDK) inhibitor was further evaluated by performing a docking calculation.
Abstract in English:Lambda-cyhalothrin is a widely employed pyrethroid insecticide and is potentially toxic to the environment and to human health. Several reports indicate the presence of this insecticide in water samples worldwide, but more data about its behavior in waters and its derivative products are required. This study shows the behavior of the pesticide lambda-cyhalothrin in aqueous solution at different pH and temperature that were simulated by using water contaminated with a toxic concentration of lambda-cyhalothrin and chemical oxidative process. Lambda-cyhalothrin and its derivative products were monitored employing stir bar sorptive extraction (SBSE), using liquid and thermal desorption, combined with gas chromatography coupled with ion trap mass spectrometry (GC-IT-MS) technology. GC-IT-MS enabled the proposal of the lambda-cyhalothrin chemical transformation pathway and the full identification of twelve derivative products. Among them, only 3-phenoxybenzaldehyde is reported as a degradation product of lambda-cyhalothrin, and this compound is an environmental pollutant with endocrine disrupting activity.