Abstract in English:Catalytic combustion of soot was performed over ZnO:CeO2 catalysts obtained via a non‑alkoxide sol-gel route. Different kinetics parameters were calculated through thermal analyses, thus, enabling the correlation between the experimental data and the decomposition mechanisms probably associated with the soot decomposition in each case.
Abstract in English:In this work, the transesterification of jupati (Raphia taedigera Mart.) oil using ethanol and acid catalyst was examined. The production of biodiesel was performed using a central composite design (CCD). A range of values for catalyst concentration (1 to 4.21%), temperature (70-80 °C), and the molar ratio of alcohol to oil (6:1-13.83:1) were tested, and ester content, viscosity, and yield were the response variables. The synthesis process was optimised using response surface methodology (RSM), resulting in the following optimal conditions for the production of jupati ethyl esters: a catalyst concentration of 3.85% at 80 °C and an alcohol-to-oil molar ratio of 10:1.
Abstract in English:In this study, we prepared the macrocyclic Schiff base ligand (L) derived from 1,4-dicarbonylphenyl- dihydrazide and pentane-2,4-dione (2:2) and its CoII, CuII and NiII complexes. The compounds were characterized by the analytical and spectroscopic methods like elemental analysis, molar conductance measurements, mass spectrometry, 1H nuclear magnetic resonance (NMR), and Fourier transform infrared (FTIR) spectroscopy. The ligand behaves as a tetradentate ligand and coordinates to the metal ions via the nitrogen atoms and the complexes have the mononuclear structures. The analytical and spectroscopic results indicated that the complexes are non-electrolytes in nature and may be formulated as [M(C26H28N8O4)X2], where M = CoII, CuII and NiII and X = Cl–. The antimicrobial activities of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against different species of bacteria and fungi and the results concluded that the metal complexes are effective drugs against the tested strains as compared to the macrocyclic ligand.
Abstract in English:A simple and sensitive method using first-derivative ultraviolet spectrophotometry (DS-UV) was developed, validated, and compared to the high performance liquid chromatography (HPLC) method for quantification of paclitaxel (PTX) in a liposomal formulation. Different analytical performance parameters such as linearity, accuracy, precision, specificity, detection, and quantification limits were determined according to International Conference on Harmonization (ICH) guidelines. No interference from the lipid compounds was detected in the HPLC and the DS-UV methods at 246 nm. Linearity determined for paclitaxel concentrations ranging from 6.0 to 24.0 µg mL-1 presented a correlation coefficient higher than 0.999 for both methods. Relative standard deviation (RSD) values lower than 2% for intra- and inter-day precision data could be obtained. Accuracy mean values ranged from 98.9 to 102.0%. Robustness data showed that the PTX content was unaffected by the alteration proposed. Both methods were adequate to quantify the drug in the liposomal formulation. DS-UV proved to be rapid, accurate, selective, sensitive, and, therefore, an attractive tool for routine determination of PTX.
Abstract in English:Enzymatic kinetic resolution (EKR) of (±)-cyanohydrins was performed by using immobilized lipase from Candida antarctica (CALB) under conventional ordinary conditions (orbital shaking) and under microwave radiation (MW). The use of microwave radiation contributed very expressively on the reduction of the reaction time from 24 to 2 h. Most importantly, high selectivity (up to 92% eep) as well as conversion was achieved under MW radiation (50-56%).
Abstract in English:This paper describes a simple and rapid methodology for determining the content of adulterants in diesel by the integration of fluorescence spectra. The procedure consists of constructing analytical curves using the concentrations of each adulterant in diesel and the relative change in the fluorescence area of each blend with respect to the fluorescence area of the diesel. The results indicated that the proposed method can be used to determine adulterants such as non-transesterified residual cooking oil, kerosene, and turpentine in diesel. The detection limits were 3, 4 and 5% for non-transesterified residual cooking oil, kerosene and turpentine in diesel, respectively. The method was also successfully used to determine the non-transesterified residual cooking oil content in B5 biodiesel-diesel blend (5% biodiesel) in the range of 0-70%, with a limit of detection of 4%.
Abstract in English:Using an orthologue-based design approach, we synthesized and assayed a series of thiazolyl-1H-benzo[d]imidazole derivatives as inhibitors of Mycobacterium tuberculosis inosine 5'-monophosphate dehydrogenase (MtIMPDH). From these experiments, a benzo[d] imidazole compound was described to inhibit the enzyme in the low micromolar range (Ki IMP = 0.55 ± 0.02 µM), which places this compound among the most potent in vitro MtIMPDH inhibitors developed to date. In addition, steady-state kinetic measurements and docking simulations were employed to determine its inhibition and interaction modes. The results described herein may be useful for the design and development of novel alternative therapeutics for tuberculosis that target MtIMPDH, a predicted to be essential (for optimal in vitro bacillus growth), druggable and assayable molecular target.
Abstract in English:In this study, MCM-41 was prepared as a carrier for poorly water soluble drugs. Meloxicam (MLX) was selected as model compound. Textural and chemical characterizations were carried out by thermal gravimetric analysis (TGA), scanning electron microscope (SEM), nitrogen adsorption/desorption, X-ray diffraction (XRD) and Fourier transform infrared (FTIR). The in vitro release of MLX was performed at pH 1.2 and 6.8. After loading MLX into MCM-41, its oral bioavailability was compared with the free drug and the marketed product Mobic® (R) in rabbits. After administration of free MLX to rabbits (5 mg kg–1), MLX presented a two distinct double-peak profile in case of R and F2 due to enterohepatic cycling. The effect of MCM-41 was mainly on the rate not the extent of MLX absorption. Administration of free MLX to rabbits resulted in an AUC0–∞ value of 11.9 µg h mL–1 and a Tmax of 4.3 h. When the same dose of MLX was introduced as R or formulated into MCM-41 (F2; MLX to MCM-41 ratio of 0.7), the systemic exposure to MLX was raised significantly by ca. 4-fold as reflected in AUC0–∞ value of 46.9 and 45.5 µg h mL–1 for R and F2, respectively. Development of an immediate formulation could enhance the curative effect of MLX by increasing its drug release and dissolution rate in the preferential absorptive region.
Abstract in English:Cancer is the major health problem affecting the mankind of today. Most of the drugs used in traditional chemotherapy are very limited and the discovery of novel, more active, more selective and less toxic ones is still very intensive. A chemometric approach was applied in the study of antiproliferative activity against human colon cancer and breast cancer as well as in the study of lipophilicity of 3-(4-substituted benzyl)-5-ethyl-5-phenyl- and 3-(4-substituted benzyl)- 5,5-diphenylhydantoins. Hierarchical clustering analysis (HCA) shows that the investigated hydantoins have higher antiproliferative activity against human breast cancer cells than against human colon cancer cells. However, some hydantoins at the highest applied concentration reverse antiproliferative effect, higher against the human colon cancer cells and lower against human breast cancer cells. Principal component analysis (PCA) gives better insight into the activity of hydantoins related to their structural changes. It distinguishes more active compounds from the less active ones according to various criteria. Generally, more lipophilic 5,5-diphenylhydantoins exhibit a higher antiproliferative activity comparing to less lipophilic 5-ethyl-5-phenylhydantoins. Also, a substituent attached to benzyl moieties affects the activity additionally. The activity is particularly pronounced for compounds with cyano, methyl, chloro and bromo group. Halogen substituent were superior in antiproliferative capacity particularly in the series of 5,5-diphenylhydantoins.
Abstract in English:Methods based on multivariate calibration and diffuse reflectance infrared Fourier transform (DRIFT) and ultraviolet (UV) spectroscopies were developed for the simultaneous determination of two veterinary pharmaceutical drugs, pyrantel pamoate and praziquantel, in commercial tablets. The best UV model was obtained with the full spectra, 200-400 nm, and partial least squares (PLS). The best DRIFT model was optimized by selecting the most predictive spectral regions with synergy interval PLS, 3998-3636 cm-1, 3274-1824 cm-1 and 1100-735 cm-1. Both methods were validated according to Brazilian and international guidelines through the estimate of figures of merit, such as trueness, precision, linearity, analytical sensitivity, bias and residual prediction deviation (RPD). These methods were applied to the determination of the drugs in three different veterinary formulations commercialized in the Brazilian market and the results were compared with high performance liquid chromatography (HPLC). DRIFT was considered more suitable for the quality control of these formulations, because it is faster, does not use solvents and does not generate chemical waste.
Abstract in English:Novel rhodanine-based amide derivatives were prepared in good yields via Passerini reaction of rhodanine-N-acetic acid with aromatic aldehydes and tert-butyl isocyanide in the presence of tetramethylguanidine immobilized on silica nanoparticles (TMG-SiO2 NPs) as a heterogeneous base catalyst. The synthesized compounds were evaluated for their antibacterial effects against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis.
Abstract in English:Homogeneous polymerization catalysts require large amounts of solvent and cannot control the polymer morphology. In order to solve this issue, a narrow-shaped spherical ZSM-5 zeolite was used in ethylene polymerization as a support for zirconocene (Cp2ZrCl2). Several heterogeneous catalytic precursors were prepared and used in ethylene polymerization reactions, which showed yields (between 980-8019 kg PE mol-1 h-1) and were efficient at promoting morphological replication of the support. So, a well-established protocol for slurry polymerization reaction was found, yielding well-defined polymer particles in an advantageous polymerization process.
Abstract in English:Solid phase microextraction, one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GC×GC) with mass spectrometric detector have been used to characterize the volatile profile of Moscatel sparkling wines. Predominant classes were esters, acids, alcohols and terpenes. The efficiency of GC×GC was apparent due to the higher number of compounds positively and/or tentatively identified through this technique (two and a half times higher than with 1D-GC), as well as by the separation of co-eluted compounds in 1D-GC. Principal components analysis showed that the volatile profile of the majority of sparkling wines is similar. Only two samples differed from others and the compounds responsible for this behavior were nerol, menthol, linalool acetate, limonene and geraniol. Furthermore, a clear separation among sparkling wines done with two Moscato grape varieties (Bianco and Giallo) was observed in cluster analysis due to the higher chromatographic area of terpenes and norisoprenoids verified in Giallo samples.
Abstract in English:Two methods for determining the iodine value in vegetable oils are described. One employs mid-infrared (mid-IR) spectroscopy and the other uses hydrogen nuclear magnetic resonance (1H NMR). The determination of the iodine value is based on either the transmittance intensity of mid-IR signals or on the 1H NMR signal integration and multivariate calibration. Both of the methods showed adequate coefficients of determination (r2 = 0.9974 and 0.9978, respectively) when compared to Wijs method, which is recommended by the norm EN 14111. A statistical comparison between the results from the proposed methods and from Wijs method shows that both instrumental methods offer equivalent results and greater precisions compared to Wijs method. The regressions obtained from the constructed models were considered statistically significant and useful for making predictions. The proposed methods present several advantages compared to Wijs method because they significantly reduce analysis time, reagent consumption and waste generation. Furthermore, an analyst can choose between the mid-IR or 1H NMR to determine the iodine value.
Abstract in English:Polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in samples of superficial sediments of the Negro River, in the Amazon region of Brazil, through analyses performed by GC/MS. Total PAH concentration that includes parent and alkylated PAHs ranged from 6.5 to 5348 ng g-1 of dry weight. The ∑16 PAHs prioritized in environmental studies by the U.S. Environmental Protection Agency (USEPA) ranged from 5.6 to 1187 ng g-1. The most contaminated places were those where muddy sediments were found, with the highest concentrations of organic matter, carbon and total nitrogen. The priority PAHs with high molecular weight represented 70% of the total abundance and showed that the main source of contamination of the sediments was pyrogenic. However, petrogenic PAHs coming from oil and derivatives input is also an important contamination source to be considered.
Abstract in English:Three new ursane triterpene saponins, together with twelve known ursane triterpenes were isolated from the stems of Firmiana simplex. The structures of the saponines were elucidated on the basis of spectroscopic and chemical methods. The cytotoxic activity of all compounds was evaluated in vitro against lung adenocarcinoma (A549), ovarian cancer (SK-OV-3), skin melanoma (SK-MEL-2), and colon cancer (HCT-15) human cell lines, using a sulforhodamine (SRB) assay. 23-Hydroxyursolic acid showed cytotoxicity against the tested cell lines with IC50 values ranging from 11.96 to 14.11 µM.
Abstract in English:The reaction of ethyl (p-methoxyphenylimino)acetate with propargyl bromide mediated by activated zinc powder afforded alkynyl amine, which was then reacted with a variety of organic azides using a microwave energy source, leading to β-1,2,3-triazolyl-α-amino esters in good yield.
Abstract in English:Physically crosslinked poly(vinyl alcohol)-hyaluronic acid (PVA-HA) hydrogel membranes composed of different amounts of HA were prepared by freeze-thawing (F-T) method. F-T cycle was repeated for three consecutive cycles. HA was chosen and routinely utilized in the local treatment of chronic wounds, because of its advantages as, HA is endogenous and biodegradable polymer. Physicochemical properties of PVA-HA membranes such as, gel fraction (GF), swelling, mechanical properties, hydrolytic degradation and in vitro bio-evaluation tests were investigated. Results revealed that introducing HA into PVA structure affected significantly the physicochemical properties of membranes than the pristine PVA, because of its crosslinking interaction with PVA. With the increase of HA content in PVA hydrogel membranes, GF and mechanical stability of PVA-HA membranes decreased. However, the swelling behavior, mechanical flexibility, protein adsorption and hydrolytic degradation of PVA membrane increased. The HA content < 20% in PVA hydrogels showed high cell viability (%) and no toxicity was observed using microculture tetrazolium assay (MTT-assay). However, less cell viability was determined with high HA incorporation. PVA-HA-ampicillin free showed antimicrobial activity against Candida albicans as a result of HA presence. Thus, ampicillin-loaded wound dressing with PVA-HA membranes could be used as promising materials with easy forming and biologically evaluated for wound care.
Abstract in English:In this study, simple and efficient ultrasound-assisted emulsification microextraction (USAEME) based on applying low density organic solvents combined with gas chromatography-flame ionization detector (GC-FID) was developed for the preconcentration and determination of mononitrotoluenes (MNTs) in water samples. In this method, the fine droplets of toluene were formed and dispersed in the sample with the help of ultrasonic waves which accelerated the formation of the fine cloudy solution without using disperser solvents. Several factors influencing the extraction efficiency such as the nature and volume of organic solvent, extraction temperature, ionic strength and centrifugation time were investigated and optimized. Using optimum extraction conditions, dynamic linear ranges of 0.5-500 μg L-1, and limit of detections (LOD) of 0.3 μg L-1 were obtained for o-nitrotoluene, m-nitrotoluene and p-nitrotoluene. Finally, the method was successfully applied to the extraction and determination of MNTs in the water samples in the range of micrograms per liter with relative standard deviations (RSD) < 12%.
Abstract in English:In this study, one particular application of in situ pulse anodic stripping voltammetry and polytetrafluoroethylene membrane-based liquid three-phase micro extraction is presented for the micro extraction and quantification of cadmium(II) ions in trace levels. The main factors influencing on preconcentration and micro extraction of cadmium ions such as organic solvent, aqueous feed solution pH and acceptor phases, complexing agent concentration, time of extraction and stirring were examined and discussed in details. The design voltammetric cell was made of three microelectrodes inserted into an extraction cell, containing acceptor solution and then the voltammetric analysis was performed in situ during the extraction time. The enrichment factor and the relative standard deviation, under the optimized conditions, were 15 and 1.7% (n = 5), respectively. The obtained calibration curve was in the range of 1.0-250 nmol L-1 CdIIwith a regression coefficient of 0.9980. The limit of detection was found 0.1 nmol L–1. Due to the high total effective area of the gold nanoparticles and the low analyte concentration, the anodic stripping voltammetric method relies exclusively on the underpotential deposition and stripping process of CdIIon gold, with little hydrogen evolution during deposition at -0.40 V and no gassing at the stripping peak near 0.0 V vs. Ag/AgCl. The good selectivity for the underpotential deposition/ stripping method is one of advantages of the proposed method. The efficiency of the method for determination of cadmium(II) for real samples was checked using fish and rice samples.
Abstract in English:Crystallinity is an important property of lignocellulosic biomass due to its significant effect on acid/enzymatic hydrolysis. Normally, physicochemical analysis, such as powder X-ray diffraction and nuclear magnetic resonance, is used to reveal the crystallinity content. However, these analytical methods are expensive and laborious. In this context, methods that rapidly predict the crystallinity are important, even if used only for screening calibration. Thus, we intend to show the potential of near-infrared spectroscopy (NIRS) and chemometrics to replace reference methods in crystallinity determination. The results show that NIRS can be used to determine crystallinity in banana residues by the use of partial least squares regression, providing good coefficients of determination (R2cal,pred > 0.82), low relative errors (< 14%) and good range error ratio (≥ 7.7). The interpretation of the regression coefficients, multivariate figures of merit and external validation results indicate a strong relationship between the NIR spectrum and crystallinity in banana samples.
Abstract in English:Synthesis of dithiocarbamates by the one-pot three-component Markovnikov addition reaction of an amine, carbon disulfide and an alkyl vinyl ether or N-vinylpyrrolidone is reported in polyethylene glycol (PEG) under a mild and green procedure with high yields and completely regiospecific. Also, the products were used as efficient starting materials for amidoalkylation of electron-rich arenes such as naphthols and indoles.
Abstract in English:This work describes the treatment of dairy industry effluent using catalytic ozonation with Fe2+ as its catalyst in a semi-batch process with recycle. A fractional factorial design 24-1 was used with a reduction percentage of total organic carbon (TOCred) as response. Optimal conditions were obtained by the reaction time of 30 min, ozonator power of 35 W, O2 flow rate of 0.125 L min-1, Fe2+ concentration of 1.0 g L-1 and pH 4.0 for a 2 L raw effluent. TOCred of 64.03% represents a decrease in concentration from 473.0 to 170.1 mg L-1, with an estimate cost of US$ 0.03 L-1effluent. The treatment performed was not sufficient to discharge it directly on surface water; however, significant reduction of TOCred, among physical and chemical characteristics makes a better product to be proceeded into a biological treatment.
Abstract in English:FeCu catalysts were prepared by co-precipitation method with or without the assistance of the surfactant, polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA) or polyethylene glycol (PEG). The effect of surfactant on the structure and catalytic behavior of FeCu catalysts was investigated. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, Brunauer- Emmett-Teller (BET) surface area, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), H2-temperature-programmed reduction (TPR) and Fourier transform infrared (FTIR) spectroscopy techniques. They were tested for Fischer-Tropsch synthesis (FTS) at 230-310 oC. The results showed that the catalysts prepared with PVA were more active than the catalysts prepared without any surfactant’s assistance, the catalysts prepared with PVP and the catalysts prepared with PEG. In addition, the morphologies of the iron catalysts can be controlled by different surfactants. Meanwhile, addition of surfactant remarkably influenced the growth orientation of hematite nanocrystals, resulting in preferential exposure of the (110) plane. The characterization results revealed that PVA can promote the dispersion of iron oxides and the formation of the more active phase on the catalyst.
Abstract in English:Phytochemical investigation of the MeOH extract of Schinopsis brasiliensis Engl. stems led to the isolation of the new biflavanone (2R*,3R*,2''R*,3''R*)-7-hydroxy-4'-methoxy-flavanone- (3→3'')-3''',7''-dihydroxy-4'''-methoxy-flavanone and 4,2',4'-trihydroxychalcone-(3→O→4'')- 2''',4'''-dihydroxychalcone, whereas methyl gallate, gallic acid, (6R,9R)-megastigma-4-en-3-one- 9-O-β-glucopyranoside, quercetin-3-O-β-D-xylopyranoside and tricetin-3'-O-β-D-glucopyranoside were isolated from the MeOH extract of leaves. Their chemical structures were elucidated using spectroscopic methods and comparison with the literature data. Both biflavonoids showed weak inhibition activities of acetyl and butyrylcholinesterase enzymes when compared with eserine.