Resumo em Inglês:

This work presents the development and characterization of a new chemically modified electrode exploiting recordable Au-rewritable compact discs (AuCDs) as substrate for drop casting of a chemically-reduced graphene-oxide slurry focusing on simple and low-cost electrochemical sensors. Increase in electrochemical responses in cyclic voltammetric and amperometric measurements were achieved using the proposed sensor. Both scanning electron microscopy and atomic force microscopy data showed increase in rugosity (about 46% higher) for the chemically reduced graphene oxide (CRGO) AuCD surface while Raman spectroscopy confirmed the presence of structural defects of graphene. The calculated charge transfer resistances (Rct) and heterogeneous electron transfer rate constants (k0) were 1638 Ω and 0.0022 cm s-1 for the bare substrate, and 91 Ω and 0.0027 cm s-1 for the modified electrode, evidencing the facilitated electron transfer of the CRGO-AuCD surface. The dopamine (DP) amperometric detection using CRGO-AuCD provided low detection limit (0.12 µg L-1) compared with other modified electrodes already reported, high precision (relative standard deviation (RSD) < 5%) and analytical frequency (370 h-1). As a proof-of-concept, DP determination in synthetic saliva samples was performed and a satisfactory recovery value (98.6 ± 0.9%) was obtained.

Resumo em Inglês:

Derivatives of the natural occurring and inexpensive terpene (R) -limonene were synthetized and completely characterized. Starting from internal olefin epoxidation, followed by epoxide opening with sodium azide and azide reduction with LiAlH4, two chiral amino-alcohols were obtained. The amino-alcohols were reacted with three different aldehydes, generating six new imino-alcohols, two of them yielding crystals suitable for X-ray diffraction characterization. The reduction of four of these compounds with LiAlH4 led to new amino-alcohols. All derivatives were obtained with good overall yields through simple reaction protocols.

Resumo em Inglês:

The essential w-3 and w-6 fatty acids have important physiological functions, such as prevention of cardiovascular diseases and atherosclerosis, and are commercially sold as fish oil capsules. In the present work, a method previously described in the literature, based on the derivatization of polyunsaturated fatty acids and their gas chromatography-mass spectrometry (GC-MS) analysis in the form of methyl esters, was partially modified and optimized for determination of w-3 and w-6 fatty acids in fish oil capsules. In addition, the w-9 fatty acid oleic acid was also determined with the optimized method, despite the lack of information about its quantities in the acquired products. The method exhibited good linearity and precision, limits of detection and quantification in the ranges from 0.16 to 0.18 mg g-1 and 0.46 to 0.63 mg g-1, respectively, and recoveries above 76%. The method was applied to analyze ten brands of encapsulated fish oil marketed in Salvador, BA, Brazil. Amongst the results, it was shown that one brand had significantly high amounts of linoleic acid, which indicates a probable adulteration of the product.

Resumo em Inglês:

This work aims to present an alternative detector for the determination of arabinose, galactose, glucose and xylose in hydrolyzed sugarcane bagasse. The detector was developed using an electrode modified with multi-walled carbon nanotubes containing cobalt oxide nanoparticles (GCE/MWCNT/CoOOH) applied in high-performance liquid chromatography (HPLC) with reverse pulsed amperometric detection (RPAD). The limits of detection obtained were 3.4 × 10-6, 4.4 × 10-6, 3.6 × 10-6 and 5.0 × 10-6 mol L-1 for arabinose, galactose, glucose and xylose, respectively. The standard addition method was used to determine the concentration of sugars in the hydrolyzed sugarcane. The determined concentrations for arabinose, galactose, glucose, and xylose were 1.0 × 10-3, 7.2 × 10-5, 3.0 × 10-3 and 2.4 × 10-3 mol L-1, respectively. The results demonstrate that this new method can be used for the detection of sugars without the interference of other electroactive species.

Resumo em Inglês:

In this study, a high-performance liquid chromatography with photodiode array detector (HPLC-PDA) method was developed and validated to simultaneously determine curcumin (CUR) and melatonin (MEL) in hyaluronic acid-coated nanoemulsions, a novel targetable delivery system to CD44 receptors overexpressed in many types of tumors. Chromatographic analyses were performed in reversed phase mode using a mobile phase consisting of acetonitrile, methanol and 0.1% formic acid (35:15:50, v/v/v) at a flow rate of 1 mL min-1, and detection at 223 and 425 nm. The method was successfully validated according to the parameters of specificity, linearity, limits of detection (LOD) and quantification (LOQ), inter/intra-day precision, accuracy, and robustness. Linearity was demonstrated in the CUR and MEL concentration range of 0.5-20.0 µg mL-1 and 1.0-40.0 µg mL-1 (r > 0.999), respectively. Relative standard deviation (RSD) values for intra-day and inter-day precision were lower than 5%, and mean drug recovery varied from 94.91 to 98.33%. Mean drug content of 85.2 and 501.4 µg mL-1 and entrapment efficiency of about 80 and 20% were obtained for CUR and MEL, respectively. These results may be correlated to the differences in the drug solubility of these drugs in the oil and water phases of the nanoemulsion.

Resumo em Inglês:

The semi-synthesis of 11 isatin derivatives was achieved through bimolecular nucleophilic substitution and click chemistry. Seven new compounds were obtained. All chemical structures were determined by infrared spectroscopy (IR), nuclear magnetic resonance spectrometry (NMR) and high-resolution mass spectrometry (HRMS) data. These derivatives were evaluated for their anti-GSK-3b activity and all isatin derivatives (N-alkyl and 1,2,3-triazolic) exhibited strong inhibitory activity, with 2b and 4h exhibiting remarkable potency. In addition, docking studies were performed with 2b and 2e models to unravel the molecular mechanism underlying the polar interactions on the GSK-3b ATP-binding site.

Resumo em Inglês:

We have prepared, by a sol-immobilization method, bimetallic catalysts with different Au:Pt atomic ratios supported on commercial SrCO3. The catalytic performance for the oxidation reaction of benzyl alcohol of such materials was compared to the monometallic counterparts, aiming at the obtaining of the best composition of the material. It was found that the Au:Pt atomic ratio presents a remarkable effect on the system performance, i.e., Pt-rich systems are more selective; however, less active. Thus, an equilibrium related to the activity and selectivity of the system was obtained by considering the yield of the system. Also, some density functional theory (DFT) insights were obtained by using a cluster of 14 atoms of Au and 1 or 2 atoms of Pt. X-ray photoelectron spectroscopy, elemental mapping in scanning transmission electron microscopy before and after catalyst usage, flame atomic absorption spectroscopy, Rietveld refinement, among other techniques, were used and associated to the experimental data, which allowed us to propose a catalytic mechanism for the system, which was important since SrCO3 has not been considered before as catalyst support for alcohol oxidation reactions.

Resumo em Inglês:

The leaves of Thunbergia laurifolia and its tea were extracted by water. The abilities to chelate heavy metal ions of the extracts were studied by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and atomic absorption spectroscopy (AAS). The results showed that the extracts exhibited high selectivity for Pb2+ chelation via a favourable-selective precipitation to Pb2+ in aqueous solutions compared to other metal ions, such as Zn2+, Cu2+ and Fe3+. The Pb2+ removal capability of the extracts were 51-52%. The selective Pb2+-trapping process of the extracts of Thunbergia laurifolia could be attributed to predominant presence of the phytochemical compounds, tannin and saponin, in the Thunbergia laurifolia leave and tea. Moreover, Thunbergia laurifolia tea also exhibited antioxidant property as demonstrating by the 2,2-diphenyl-1-picryl-hydrazyl (DPPH) free radical method.

Resumo em Inglês:

A new bis-iridoid glucoside minutifloroside (1) was isolated from Palicourea minutiflora, together with asperuloside, (-)-epicatechin, catechin, quercetin, rutin, ursolic acid, oleanolic acid, daucosterol and two monoterpenic indole alkaloids strictosidinic acid and vincosamine. Structural characterization of the compounds was established on their spectral data basis, mainly mass spectrometry (MS) and 1D and 2D nuclear magnetic resonance (NMR). The bis-iridoid showed high activity against Candida albicans strain and antioxidant activity.

Resumo em Inglês:

Thermal analysis can be used to determine shelf-life and kinetic parameters in pharmaceutical systems. This work investigates the kinetic of lumefantrine thermal decomposition, an antimalarial, using non-isothermal and isothermal experimental data. The non-isothermal conditions are analyzed applying Vyazovkin method, while isothermal conditions employ models fitting procedure and artificial neural network. Lumefantrine was characterized by powder X-ray diffraction and Fourier transform infrared spectroscopy. The initial stage of lumefantrine thermal decomposition, about 5% of conversion, corresponds to the loss of chlorine and hydroxyl, being correctly predicted by the neural network as a complex event. At room temperature, the D3 model is appropriate to describe the process, once the half-life time is 19 months, in agreement with manufacturer. Isoconversional model determined the activation energy along the whole process while isothermal methodology determined the global value considering the entire process. The results provide important information for the pharmaceutical industry to assay levels of acceptable lumefantrine contents.

Resumo em Inglês:

On November 19, 2018, 30 years after establishment, the updated Brazilian National Air Quality Standards (NAQS) were published. These NAQS were formulated as a fundamental part and instrument of the National Program for the Control of Air Quality and considering, as a reference, the World Health Organization Air Quality Guidelines, published in 2005. An important contribution is the inclusion of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 µm) as a criteria pollutant and a more restrictive target limit for PM10 (particles that have aerodynamic diameters less than or equal to 10 µm). In this work, the NAQS were discussed using, as a case study, data collected during the 2016 Olympic and Paralympic Games. The lack of PM2.5 data for Brazilian cities results in the calculation of a lower air quality index (AQI), leading to ostensibly good air quality. The results presented in this study clearly support the requirement of improvement of the new resolution since, in the present form, it does not meet the main goal of protecting public health.

Resumo em Inglês:

Herein we present four new ruthenium(II) complexes: [Ru(mtz)2(dppb)] (1), [Ru(mmi)2(dppb)] (2), [Ru(dmp)2(dppb)] (3), and [Ru(mpca)2(dppb)] (4), where mtz = 2-mercaptothiazoline; mmi = 2-mercapto-1-methyl-imidazole; dmp = 4,6-diamino-2-mercaptopyrimidine; mpca = 6-mercaptopyridine-3-carboxylic acid; dppb = 1,4-bis(diphenylphosphino)butane. In vitro cell culture experiments revealed cytotoxic activity for complexes 2, 3 and 4 against MCF-7 (breast, non-invasive), MDA-MB-231 (breast, invasive), A549 (lung), DU-145 (prostate) and HepG2 (liver) tumor cells, in some cases lower than the half maximal inhibitory concentration (IC50) for the reference drug (cisplatin). The deoxyribonucleic acid (DNA) interactions studied by viscosity measurements, gel electrophoresis and square-wave voltammetry indicated that the DNA binding affinity primarily occurs through non-covalent interactions. Only complex 2 was able to fully inhibit the DNA supercoiled relaxation mediated by human topoisomerase IB (Top IB). The analysis indicates that complex 2 inhibits the cleavage and the reconnection steps of the catalytic cycle, being both a poison and a catalytic inhibitor.

Resumo em Inglês:

Tea and yerba mate are traditional beverages prepared through the infusion of leaves of Camellia sinensis and Ilex paraguariensis, respectively. During this process, the leaching of pesticides onto the beverage, such as endosulfan, may occur. In this study, a bar adsorptive microextraction (BAµE) method prior to large gas chromatography mass spectrometry analysis was developed to analyze a- and b-endosulfan in teas and yerba mate infusions. Different sorbent coatings for BAµE were compared and the hydrophilic-lipophilic balanced polymer showed the best selectivity for endosulfan isomers. The method was validated providing good recoveries (varying from 80.4 ± 1.8 to 108 ± 4.9%) and linearities (r2 > 0.99), limits of detection from 8.0 to 4.0 µg kg-1 and limits of quantification from 40 to 20 µg kg-1 for a- and b-endosulfan, respectively. The application of the method in the analysis of real samples showed all free of endosulfan at the limit of detection of the analytical method.

Resumo em Inglês:

New Schiff base compound N, N’-bis-(4-hexadecanate)-salicylethylenediamine (named IM) was synthesized, and characterized via infrared and nuclear magnetic ressonance spectroscopies. IM was tested as corrosion inhibitor and antioxidant in soybean biodiesel. Corrosion studies were developed with AISI 1020 carbon steel in a three-step accelerated corrosion assay and IM inhibitory activity was evaluated using microscopic techiniques: optical microscopy (OM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). In 750 ppm concentration, IM showed better inhibitory activity compared to commercial compounds tert-butylhydroquinone and pyrogallol, reducing root-mean-square roughness (Rq) from 37.8 to 11.7 nm and peak-peak height (PP) from 454.1 to 120.2 nm after 8 days of immersion. Antioxidant studies were conducted using the PetroOXY equipment. In 250 ppm concentration, IM showed better antioxidant activity as metal chelator, reducing biodiesel oxidation induced by copper on biodiesel. In this concentration, IM increased the induction period from 3.0 to 5.8 h. Furthermore, the new Schiff base acts as an oxygen scavanger. This is a great property because it reduces oxygen concentration in biodiesel, reducing metal corrosion reactions.

Resumo em Inglês:

The purpose of this work was to optimize the synthesis yield of {[Ce(BTC)(H2O)]·DMF}n, a metal-organic framework (MOF)-76 family member, by solvothermal method. CeCl3.7H2O and 1,3,5-benzenetricarboxylic acid, 2:1 molar proportion, were added to N, N-dimethylformamide (DMF). Reaction time and temperature were evaluated to optimize the synthesis through a factorial design followed by a statistical analysis of the response variable (reaction yield). Infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analyses were performed to characterize the obtained white powders. Reaction yield was estimated based on {[Ce(BTC)(H2O)]·DMF}n molecular formula, which was confirmed by analytical techniques. The proposed statistic model of the response variable showed good agreement with the experimental values. Temperature parameter was the only significant variable on the reaction yields, being the highest yield (94.4%) obtained at 115 ºC for 36 h, and it was accompanied by an improvement on the particle morphology (uniformity of shape and size), forming particles with strawsheave-like morphology.

Resumo em Inglês:

The fungus Aspergillus sp. was isolated from copper mining rejects and cultured in a liquid culture medium (potato dextrose, PD) enriched with CuSO4.5H2O and Pb(NO3)2 in different concentrations. By flame atomic absorption spectrometry (FAAS) it was observed that fungus absorbed 86% of both copper and lead, with initial concentrations of 100, 500 and 1000 mg L-1. The additional results provided by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction showed ability of the microorganism to act as a biosorbent as well as its capacity to transform the tested salts into other inorganic compounds. Chromatographic profile comparison of extracts obtained from the biotic, abiotic control and the cultivation enriched with the metals showed changes in the profile of the secondary metabolism. When the copper and lead salts were tested separately, there was an increase in the production of the compounds as function of the increase of the concentration and when associated promoted the decrease and disappearance of some substances produced by Aspergillus sp.

Resumo em Inglês:

A continuous sample drop flow microextraction (CSDF-ME) technique was modified for the pretreatment of plasma samples in the determination of methadone and codeine. The limit of detection and linear range for methadone were 15.0 µg L-1 and 0.1-10.0 mg L-1, respectively. The detection limit and linear range for codeine were 25.0 µg L-1 and 0.2-15.0 mg L-1, respectively. The extraction recoveries were 41.6-52.1%, and the enrichment factors ranged from 65 to 80 for codeine and methadone, respectively. Intra- and interday precisions of the technique were calculated for codeine and methadone concentrations of 0.4 mg L-1 and were 4.2-7.6% and 2.5-5.1%, respectively. Also, the accuracy (error%) of method was in the range -10 to +7.5%. The applicability of the CSDF-ME-gas chromatography-flame ionization detector (GC-FID) technique was illustrated by the determination of the mentioned drugs in human plasma. The attained relative recoveries of methadone and codeine in the 90.0-107.5% range demonstrated the excellent capability of the optimized technique for the microextraction of the mentioned drugs from plasma. The CSDF-ME-GC-FID is a rapid, repeatable and very simple technique that requires a low sample amount.

Resumo em Inglês:

By using HAuCl4 as the gold precursor, spherical Au@SiO2/TiO2 core-shell nanostructures were prepared with the sol-gel method and ethanol reflux. The preparation process was convenient and fast. The obtained samples were characterized by UV-Vis, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The results suggested that these spherical particles were in uniform distribution of particle size and with excellent monodispersity. Gold nanoparticles were successfully loaded on the core-shell structure, and TiO2 nanoparticles were functionalized. With the functionalization of gold nanoparticles, Au@SiO2/TiO2 nanoparticles showed excellent photocatalysis activity for the degradation of methyl orange. The possible mechanism of catalytic degradation was discussed in the paper.

Resumo em Inglês:

7a-Hydroxyroyleanone is a bioactive diterpene isolated from leaves of Tetradenia riparia, active against tuberculosis and T. cruzi. In order to use this compound as starting material for the synthesis of compounds with enhanced bioactivity we aimed the dehydration of the 7-alpha-hydroxyl group of royleanone. The reaction performed in acetic acid and hydrochloric acid under reflux gave an unexpected chlorinated naphtoquinone, with aromatization and opening of one of the rings of the starting material, as major product, besides 6,7-dehydroroyleanone and a complex mixture of other products. The reaction products were purified by high-speed countercurrent chromatography with hexane-acetonitrile 1:1. Compounds were tested for their anti-leishmanial activity (L. amazonensis) pointing out a potential leishmanicidal agent which may favor the development of more effective therapies.

Resumo em Inglês:

In order to provide an effective and environmentally correct alternative for oil extraction, subcritical n-propane was used under different temperature and pressure conditions to obtain Brazil nut oil. The composition of the oil was determined and compared to the oils obtained by conventional methods. The result of the extraction yield obtained using subcritical fluid extraction (SFE) at 60 ºC, 6 MPa and granulometry < 1.40 mm (63.13%) presented minor differences to the yield obtained by Soxhlet extraction (SE) (68.44%) and Bligh and Dyer extraction (BD) (59.54%). The composition in fatty acids was similar regardless of the method of extraction used. Oxidized triacylglycerols (TAGs) were found in the oils extracted by SE and BD while they were not detected in the oils extracted by SFE. The quantity of bioactive compounds was higher in the oils obtained by SFE. Thus, the SFE using n-propane preserves the nutritional characteristics and lipophilic components of the oil, besides improving the availability of bioactive compounds from an effective “green extraction” without the use of toxic solvents.

Resumo em Inglês:

The fact that the dissymmetry lgeb (g-factor) of camphor is large has been known for decades, and the interpretation of the observed data has also been known for a long time. However, due to the ability of quantum chemical methods to describe chiroptical phenomena more appropriately, additional approaches based on these methods have been successful employed. The g-factor lgebra in S-camphor and L-tryptophan have been investigated by UV-Vis and electronic circular dichroism (ECD) spectroscopies of the n ® p* electronic transition. Time-dependent density functional theory (TD-DFT) calculations at CAM-B3LYP/6-311++G(3df,2p)//B3LYP/6-311++G(2d,p) level of theory including Grimme’s dispersion effects have been performed. The lgebra effect was added using solvation model based on density (SMD) approach in solvation environment. The results permit insights into the ground and excited states electronic properties associated with the g-factor. The theoretical spectra showed good similarity with the experimental ones. The theoretical ECD of camphor was found at 282 nm, whereas the experimental shows its maximum at 290 nm. Regarding the maximum value of the molar absorptivity lgebrante, the theoretical and experimental values were 16.2 and 30.2 M-1 cm-1, respectively. The same concordance was obtained for g-factor, as follows: -0.0445 and -0.0886, for experimental and theoretical results, respectively.

Resumo em Inglês:

Polychlorinated biphenyls (PCBs) are carcinogenic to humans and can be found in Fuller’s earth used for the regeneration of used transformer oil. This work describes a highly selective gas chromatographic-selected ion monitoring mass spectrometric method (GC-MS/SIM) for the simultaneous determination of three Aroclor PCB congener mixtures (1242, 1254, and 1260). The separation of the PCBs could be systematically varied by changing the temperature conditions of the chromatographic column. Methods were first selected from the literature, and the resolution of the PCBs was then optimized by adjusting k* (effective retention), a (selectivity), and N (column efficiency), enabling the detection of 83 PCBs in 35 min. The extract of PCBs from Fuller’s earth was obtained by ultrasonication (employing hexane and acetone as solvents) and cleanup with Florisil and was concentrated to about 500 µL. The ions analyzed in SIM mode were divided into groups according to the similarity (m/z) of the PCB fragmentation profiles. The limits of detection (LOD) and quantification (LOQ) were 0.19 and 0.64 µg kg-1, respectively. The method developed was used to determine the PCBs present in Fuller’s earth provided by an electric power company. The mean total PCBs concentration was found 1.9 µg kg-1 in Fuller’s earth.