Resumo em Inglês:

The crescent number of scientific articles published per year shows that research on biodiesel continues to play an important role to support the growing demand for this biofuel. The second edition of Biodiesel: An Overview presents the worldwide research in the last 15 years. Microalgae biomass is the most studied raw material alternative in this period and several studies have been carried out to develop basic heterogeneous catalysts for biodiesel production. Concerning to production technologies, supercritical conditions and intensification process have been extensively investigated. The development of new antioxidants additives has focused mainly on biomass-derived formulations and there are few studies on biocide candidates. In terms of pollutant emissions, in general, the studies showed that the addition of biodiesel generates lower concentrations of polycyclic aromatic hydrocarbons (PAH), CO and n-alkanes pollutants, but carbonyl compounds, major ions and NOx are emitted in a higher concentration compared to pure diesel.

Resumo em Inglês:

Ternary oxide silica-alumina-zirconia (SiO2/Al2O3/ZrO2) obtained by the sol-gel process was applied as novel adsorbent of ions in aqueous solution. Batch isotherms were performed using standard CuII, CdII and CaII solutions at variable pH and different concentrations. Adsorption capacity was best at weakly acidic pH. The maximum adsorption capacities were 2.28 mg g−1 for CaII, 9.89 mg g−1 for CdII, and 14.88 mg g−1 for CuII. The adsorption data fitted well to the single and dual-site Langmuir-Freundlich isotherm models. However, since the adsorption is very low in the sites with high energy, the single-site Langmuir-Freundlich provided a good fit as well. Whereas, the site responsible for the most ion adsorption was assigned to the Zr−OH group. A real sample of produced water was also tested. The new adsorbent showed a wide ability to retain many metal ions (alkali-earth, transition, and p-block metals) and even some anions were also caught by the adsorbent. The ternary oxide silica-alumina-zirconia was found to be a promising alternative adsorbent for metal ions in aqueous media.

Resumo em Inglês:

The molecular mechanism of cytoprotective effect on human erythrocytes of aminophenol and salicylates associated derivatives was related to their antioxidant capacity. The oxidative hemolysis induced by water-soluble free-radical initiator 2,2’-azobis-(2-amidine-propane)-dihydrochloride (AAPH) was inhibited by drug candidates named benzaminophen (BZL), salicytamide or 5-acetamide-salicylic acid (ASL), and salibenzamide or 5-benzamide-salicylic acid (BSL) when compared to their parents salicylic acid (SAC) and acetaminophen (ACP). Trolox (TLX) was the most powerful compound and used as positive control. BZL showed a potent effect followed by ACP > BSL > ASL. SAC did not show protective effect in any evaluated concentrations. These results are in accordance with the molecular mechanism by using theoretical calculation of single electron transfers (SET), hydrogen atom transfers (HAT), and sequential proton loss electron transfer (SPLET) by means of DFT/B3LYP/6-31++G(d,p) level of theory. [1,5] Hydrogen shift between carboxyl and phenol moieties and electronic properties related to pKa and other physical-chemical properties can be involved. The molecular association approach provides protective compounds more effective than SAC.

Resumo em Inglês:

An analytical method for multi-elementary determination in powder refreshment, based on sample digestion using dilute mineral acids and detection by inductively plasma coupled optical emission spectrometry (ICP OES) is proposed. Chemometric tools, such as fractional factorial design and principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to optimize the sample preparation conditions in closed block digester, and Doehlert design for spectrometer operation. Addition and recovery tests and analyses of certified reference material were performed to evaluate the precision and accuracy, and the results confirm the reliability of the proposed method. Limits of quantification (LOQ) between 0.02 and 36 µg g−1 were obtained. The analytical method was applied for determination of 24 inorganic constituents in 20 powder refreshment samples. Calcium, K, Mg, Na, P, S and Ti presented the highest concentrations. The analytical method was adequate for the determinations of inorganic constituents in powder refreshment samples by ICP OES.

Resumo em Inglês:

This paper presents an innovative pathway for the synthesis of triazoles using the well-known “click chemistry” assisted by the electrochemical oxidation of metallic Cu0. The click reaction is used to couple a wide range of biological interest compounds. In this case, faster and less polluting methods for a biological environment was achived by in situ Cu0 electrooxidation, providing the suitable quantity of catalyst required by click reaction. The electrochemical cell was composed of a copper foil as the working electrode, a platinum wire serving as a counter electrode, and an Ag/AgCl wire as the reference electrode. Linear anodic sweep voltammetry in a tert-butanol-water medium (1:1), an electrolyte of tetrabutylammonium tetrafluoroborate (TBATFB), showed the onset potential of Cu0 electrooxidation. Using the same electrode configuration three different triazoles were prepared under constant electrode potential, in a short time (60 min), and splendid yields (78-90%). These results indicate that the in situ CuI formation occurs on the surface of the copper foil. A pulse potential program has also been implemented in which a yield of 92% was achieved, reducing electrode passivation and consequently increasing the process efficiency. The electro-assisted click reactions are highly efficient to produce triazoles by an innovative electrochemical reaction. The products were characterized by infrared (IR), nuclear magnetic resonance (1H and 13C NMR), and mass spectrometry (MS).

Resumo em Inglês:

Essential oils (EOs) of the leaves of three Eugenia punicifolia specimens from two different Reservation Parks, namely Parque Nacional das Nascentes do Rio Parnaíba (EpNRP-I and EpNRP-II) and Parque Nacional da Chapada das Mesas (EpCM), in the state of Maranhão, Brazil, were extracted by hydrodistillation and investigated by gas chromatography coupled to mass spectrometry. Principal component and hierarchical cluster analyses indicated differences between the samples. Antiproliferative EOs activity was determined for U-251 (glioblastoma), MCF-7 (breast adenocarcinoma), NCI/ADR-RES (multidrug-resistant ovarian adenocarcinoma), OVCAR-3 (ovarian adenocarcinoma), HT-29 (colorectal adenocarcinoma), and HaCaT (non-tumor keratinocyte) cell lines applying the colorimetric method using 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) to determine the GI50 (50% growth inhibition) concentration. The extraction yields of the analyzed EOs were 0.58, 1.42 and 0.84%. The main constituents identified in two samples were α-pinene (49.75%), 1,8-cineole (13.77%) and (-terpineol (7.32%), and in the third sample, germacrene B (16.25%), (E)-caryophyllene (13.21%) and β-pinene (12.81%). The main GI50 results for sample EpNRP-I were noted for the U-251 (2.13 µg mL−1) and MCF-7 (6.72 µg mL−1) tumor lines. For the non-tumoral line HaCaT, the calculated GI50 was higher than the positive control comprising doxorubicin hydrochloride (13.35 µg mL−1). In addition, a flow cytometry analysis revealed that this same sample arrests the cell cycle of the MCF-7 line in the second interphase stage.

Resumo em Inglês:

4-Aminopyrrolo[2,1-f][1,2,4]triazine is a fundamental raw material in the synthesis of remdesivir, which demand has increased due to the tests and potential repositioning of this drug against Coronavirus disease 2019 (COVID-19). Here, three chemical steps route for the preparation of remdesivir’s nucleobase is described. Particularly, a highly chemoselective cyanation of Klein’s route and successful application of monochloramine prepared from commercial bleach as an N-amination reagent are presented.

Resumo em Inglês:

The presence of plastic waste in water bodies has led to a growing concern due to the impact on human health. Among the most important plastic additive molecules is bisphenol-A (BPA). On the other hand, micro-pollutant removal processes that make use of agro-industrial waste have aroused the interest of researchers. This is because the accumulation of lignocellulosic materials is also an environmental problem. The objective of this work is to use corncob agro-industrial residue (CC) as an adsorbent in the removal of BPA in aqueous matrix. The adsorption studies were carried out in reaction media containing the ground vegetable fiber and BPA solution in concentrations of 10, 25 and 50 mg L-1, as well as at pHs 3, 5, 7 and 9. Isotherms models and kinetic models were evaluated. The results showed that CC is a potent BPA adsorbent in aqueous solution, leading to about 90% of removal. The adsorption kinetics followed the pseudo-second order model and isotherm that best suited was the Lagmuir model, and the maximum adsorption capacity was 51.25 mgper gram of adsorbent fiber, after 20 min of contact. The thermogravimetric analysis allowed us to conclude that CC is a material resistant to high temperatures, due to the presence of a considerable amount of lignin. Finally, the best results of BPA removal efficiency by CC compared to activated carbon corroborate its high biosorption capacity.

Resumo em Inglês:

Growth in the international popularity of Brazil nuts oil (Bertholletia excelsa, Bonpl.) has demanded a closer look at quality aspects of the nuts. In this context, time-domain 1H nuclear magnetic resonance spectroscopy (TD-NMR) can be a useful tool for assessing the lipid portion of such matrices. In this work, a TD-NMR method was developed and validated to assess the oil content directly from Brazil nuts following the ISO 10565:1998 and DOQ-CGCRE-008. Full validation was addressed covering the working range from 0.67 to 25.00 g (coefficient of determination, R2= 0.9993). Limits of detection (LOD) and quantification (LOQ) were 0.20 and 0.67 g, respectively. The repeatability and intermediate precision assays met the guide requirements. Oil contents obtained in two laboratories (different equipment) were statistically similar (66.93 ± 4.69 and 70.13 ± 4.15%), highlighting the method’s robustness. The developed approach has the potential to be adopted as an industrial reference method for in situ monitoring of Brazil nuts oil contents.

Resumo em Inglês:

Using molecular simplification and molecular hybridization approaches, a series of 2-(benzylthio)-1H-benzo[d]imidazoles was synthesized and evaluated as in vitro inhibitors of Mycobacterium tuberculosis (M. tuberculosis) growth. Compounds 6p and 6z were considered the lead compounds from this series of molecules, with minimal inhibitory concentration (MIC) values of 6.9 and 3.8 µM against M. tuberculosis H37Rv, respectively. Additionally, the leading compounds were active against multidrug-resistant strains and were devoid of apparent toxicity to Vero and HepG2 cells, from 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and neutral red assays. Finally, the compounds presented good aqueous solubility and high plasma stability. These data together indicate that this class of molecules may furnish new anti-tuberculosis drug candidates for future development.

Resumo em Inglês:

The phytochemical reinvestigation from the heartwood of the extracts of Cordia glazioviana led to the isolation of four still undescribed hydroquinones derivatives designated as cordiaquinol D (1), cordiaquinol E (2), (10R)-10,11-dihydrofuran-1,4-dihydroxy-globiferin (3) and 2-[(1’E,6’E)-3’,8’- dihydroxy-3’,7’-dimethylocta-1’,6’-dienyl]-benzene-1,4-diol (4), along with the naphthoquinone 6-[(2’R)-2’-hydroxy-3’,6’-dihydro-2H-pyran-5’-yl]-2-methoxy-7-methylnaphthalene-1,4-dione (5). Additionally, six previously known compounds were also isolated: rel-1,4-dihydroxy-8(,11(;9(,11(-diepoxy-2-methoxy-8a(-methyl-5,6,7,8,8a,9,10,10a-octahydro-10-antracenone (6), didehydroconicol (7), 1(,6(-dihydroxy-7-epi-eudesm-3-ene (8), 1(,6(-dihydroxy-7-epi-eudesm-4(15)-ene (9), 10,11-dihydroxybisabolol (10), and hamanasal-A (11). The structures of the new compounds were assigned by high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) analyses. The relative stereochemistry of 3, 4, and 5 was improved by quantum mechanical calculations. Eight, out of the eleven isolated compounds (2-9), were tested through cellular viability and lipopolysaccharide (LPS)-induced inflammation assays against RAW 264.7 macrophage-like cells. Compounds 3-5 exhibited a stronger effect on LPS-induced NO production (half-maximal inhibitory concentration (IC50) 50.34, 105.83, and 66.73 µM, respectively).

Resumo em Inglês:

The comprehended knowledge of the metabolic profile of the fecal matter has been recognized as an important point for understanding metabolic changes in the human systemic metabolism and it can provide precious information about host-gut microbiota interactions. However, few analytical strategies have been addressed for a broad analysis of metabolites with different chemical properties to better understand the chemical space of fecal samples. Here we report a systematic pipeline to achieve comprehensive coverage of the fecal metabolome, from high polar to nonpolar metabolites, using dog fecal samples as a proof-of-concept. This pipeline comprises a monophasic (ACN/H2O) and a biphasic extraction (methyl tert-butyl ether (MTBE)/MeOH/H2O) of the sample, followed by three liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS) methods using HILIC-amide, RP-C18 and CSH-C18 columns, and a switch polarity acquisition mode in the electrospray ion source. This approach allowed the annotation of 376 metabolites from 70 different chemical classes. The chemical space analysis by molecular networking and the pathway analysis revealed the complexity of the fecal sample and the importance of combined methods to better understand biochemical pathways. This pipeline can be used as a valuable tool to comprehend the relationship between host-gut microbiota metabolites and the influence of diet, medication, or environmental changes.

Resumo em Inglês:

The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths.

Resumo em Inglês:

This paper reports the use of polished silver solid amalgam electrode (p-AgSAE) allied to square wave voltammetry (SWV) in the development of a simple, sensitive, fast and green electroanalytical methodology for the trifluralin herbicide determination in fresh food samples. The experimental (supporting electrolyte and potential and time accumulation) and voltammetric (pulse frequency, pulse amplitude and scan increment potential) parameters were previously optimized, which were employed in the construction of analytical curves. Therefore, these curves have enabled the calculation of analytical parameters (linearity range, equation of the analytical curves, coefficients of determination, limits of detection and quantification, recovery efficiency, and relative standard deviations for intraday and interday experiments) and they indicated that the use of the p-AgSAE is suitable for determining any contamination by trifluralin. So, the proposed methodology had to minimize the toxic residues due to the use of liquid mercury or the adsorbed products from the redox reaction that promotes passivation in the other solid surfaces. Furthermore, the optimized methodology was used to trifluralin determination in eggplant, carrot, tomato, grape juice and orange juice, and the results indicated that the proposed methodology presented high robustness, stability and sensitivity, good reproducibility, and hence it is applicable for complex samples.

Resumo em Inglês:

A simple analytical procedure is proposed for the direct analysis of guarana-based beverages in order to determine nutrient elements by inductively coupled plasma optical emission spectrometry (ICP OES). A Box-Behnken design, combined with Derringer’s desirability function, was applied to the simultaneous optimization of the ICP OES radiofrequency (RF), sample volume and nitric acid concentration. Using this approach, optimal conditions were established as RF power of 1.40 kW, and 5.0 mL of sample diluted twice with 0.5 mol L-1 HNO3. The optimized procedure allowed the determination of Cu, Fe, Mn, Zn, K, Ca, S, P and Mg with limits of quantification of 10.0, 2.0, 0.6, 6.0, 66.0, 65.0, 235, 40.0 and 20.0 µg L-1, respectively. Accuracy of the method was evaluated through analysis of water standard reference material (SRM NIST 1643f) and by addition-recovery experiments, in which satisfactory recoveries were obtained. The procedure was applied for the analysis of guarana-based soft and energy drinks. The concentration ranges (mg L-1) were: 0.36-43.3 (Ca), 4.04-192 (K), 0.36-44.8 (Mg), 10.1-1,073 (S), 0.04-92.4 (P), < 0.010-0.0174 (Cu), < 0.002-0.294 (Fe), < 0.006-0.06 (Zn) and < 0.0006-0.168 (Mn).

Resumo em Inglês:

Leishmaniasis, a neglected tropical disease with a high worldwide incidence, is considered a public health issue in Minas Gerais and Brazil, with a high degree of morbidity, not to mention the lack of therapeutic arsenal. The cysteine protease (rCPB2.8) and cyclin dependent kinase (CRK3), important enzymes for the parasite’s feasibility, were the targets chosen for investigation of the new drugs. The following study aimed to analyze several oximic derivatives starting from safrol, which can present an affinity profile for selected molecular targets using tools from molecular modeling and bioinformatics, planning and synthesis of brand new substances being tested for leishmanicidal drugs. The study allowed to verify that three oximic derivatives (5a, 5f and 5h) presented high affinity for the CRK3 enzyme, and that the compounds 5c and 5g presented good interaction by the amino acids of the catalytic site of the rCPB2.8 enzyme with atomic distances capable of generating covalent bonds, which are essential for enzyme inhibitory activity.

Resumo em Inglês:

In this study, we assessed the cytotoxic effect of 1,3-diphenyl-2-allyl-1,3-propanedione (DPAP) on B16F10 and Tm5 melanoma cells and investigated its interaction with DNA (deoxyribonucleic acid) using optical tweezers. The compound showed to be effective against B16F10 cells with selectivity index (SI) of 7.92 and interaction to the outer surface of the double helix, probably at the minor groove of DNA. This likely induced a bending deformation of the polymer chain, decreasing persistence length, and indicated that each DPAP molecule occupies a single base pair upon binding to the double helix.