Resumo em Inglês:

The chemists from Latin-America need to do more to achieve equality in the scientific world and gain greater recognition by the broader chemical community. For this, we should rethink our strategy to fight for a more inclusive science, not only internationally but also within our region. Raise your hands and take actions to support this movement.

Resumo em Inglês:

Partially hydrogenated soybean oil and palm olein are oils that are widely used in the food industry. Continuous contact with air may cause changes of the triglycerides chemical structure, to eventually produce substances of lower molar masses that may be toxic to mammals. This study aimed to determine the kinetic parameters for the thermal oxidation of these oils and of their residual used oils from the pre-frying industrial step on preparing breaded chicken meat. The main reactions were followed by thermogravimetry (TG) and differential scanning calorimetry (DSC); the formation of the produced substances was monitored by gas chromatography flame ionization detector (GC-FID) and Fourier transform infrared spectroscopy (FTIR). These analyses indicated different chemical pathways, according to the type of unsaturation and changes in the molecular structures of the fatty acids in the oils. From the thermal analysis, more than one decomposition event was observed during the thermal oxidation process. As the soybean oil has a lower oxidation onset temperature than palm olein, it has lower rate of mass loss, with a higher activation energy value.

Resumo em Inglês:

Chitin synthase (CHS) is the enzyme specifically associated with chitin synthesis, an important component of diverse organisms including insects. Two alternative spliced transcripts of the CHS gene (AsCHS-A1 and AsCHS-A2) were identified by quantitative reverse-transcription polymerase chain reaction (RT-qPCR) during the development of the leaf-cutting ant Atta sexdens. Expression profiles of AsCHS-A transcripts increased from larva to pupae and decay in workers. Phylogenetic analysis showed both transcripts are classified within class A insect CHSs. AsCHS-A1 showed the highest expression level in larvae and pupae, while AsCHS-A2 is the main CHS transcript in workers. Our results suggest that these variants should be under regulation of different promoters. AsCHS-A1 has topology expected for insect CHSs, while the predicted AsCHS-A2 topology, with a missing A domain, is similar to some fungal CHSs. CHS-B (class B) was not identified in A. sexdens transcriptome. Ribonucleic acid interference (RNAi)-mediated gene silencing in pupae revealed that low reduction in CHS transcript levels (18%) was enough to cause morphological changes in the pupa exoskeleton impairing the process of cuticle sclerotization. To our knowledge, this work was the first to use and to show the feasibility of using RNA interference techniques on leaf-cutting ants.

Resumo em Inglês:

Pesticides are used globally to protect food against pest attack. This study evaluates the dissipation of bifenthrin and deltamethrin residues in unhulled rice and the translocation of these insecticide residues in husked rice stored at 25 °C in a biochemical oxygen demand (BOD) incubator for 35 days. For pesticide determination, the simple and efficient solid-liquid extraction methods with low temperature partition (SLE/LTP) followed by gas chromatography with electron capture detection (GC-ECD), for unhulled and husked rice were optimized and validated. These methods produced results of validated parameters consistent with Brazilian legislation, showing good efficiency (recovery rate above 95%) and limit of quantification (LOQ) < 0.090 mg kg−1 for bifenthrin and LOQ < 0.070 mg kg−1 for deltamethrin. There was a 40% dissipation of deltamethrin residues after 15 days of storage of the unhulled rice. For the insecticide bifenthrin, dissipation during the 35 days of storage was not verified. The remaining residues of dissipation in the rice grains were below the maximum residue level (MRL) prescribed by the law. The insecticide residues did not translocate in the husked rice grains destined for final consumption.

Resumo em Inglês:

The objective of this work is the identification of cheese maturation time using attenuated total reflection Fourier transform spectroscopy (FTIR-ATR) data and analytical measurements associated with chemometrics techniques. Minas artisanal cheeses were collected from 8 producers matured at times 1, 7, 14, 21, 28, 45 and 60 days, fractioned in rind and crumb for moisture, water activity (aw), dry in fat extract, pH, acidity, ashes, protein, extent and depth of proteolysis, color and identification of functional groups in FTIR-ATR. Principal component analysis (PCA), multiple linear regression (MLR) and partial least squares (PLS) techniques were performed on the dataset. PCA was used to assess differences and similarities of the samples. The best results to predict the maturation time were using MLR for analytical measurements in the portion of the crumb, with coefficient of determination (R2) = 0.92, root mean square error of validation (RMSEV) = 5.4 days and PLS for FTIR-ATR with R2 = 0.92, RMSEV = 5.3 days. The results indicated that the FTIR-ATR was adequate to predict maturation times. Although, it does not eliminate the need for more detailed chemical analysis.

Resumo em Inglês:

Processes such as ablation, erosion and corrosion generally create roughness patterns on solid surfaces. Despite the randomness of this phenomenon, some patterns can be described mathematically by studying statistically the mechanisms behind them. This paper reports an experimental study on the temporal evolution of the roughness development of polymer surfaces exposed to argon non-thermal plasma under reduced pressure of 5 mbar and 65 W of applied power. The substrates studied were polypropylene, high density polyethylene, polyamide-6 and poly(ether ether)ketone. The mean roughness data as well as the saturation roughness values showed differences between polyolefin and polymers containing heteroatoms and notably the dependence of the etching on the packing density of the polymer chains. The plasma-etched surfaces were described statistically as self-affine surfaces using scaling law analysis, exhibiting roughness exponents of α ca.0.73 ± 0.2 and growth exponents of β ca. 1.0 ± 0.1. The roughness increases and decreases successively during treatment although presenting a general linear behavior in a non-monotonous way, as a function of time. The models for the shadowing and redistribution of active species can be complemented with the transient crosslinking model of the observed flattening stages.

Resumo em Inglês:

Due to the ability to catalyze the oxidation of several substrates, the enzyme laccase has been used in several applications, among them the bioremediation of emerging pollutants. This work evaluate the capacity of the cocoa agro-industrial residue to induce the production of Pycnoporus sanguineus laccase and to apply the enzymatic extract in the biodegradation of 17-α-ethinylestradiol (EE2). The macro and micronutrient levels of the cocoa residue were previously evaluated to establish correlations with induction of enzymatic production. The fungus was cultured for 7 days at 28 °C and shaking at 150 rpm. For the biodegradation, the enzymatic extract of laccase was added to the solution of EE2 and the percentage of removal was evaluated. The production of enzyme extract was notably increased by the addition of only 1% (m v−1) of agro-industrial cocoa residue. Laccase activity reached 3920 U mL−1 on the 7th day of cultivation, being superior to the positive control (511 U mL−1). The percentage of EE2 removal was 63% after 4 h, and after 8 h of reaction the EE2 concentration was below the limit of detection (LOD, 0.35 µg mL−1). Analysis showed the presence of kojic acid in the enzyme extract, constituting a powerful redox mediator, capable of enhancing the action of laccase.

Resumo em Inglês:

This work describes the first determination of the absolute configuration (AC) of (−)-cubebin by means of electronic circular dichroism (ECD), supported by quantum chemical calculations. The comparison of experimental ECD with the corresponding quantum chemical prediction for the proper diastereoisomer resulted in the definitive assignment of the AC of the naturally occurring (−)-cubebin as (8R,8aR,9S). The challenging determination of the relative configuration (RC) of cubebin based only on experimental nuclear magnetic resonance (NMR) methods is stressed. Computation of the 13C and 1H NMR chemical shifts for all the possible diastereoisomers leads to values of mean absolute error and root mean square deviation that do not allow distinguishing among them. Thus, errors in stereochemical determination can easily occur even when using two-dimensional methods, which clearly demonstrate the complexity of this special case. To determine the RC of this bioactive natural compound with high level of confidence, it was necessary to combine the DP4+ method with X-ray crystallography. Therefore, employing the commonly used empirical methods to determine the AC of (−)-cubebin can easily lead to misassignment of its stereochemistry.

Resumo em Inglês:

A new methodology using gas-diffusion microextraction (GDME) was developed for the analysis of volatile corrosion inhibitors (VCIs). The evaluation of the inhibition efficiency and corrosion rate (ν) was performed by NaCl deliquescence tests and correlated with measurements of polarization resistance (Rp) obtained from electrochemical impedance spectroscopy (EIS) analysis and with the pH resulting from the atmosphere of the inhibitor (pHGDME). The correlation obtained between n and pHGDME indicates that the higher the value of pHGDME the lower the corrosion rate. The Raman spectra of steel was used to monitor in situ adsorption of VCI and the surface modifications caused by the inhibitors. The scanning electron microscopy (SEM) images corroborate the data of ν, both indicating that the cyclohexylamine vapor showed the best corrosion resistance performance.

Resumo em Inglês:

An organic-inorganic hybrid material based on a silica matrix and functionalized with imidazole group was successfully synthesized by the sol-gel process. The characterization techniques enabled the confirmation of the proposed structure as well as the effectiveness of the imidazole ring functionality in the structure of the material. It is insoluble in water and showed an anion exchange capacity of 2.944 mmol g-1, an excellent capacity for the adsorption of metal ions according to the literature. Thus, the metal halides CuCl2, CdCl2 and NiCl2 were adsorbed by the modified silsesquioxane from aqueous solutions. The adsorption isotherms results showed the availability of 3-n-propylimidazolium silsesquioxane chloride (SiImi+Cl-) as an efficient adsorbent material in the adsorption of metal ions, exhibiting a higher affinity for the Cu2+ ions at pH 4, with a maximum adsorption capacity of 2.80 mmol g-1. The Langmuir, Freundlich and Sips models were applied to the adsorption isotherms, both the pH and the nature of the ion were observed to be factors that influence the adjustment of the isotherms to the proposed models.

Resumo em Inglês:

In this study, a series of unsymmetrical N,N-disubstituted benzimidazolium salts were synthesized as N-heterocyclic carbene (NHC) (2a-2j) and their AgI complexes. Their structures were characterized by elemental analyses, 1H and 13C nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy techniques. Further, both the salts and their silver(I)-NHC complexes have been evaluated for their potential antibacterial properties against a panel of bacterial strains namely, Micrococcus luteus, Listeria monocytogenes, Salmonella Typhimurium, Staphylococcus aureus and Pseudomonas aeruginosa. The results show that silver complexes are effective against SalmonellaTyphimurium, Listeria monocytogenes, and Micrococcus luteus with moderate to high activity, and their minimum inhibitory concentrations ranging from 0.0034 to 1.26 mg mL−1. In addition, the benzimidazoles salts 2a-2j and silver-NHC complexes 3a-3j were screened for their antitumor activity. Complex 3e exhibited the highest antitumor effect with half-maximal inhibitory concentration (IC50) value of 4.2 µg mL-1 against MCF-7.

Resumo em Inglês:

Ultrafiltration coupled with liquid chromatography-mass spectrometry (LC-MS) was established to screen xanthine oxidase (XO) inhibitors from Pueraria lobata root extract. Four compounds were screened out and identified as puerarin, daidzin, daidzein and genistein with half-maximal inhibitory concentration (IC50) values of 30.8, 5.31, 14.5 and 3.02 µg mL−1 on XO, respectively. The interactions between these compounds and XO were investigated by fluorescence spectroscopic method. The hydrogen peroxide induced oxidative stress model of human normal gastric epithelial cell lines (GES-1) was used to investigate the protections on injured cell. As a result, four XO inhibitors exhibited protective effects without cytotoxicity. With the increased concentrations of four inhibitors, cell viability was higher with decreased mortality rate, the decrease of superoxide dismutase activity, leakage of lactate dehydrogenase and increase of intracellular superoxide anion production induced by hydrogen peroxide were restrained. It showed that these four XO inhibitors could effectively enhance cell viability and protect injury of GES-1 cells from oxidative stress.

Resumo em Inglês:

This study presents a microwave-assisted procedure for sample preparation of cocoa beans using diluted HNO3 with H2O2 for the determination of Ba, Ca, Cu, K, Mg, Mn, P, S, Sr and Zn by inductively coupled plasma optical emission spectrometry (ICP OES). Doehlert modified design was used for optimization of experimental condition, and the volume of H2O2 (0, 0.5, 1.75 and 3 mL) and concentration of HNO3 (0.5, 3.75 and 7 mol L-1) were evaluated. The best experimental conditions were chosen considering lower residual acidity (RA), lower dissolved organic carbon (DOC) and the acceptable trueness range (80-120%), were 5 mL of 3.75 mol L-1 HNO3 and 1.75 mL of 30% v v-1 H2O2. The procedure was validate using certified reference materials (CRMs), digested using the optimized conditions. The proposed procedure was applied in twelve samples of cocoa beans, and the concentrations (mg kg-1) ranged from: 7.6-27 (Ba), 520-1955 (Ca), 11-26 (Cu), 6212-10855 (K), 1677-2516 (Mg), 13-29 (Mn), 4679-6104 (P), 1499-1898 (S), 7-32 (Sr) and 34-46 (Zn). A Pearson correlation plot was proposed to evaluate the correlation between elements, revealing high correlations between Mg and K; K and P; Cu and Mn; Cu and Zn; Cu and S.

Resumo em Inglês:

Ten imides derived from safrole, 4a-4j, were synthesized and their structures were fully characterized by infrared (IR) spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and high resolution mass spectrometry (HRMS) analysis. Among the ten imides studied, eight are new. The compounds were evaluated in an in silico study and showed strong to moderate antifungal activity against various strains of Candida and Cryptococcus. In particular, compounds 4b, 4c and 4h exhibited strong antifungal activity, with minimum inhibitory concentration (MICs) between 0.17-0.73 µmol mL-1. The compound 4j exhibited antifungal activity with MIC 1.28 µmol mL-1 for all strains tested. In silico studies of the parameters of Lipinski’s rule of five indicated that these compounds are potential new drug candidates. The predict oral bioavailability can be evaluated through these parameters. In addition, a computational study helped assigning the stereochemistry of compound 4j, where the synthesized mixture is composed by two stereoisomers, 4j(1) (SRR) and 4j(2) (RSS).

Resumo em Inglês:

The leaf MeOH extract of Psychotria leiocarpa (Rubiaceae) showed in vitro non-cytotoxic and anti-dengue virus serotype 2 (DENV2) activity in human hepatocarcinoma cell lineage (HepG2). A one-step and cost-effective reversed-phase solid-phase extraction method based on high-performance liquid chromatography (HPLC) parameters allowed the isolation, directly from this bioactive extract, of the monoterpene indole alkaloids: N-glucopyranosyl vincosamide (1), vincosamide (2) and strictosidinic acid (3). The chemical structures were characterized based on 1D and 2D nuclear magnetic resonance (NMR), UV and high-resolution mass spectra (HRMS). The methodology has also allowed yielding a polyphenolic-rich fraction that was analyzed by high-performance liquid chromatography coupled to diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) revealing two flavonol triglycosides (4, 5) and three caffeoylquinic acid isomers (6-8). Compound 3 is reported for the first time in P. leiocarpa and all the phenolic compounds (4-8) are described for the first time in the genus Psychotria. Compounds 1-3 showed to be non-cytotoxic and anti-dengue active towards DENV2, highlighting vincosamide (2).

Resumo em Inglês:

The objective of this work was to carry out a bibliographic survey of secondary metabolites isolated from the Velloziaceae family, creating a bank of compounds. After the bank was created, four prediction models for potentially active compounds against pathogenic microorganisms (Candida albicans, Escherichia coli, Pseudomonas aeruginosa and Salmonella sp.) were obtained trying to identify which metabolites would be more active against the strains. Four sets of compounds with known activity for microorganisms were selected for the construction of predictive models from the CHEMBL database. Another bank with 163 unique molecules isolated from the Velloziaceae family was built. The Volsurf+ v.1.0.7 software obtained the molecular descriptors and Knime 3.5 generated the in silico model. The performances of the internal and external tests were also analyzed. The study contributed through the virtual screening of a bank of metabolites to select several compounds with potential antimicrobial activity, highlighting the biflavonoid amentoflavone which showed potential activity against the four strains.

Resumo em Inglês:

A vortex-assisted liquid-liquid microextraction method combined with high performance liquid chromatography-diode array detector has been developed for the determination of parabens in foods, cosmetics and pharmaceutical products. In this work, polymeric deep eutectic solvents composed of DL-menthol and polyethylene glycol with three different light grades were prepared successfully for the first time and used as extraction solvents. The influencing parameters on the extraction efficiency including type of extraction solvent, salt addition, composition of deep eutectic solvent, volume of extraction solvent, extraction time and solution pH were evaluated. Under the optimized conditions, using DL-menthol and polyethylene glycol 400 at a molar ratio of 1:1 as the extraction solvent, the method exhibited good linearity with linear coefficients greater than 0.9995. Limits of detection and limits of quantification were in the range of 0.3-2 ng mL-1 and 1-5 ng mL-1, respectively. The proposed method was successfully applied to determine four parabens in seven commercial products. The proposed method is simple, green and efficient, and could be applied to determine parabens in complex matrices.

Resumo em Inglês:

Despite the obvious importance of nectar, the composition of this solution remains surprisingly understudied to most of the flowers. Here we describe a simple, low-cost, and reliable methodology to analyze the three main sugars present in 210 nectar samples of Christmas Bellflowers using capillary electrophoresis (CE) and enzymatic assays. CE separation (-16 kV) was made using an electrolyte containing 36 mM NaOH pH 12, 15 mM sorbic acid, 0.5 mM hexadecyl trimethylammonium bromide (CTAB), and indirect UV detection. 72.9% of analyzed nectar samples were sucrose dominant; 13.3% sucrose rich only and 13.8% were fructose rich. The concentrations of fructose and glucose present in most of the samples were very similar, while the amount of sucrose varied considerably. The average amounts of fructose, glucose, sucrose and total sugar were 0.22, 0.21, 0.34 and 0.8 M, respectively. The nectar sample shows a pH average of 5. α-Glucosidase activity was observed in 65% of the samples with an average activity of 0.013 µU µL-1 providing a possible explanation for the similar concentrations of fructose and glucose in the samples. Under our knowledge, this is the first article that shows the analysis of sugars in nectar flowers using CE.

Resumo em Inglês:

The phytochemical study of Hippeastrum goianum led to the identification of 13 compounds by means of gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR). Compounds 7-demethoxy-9-O-methylhostasine (1) and 7-deoxi-trans-dihydronarciclasine (2) had their absolute configurations determined by vibrational circular dichroism (VCD). This is the first time that compound 1 is described in the Amaryllidaceae family. The cytotoxicity of all isolated compounds was tested against colorectal carcinoma (HCT 116), breast carcinoma (MCF-7), and non-tumor human retinal pigment epithelium (RPE) cell lines. The half-maximum inhibitory concentration (IC50) of compound 2 against each cell line was equivalent to the positive control (doxorubicin), indicating a considerable cytotoxic activity.

Resumo em Inglês:

In this study, a simple and fast procedure was developed and validated for the determination of bisphenol A (BPA) in paper products using synchronous fluorescence spectroscopy. The method was used for the determination of BPA in thirteen types of paper products, including thermal receipt papers, lottery tickets, bus tickets, business cards, mailing envelopes, flyers, napkins, printing paper, food contact paper, kitchen rolls, toilet paper, newspapers, and magazines. BPA was found in 98% of thermal receipt papers (n = 341) at concentrations ranging from below the limit of quantification (LOQ) to 27.7 mg g−1 with a geometric mean of 14.6 mg g−1 and a median of 17.7 mg g−1. The detection rate for other paper products was 96%, with BPA concentrations ranging from below the LOQ to 379 µg g−1 and a median of 17.3 µg g−1. The estimated daily intake for the adjusted bodyweight of BPA (calculated at median concentrations) through dermal absorption from handling papers was 14.5 and 1070 ng day−1 for the general population and occupationally-exposed individuals, respectively. The proposed analytical method is simple, fast, and cost-effective for the determination of BPA in paper samples. Moreover, an estimated daily exposure of Brazilians to BPA through dermal absorption from handling different types of papers is shown.

Resumo em Inglês:

Diphenylacetylene (DPA) is a precursor of stilbene and benzil, and reduction of DPA or its derivatives with metallic reagents is both an old and contemporary topic of research. By means of density function theory (DFT) calculations, a detailed investigation of the mechanism of the hydrogenation of DPA over Pd clusters was carried out at the molecular level. The various species structures in the hydrogenation of DPA over Pd clusters were optimized and analyzed. The calculations indicate that the reactions over different Pd clusters share similar reaction mechanisms, and the entire reaction path could be divided into approximately two stages: stage 1: the hydrogenation of DPA to stilbene by the addition of one hydrogen molecule; and stage 2: the hydrogenation of stilbene to the final product diphenylethane (DPE) with the recovery of the catalyst. The Pd2- and Pd3-catalyzed systems exhibit the smallest rate-determining step (RDS) energy barrier, and these systems might be the most active and effective catalytic species among the Pd clusters. Although the Pd clusters used in the current work are simple systems, these clusters could eventually provide insights into the specific structure of the Pd catalyst, since Pd and/or clusters and/or nanoparticles could be envisioned as active catalysts in experiments.

Resumo em Inglês:

The use of a polypyrrole (PPy) is described as an efficient extraction phase for disposable pipette extraction (DPX), in a fast and ruggedized analytical method for simultaneous determination of 18 organic micro-pollutants in water using gas chromatography-mass spectrometry (GC-MS). The DPX-blank pipettes were filled with PPy, a material produced through the chemical polymerization of PPy using iron(III) chloride hexahydrate. The optimized conditions were 5 extraction cycles with 600 µL of sample, adjusted to pH 9, and desorption with 150 µL of ethyl acetate using 7 cycles with the same aliquot. The calibration curves resulted in determination coefficient (R2) higher than 0.9963, the limit of detection (LOD) ranged from 0.4 to 1.5 µg L−1, and the limit of quantification (LOQ) were from 1.4 to 5.0 µg L−1. Excellent results were obtained for repeatability (2.3 to 15%, for 5 µg L−1) and intermediate precision, varying the day of analyses (3.9 to 15.5%) and the pipette tip (3.4 to 22.4%). The analyte recovery ranged from 75.4 to 115.0% for river water, and from 74.9 to 116.2% for tap water, in three different levels of concentration. The DPX-GC-MS method with PPy was successfully applied to determine the 18 analytes in river and tap water from the cities of Joinville and Florianópolis, Santa Catarina, Brazil.