Resumo em Inglês:

A novel anti-inflammatory hybrid 3-ibuprofenyl-copalic acid (3-IbuCA) was synthesized from 3-hydroxy-copalic acid isolated from Amazonian copaiba oil (Copaifera multijuga Hayne), and the anti-inflammatory ibuprofen. After full characterization, several assays to verify its anti-inflammatory effects were performed in vitro, in vivo and in silico (molecular docking). Induced fit docking was performed to observe the interactions with the enzymes cyclooxygenase-1 (COX-1) and cyclooxygenase-2 (COX-2). In vitro tests of cytotoxicity and tumor necrosis factor (TNF)-α inhibition, and in vivo tests of pleurisy, protein expression and gastrocytotoxicity were performed. Molecular docking studies with COX-1 and 2 showed binding free energies (ΔG) of -2.2 and -7.8 kcal mol-1, respectively, while for mofezolac and indomethacin, the binding free energies ΔG presented values of -8.5 and -10.1 kcal mol-1, which makes 3-IbuCA selective for COX-2 inhibition. This hybrid showed no toxicity against human macrophage at concentrations up to 2 µM, and inhibited TNF-α production in lipopolysaccharide (LPS)-stimulated macrophages. In the pleurisy assays, 3-IbuCA reduced the total leukocytes and mononuclear cells, which was followed by reduction of p-IKBα (phosphorylated nuclear factor of kappa light polypeptide gene enhancer in B-cells inhibitor, alpha) protein expression. Compared with ibuprofen alone, the hybrid caused less gastric damage. Thus, the docking, together with in vitro and in vivo studies suggest that this novel hybrid has potential as a new anti-inflammatory agent.

Resumo em Inglês:

To improve 17-α-estradiol targeting in alopecia treatment, a formulation of nanostructured lipid carrier (NLC) prepared by the sonication method was developed. The physicochemical characterization showed an average diameter of 96 ± 15 nm and the average zeta potential of -17 ± 6 mV. In addition, the encapsulation efficiency (EE) of 17-α-estradiol, assessed by ultra-performance liquid chromatography (UPLC) fluorescence, was 99.6 ± 0.3%. Physical stability of NLC stored at room temperature was followed for 42 days through several physicochemical parameters, such as diameter, zeta potential, pH and EE. No changes were observed in the physicochemical parameters during this period, demonstrating the potential of NLC as a delivery system of 17-α-estradiol. NLC dermal penetration, investigated by Franz diffusion cell and confocal microscopy using rhodamine-labeled NLCs, showed an accumulation of NLC in the outer portions of the epidermis, precisely in the hair follicle. The NLCs distribution in the skin suggests that 17-α-estradiol targeting was improved.

Resumo em Inglês:

The preparation, characterization, theoretical calculations and biological application of four RuII complexes with 2-picolinate (pic), 2,2’-bipyridine (bipy) and P-P as ligands [P-P = 1,1-bis(diphenylphosphino)methane (dppm-1), 1,2-bis(diphenylphosphino)ethane (dppe-2), 1,3-bis(diphenylphosphino)propane (dppp-3) or 1,1’-bis(diphenylphosphino)ferrocene (dppf-4)], is here presented. The complexes 1-4, with general formula [Ru(pic)(P-P)(bipy)]PF6, were characterized by elemental analysis and by infrared (IR), UV-Vis, nuclear magnetic resonance (NMR 1H and 13P{1H}) spectroscopies, cyclic voltammetry and X-ray crystallography technique. Additionally, preliminary in vitro tests against human breast (MDA-MB-231) and murine ascitic sarcoma 180 (S180) tumor cell lines were carried out, and compared with cisplatin, a reference drug. The drug concentration at which 50% of the cells are viable relative to the control (IC50) values found for complexes 1, 2, 3 and 4 against MDA-MB-231 tumor cells were around 14.6, 7.6, 3.3 and 0.4 µM, respectively, while against S180 tumor cells these complexes showed IC50 values of 71.9, 31.3, 11.2 and 3.5 µM, respectively. Therefore, the complexes were more active against MDA-MB-231 than S180.

Resumo em Inglês:

This work presents the results obtained for the gas chromatography-mass spectrometry (GC-MS) monitoring of the liquid-phase hydrodeoxygenation (HDO) reaction of furfural (FFR) to 2-methylfuran (MF) over a bifunctional Ru/RuOx/C catalyst in the presence of a direct source of H2. Hydrogenation and hydrogenolysis reactions of FFR and of the intermediate furfuryl alcohol (FA), respectively, were independently studied to provide insights on the HDO mechanism. The mass spectra monitoring of the kinetic isotope effect indicated the HDO reaction occurs through a two-step mechanism comprising of an initial ruthenium-mediated hydrogenation reaction of FFR to FA. In the second step, the FA thus formed experiences a hydrogenolysis reaction via ring activation where the hydrogen atoms are firstly attached to the C3 carbon generating a ring activated structure and removing the OH group. The observation of the peaks at m/z 85 and 84 in the mass spectrum of the MF product confirms this reaction pathway.

Resumo em Inglês:

In this work, Raman spectroscopy and density functional theory (DFT) calculations have been used in order to understand the nature of the interaction between the carotenoid bixin and organic solvents with dielectric constant varying from ca. 2 (toluene) to ca. 47 (dimethyl sulfoxide). Raman shifts registered for the main carotenoid marker band, the C=C stretching mode (1525-1533 cm-1), were used as a probe to monitor spectral changes due to chemical interaction between bixin in the solid state with the analogous solvated species. Raman spectra of bixin in solution showed significant bathochromic shifts in the wavenumber position of ν(C=C) when compared with the solid state. Among the solutions, subtle differences were observed and the polarizability rather than dielectric constant of the solvents seems to be a more appropriate parameter to explain the differences in Raman shifts which could be correlated with the solvation degree of bixin. Correlation between DFT analysis and molecular dynamics simulations obtained for cis-bixin in DMSO and CHCl3 demonstrated that the interaction of the solute with the respective solvents occurs in specific portions of the molecule, however, this result was not confirmed by the experimental data since bixin is solvated by larger numbers of solvent molecules.

Resumo em Inglês:

In the current search for renewable energy sources, residual biomass has gained ground in the concept of biorefinery. Furanic compounds such as 5-hydroxymethylfurfural (HMF), furfural (FF) and derivatives such as levulinic acid (LA), obtained from biomass, have emerged as important industrial chemical platforms. In this sense, this work aimed to use pequi bark, typical biomass and abundant in the Brazilian cerrado, in the production of HMF, FF and LA using the ionic liquid 1-n-butyl-3-methyl-imidazole bromide ([BMIM][Br]). The analysis of chemical composition of pequi bark showed that it has potential for use in the production of bioproducts, FF, HMF and LA, with yields of 65, 3 and 23.7%, respectively. High glucose conversion rates were found (> 90%). The analysis of variance (ANOVA) was applied to obtain the mathematical model with α = 0.05, verifying the significance of the second order model established for HMF (F = 0.00167) and FF (0.004494). The model fit is satisfactory, obtaining the coefficient of determination (R2) for the HMF and for the FF of 0.9599 and 0.08422, respectively. From the results obtained, it can be concluded that pequi bark has good precursor capacity for use in biorefinery processes.

Resumo em Inglês:

A general kinetic equation to simulate differential scanning calorimetry (DSC) data was employed along this work. Random noises are used to generate a thousand data, which are considered to evaluate the performance of Levenberg-Marquardt (LM) and a Hopfield neural network (HNN) based algorithm in the fitting process. The HNN-based algorithm showed better results for two different initial conditions: exact and approximated values. After this statistical analysis, DSC experimental data at three heating rates for losartan potassium, an antihypertensive drug, was adjusted by the HNN method using different initial conditions to obtain the activation energy and frequency factor. Additionally, it was possible to recover the parameters for the kinetic model with accuracy, showing that the conversion is described by a complex process, once these values do not correspond to any ideal models described in the literature.

Resumo em Inglês:

Biodiesel, known as a mixture of fatty acid ethyl/methyl esters, is seen as an alternative, ecofriendly, biodegradable and renewable non-fossil fuel. The use of heterogeneous catalysts for biodiesel synthesis can solve several problems associated with the homogeneous alkaline catalyzed-transesterification. Therefore, this work reports the evaluation of the commercial resin Amberlyst A26OH, a strong anion exchange resin, as a heterogeneous catalyst for the batch transesterification of refined palm olein with ethanol. It was studied the effects of the main operational parameters, considering the molar ratio of the reaction mixture (MRRM), namely the molar ratio of ethanol to olein taking into account only the ethanol added to the reaction system, and the total molar ratio (TMR), in this case considering also the amount of ethanol carried by the resin after its pretreatment. It was determined an optimal range of operational conditions by response surface methodology, guaranteeing conversion to ethyl esters higher than 96% with a catalyst amount corresponding to a range from 10.4 to 11.4% of the oil quantity, a temperature within the range of 55 to 60 ºC and a MRRM within the range from 3.5:1 to 6.0:1.

Resumo em Inglês:

Birnessite type manganese oxide (δ-MnO2) was synthesized for use in degradation of the cationic dye methylene blue in aqueous solution. The material was characterized using infrared spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller (BET) surface area calculations. The removal of the dye from aqueous solutions was evaluated considering the effects of the following variables: pH, manganese oxide concentration, contact time, and temperature. UV-Vis spectroscopy analyses indicated achievement of 99 and 95% removal of methylene blue (7 mg L-1) at pH 2.0 and 4.0, respectively, after 120 min of contact with the birnessite (100 mg L-1). At higher pH of 6.0 and 8.0, removals of around 99 and 80%, respectively, were obtained after a longer time of 1860 min. Analyses of total organic carbon (TOC) revealed that 80% reduction of organic matter was obtained at pH 4.0. The method of multivariate curve resolution-alternating least squares (MCR-ALS) was used together with UV-Vis spectroscopy to evaluate the removal process, confirming the degradation of methylene blue. Thionine (λmax = 601 nm) was identified as one of the byproducts of N-demethylation of methylene blue. The results indicated that the degradation process started with N-demethylations of the methylene blue molecule.

Resumo em Inglês:

Mango (Mangifera indica) has many nutritional attributes that stimulate its consumption, such as sweetness, balanced acidity and intense fruity aroma. In this study, it was demonstrated that both the variety and ripening stage have a significant impact on the aroma of mango. The volatile compound profile of “Tommy Atkins”, “palmer”, “espada” and “Carlota” varieties in green and ripe stages were characterized by headspace solid-phase microextraction gas chromatography mass spectrometry (HS-SPME/GC-MS). Thirty-three volatile compounds were identified, 30 from “Tommy Atkins”, 29 from “espada”, 25 from “palmer” and 10 from the “Carlota” variety. The major compounds were monoterpene and sesquiterpene hydrocarbons, regardless of the degree of maturity. However, the oxygenated monoterpenes, esters and lactones were also identified as minor compounds. δ-3-Carene terpene is the most abundant in the varieties “Tommy Atkins” and “palmer”, α-terpinolene is the most abundant in the cv. “espada”, and myrcene in cv. “Carlota”. The profile’s aroma obtained by HS-SPME/GC-MS associated with multivariate data analysis lead to discrimination of four mango varieties in green and ripeness stages. Therefore, the volatile compounds markers of fruit maturation identified in this study can be used to increase the efficiency of mango sorting to improve quality control and meet the consumer market requirements.

Resumo em Inglês:

Over the last twenty years, the Groebke-Blackburn-Bienaymé (GBB) reaction has been emerged as a powerful tool to access different nitrogen-based heterocycles as privileged scaffolds in medicinal chemistry. This multicomponent reaction is usually catalyzed by ordinary Brønsted or Lewis acid catalysts. Herein, we present a comparative study on the catalytic efficiencies of different rare earth triflates in GBB reactions under microwave heating, involving 2-aminopyridine or 2-aminothiazole, as aminoazole component, and different aldehydes and aliphatic isocyanides. The use of gadolinium(III) triflate as cheaper alternative catalyst for the most commonly used scandium(III) triflate was acknowledged for the first time, and a library of twenty three imidazo[1,2-a]pyridines and imidazo[2,1-b]thiazoles could be obtained in good to excellent yields.

Resumo em Inglês:

Plant litter has several functions in a forest ecosystem. Studies about plant litter are of great importance to better understand and conserve ecological environments. The objective of this study was to investigate the concentration of metals (Fe, Co, Ca, Cu, Ni, Mg, Mn and Zn) in Caatinga plant litter in the southwest region of Bahia. Plant litter was collected in summer (January/2017) and winter (August/2017). Concentrations were determined by flame atomic absorption spectrometry (FAAS). The results were submitted to multivariate analysis, principal component analysis (PCA), and hierarchical cluster analysis (HCA). The average amount of plant litter found in January and August was 1190 and 1329 kg ha-1, respectively. The twigs fraction provided the largest amount of biomass to the plant litter since this deposition occurred in greater quantity in August, a period of drought. Metal concentrations (g kg-1) in the analyzed samples ranged from 1.39-257 (Fe), < limit of quantification (LOQ)-0.269 (Co), 0.0036-0.61 (Cu), 1.39-8.76 (Ca), 0.0022-0.56 (Ni), 0.137-1.52 (Mg), 0.033-1.91 (Mn) and 0.0022-0.8 (Zn). The multivariate analysis showed that the composition of plant litter is altered seasonally.

Resumo em Inglês:

Mid-infrared spectroscopy (MID), chemical composition and physicochemical characteristics associated with chemometrics were used to rapidly detect and quantify the amount of cow’s milk added in buffalo’s milk. A total of 165 samples, divided into buffalo’s milk, buffalo’s milk added with cow’s milk (10 to 90%) and cow’s milk were evaluated to obtain fat, protein, lactose, total and defatted solids, urea, pH, acidity, cryoscopic index and band absorbances in the spectra associated with principal component analysis (PCA), multiple linear regression (MLR) and partial least squares regression (PLS). The treatments were separated into groups by PCA, allowing the classification of samples. MLR and PLS models were able to predict cow’s milk contents in buffalo’s milk. MID and results of the analytical measures studied when associated with chemometrics are efficient in the rapid quantitative detection of adulteration in buffalo’s milk.

Resumo em Inglês:

This paper describes the monitoring of ethyl carbamate concentration in sugar cane spirit from industrial distilleries in Brazil. In total, 18 distilleries from Minas Gerais and São Paulo states were evaluated, with, a total of 336 samples from August 2017 to August 2019. The ethyl carbamate was analyzed using a previously validated mass spectrometric method. Analytical curves presented coefficient of determination (R2) values higher than 0.99, and quality control samples showed a relative standard deviation (RSD) below 9%. Concentrations of ethyl carbamate ranged from not detected to 1608 µg L-1, with mean values of 294.2, 280.7 and 230.0 µg L-1 in 2017, 2018, and 2019, respectively. On average, 46, 44 and 69% of samples presented levels of ethyl carbamate below 210 µg L-1. A variety of factors may have led to distillery A having a low level (ca. 115 µg L-1) of ethyl carbamate, including controlled temperature, yeast strain, post-harvesting quality, sugar cane variety choice, and the treatment process on the sugar cane juice, which goes towards the addition of Ca(OH)2, heating and freezing. These results showed the importance of internal quality control, and that sugar cane juice treatment may be a way to decrease ethyl carbamate in the distilleries.

Resumo em Inglês:

The quantification of the low levels of catecholamines and metanephrines in biological fluids is important for clinical screening of pheochromocytoma/paraganglioma and diagnosis of overtraining syndrome in athletes. We introduce a novel, accurate and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for simultaneous quantification of these biogenic amines in human plasma. Simple protein precipitation combined with rapid 2-aminoethyl diphenylborinate-assisted liquid-liquid extraction allow us to quantify catecholamines and metanephrines over broad concentration ranges. Target analytes were monitored in positive electrospray ionization mode by multiple reaction monitoring. Method performance was validated for linearity, lower limit of quantification, limit of detection, intra-day and inter-assay precision, carry-over, recovery, and matrix effect. The assay was linear within analytical range 25-1000 pg mL-1 for epinephrine, 30-2500 pg mL-1 for norepinephrine, 15-1000 pg mL-1 for dopamine, 25-2000 pg mL-1 for metanephrine and 50-10000 pg mL-1 for normetanephrine, with lower limits of quantification of 15, 20, 10, 15 and 30 pg mL-1, respectively. The intra- and inter-day precisions for all compounds ranged from 0.4 to 6.9% and from 0.9 to 6.6%, respectively. The efficiency of novel method was confirmed by assaying external quality control samples which demonstrated consistent and accurate results.

Resumo em Inglês:

Qualea grandiflora Mart. (“pau-terra”) is a medicinal plant symbolic from Cerrado biome. Qualea species reportedly have antiparasitic properties, but their active compounds have yet to be identified. In this study, we investigated the antiplasmodial activity of Q. grandiflora fruit and stem extracts against Plasmodium falciparum. The polar extracts of both fruits and stems showed promising in vitro antiplasmodial activity against sensitive and resistant P. falciparum strains (half-maximal inhibitory concentration (IC50) = 1.2 and 4.2 ng mL-1, respectively), low cytotoxicity against human hepatic cells (IC50HepG2 ≥ 400 ng mL-1), and a noteworthy selectivity index (SI ≥ 322 and ≥ 96, respectively). The fruit ethanolic extract revealed significant oral efficacy at 100 mg kg-1 in a mouse model of P. berghei malaria (100% reduction in parasitemia on day 5 post-infection). To investigate the chemical composition of the extracts, we developed a method involving liquid chromatography-high resolution quadrupole-time of flight mass spectrometer. The chemical profiling of active extracts indicated 32 compounds, including gallotannins, ellagic acid derivatives and flavonoids. The common component in the active polar extracts was found to be ellagic acid (EA), which may contribute favorably to the in vitro and in vivo inhibitory activity observed in this study.

Resumo em Inglês:

Tea infusions are a source of mineral nutrients, including manganese. Although it is classified as an essential element, the excess of manganese is toxic for humans and its toxicity depends on its bioavailability. In this context, we propose a simple procedure to determine free and total manganese in black tea infusions by square-wave voltammetry (SWV). Free manganese was directly quantified in the samples after simple sample dilution in 0.1 mol L−1 acetic acid/acetate buffer (pH = 4.5) while total manganese determination was carried out after sample digestion with oxidant mixture (HNO3 + H2O2). For comparison, cloud point extraction was performed to remove organic-bound manganese and the content of free metal (not extracted) measured by flame atomic absorption spectrometry (F AAS) agrees with the values obtained by the proposed SWV procedure. The limit of detection and quantification were estimated for manganese determination as 0.06 and 0.20 µg L−1, respectively, with a linear range observed between 20 and 250 µg L−1. The coefficient of variation was 9.7% (50 µg L−1, n = 10). The procedure was applied to determination of free and total manganese in black tea bags and the results were compared with literature procedures employing F AAS.

Resumo em Inglês:

This study provides a risk assessment and risk maps related to the consumption of water contaminated by Al, Ba, Fe and Pb in an industrial area in the Brazilian Amazon. A total of 120 samples of drinking water were collected from 26 locations in the municipality of Barcarena, Pará State. Multiple elements were analyzed by inductively coupled plasma optical emission spectrometry. The quantifiable elements in the samples were Al, Ba, Fe and Pb. Risk assessment was performed according to U.S. Environmental Protection Agency (USEPA) procedures. Results indicate that the highest potential risk of non-carcinogenic adverse health effects for Al was in São João Island; for Ba, Fe and Pb (hazard quotient (HQ) > 1) were in Porto da Balsa community, in the city of Barcarena and Distrito Industrial community, respectively. Maps showed that areas located near Barcarena’s industrial complex are the most affected by water contamination. Therefore, these populations are at higher risk of non-carcinogenic problems, especially children and the elderly, since the majority of the population resides in these areas. Geospatial analysis contributed to delimiting and analyzing risk-change trends in the region, expanding the scope of results to a decision-making process.

Resumo em Inglês:

In this study, a novel deep eutectic solvent (DES) containing choline chloride and ethylene glycol was synthesized, and the magnetic polydopamine (PDA) was modified with this deep eutectic solvent to form Fe3O4@PDA-DES. Fourier transformed infrared spectroscopy, scanning electron microscopy, and vibrating sample magnetometer were used to characterize the proposed adsorbent. Then, this magnetic material was used as an adsorbent in the magnetic solid phase extraction process for the extraction of four sulfonylurea herbicides in water samples. The main parameters relevant to this method were investigated. Under the optimum conditions, the linearity was obtained by five points in the concentration range of 1.0-200 µg L-1 and with the correlation coefficients (r) ≥ 0.9927. The enrichment factors were in a range of 495 to 615 and the relative standard deviations were less than 4.3%. The limits of detection varied from 0.0092 to 0.0113 µg L-1. The recoveries of environmental water samples were 61.9 to 100.1%, and the recoveries of drinking water samples were 71.1-101.9%. All results highlighted the excellent potential of magnetic solid phase extraction coupled with ultra-high performance liquid chromatography strategy in selective separation and extraction of sulfonylurea herbicides in water samples.

Resumo em Inglês:

In this study, the efficiency of biochar (BC) produced from sugarcane bagasse at different pyrolysis temperatures (300, 400, 500 and 600 ºC) for simultaneous removal of CdII, PbII, CuII, CrIII, NiII and ZnII ions from aqueous solutions was assessed. All BC were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FTIR), 13C nuclear magnetic resonance (13C NMR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The effects of pyrolysis temperature, initial adsorbate concentration and adsorbent dosage on adorption capacity of BC were examined through batch experiments. The BC efficiency was also evaluated after a desorption cycle. The maximal adsorptions (CdII: 51.50%, CrIII: 74.35%, CuII: 91.18%, NiII: 47.05%, PbII: 96.17% and ZnII: 40.50%) were observed for BC produced at 500 ºC, probably because of its higher porosity and presence of functional groups detected by SEM and FTIR. The maximum adsorption capacity for CdII, CrIII, CuII, NiII and ZnII (ions fitted to Langmuir model) were 175, 303, 455, 156 and 128 µg g-1, respectively. The predominance of phenolic groups observed in Py-GC-MS data may explain the high percentage of multi-element removal. Experimental data were best fitted to pseudo-second order, Sips and Freundlich models. The BC presented good removal results after a desorption cycle.

Resumo em Inglês:

The present study investigated the activity of pyrimidine derivatives against Aedes aegypti. Two compounds, 3c and 3d showed excellent larvicide activity. Additionally, quantitative structure-activity relationship (QSAR) models were built using multiple-linear regression and partial least squares with descriptors generated from Dragon and VolSurf+ software, respectively. The best model is obtained with multiple linear regression (MLR), leading to a robust model. Moreover, the QSAR model is validated by means of some internal validation techniques in order to check its reliability, quality and robustness for predicting the larvicidal activity against A. aegypti. The models confirmed that the three-dimensional structure of molecules, steric properties, hydrophobic polar surface area, log partition (logP) and a simple pattern of substituent groups as methyl, methoxy, and succinimide in the pyrimidine derivatives are responsible for the larvicidal activity of the pyrimidine derivatives. Even more, the activity decreases by an electron-withdrawing group in R1 and increases when it is replaced by an aromatic ring activator group. These findings will aid in further studies of new pyrimidine derivatives active against Aedes aegypti.

Resumo em Inglês:

In this study we have expanded upon a family of substituted pentacyclic oxadiazadiborinane derivatives from the condensation of carbohydrazide with ortho-formylphenyl boronic acid derivatives containing a variety of chemical and physical properties. All new complexes have been characterized fully including two single crystal X-ray diffraction studies which confirm the solid-state structure of these species along with an unusual methanol activation product, which appears to be a minor solid-state side product. The lack of inherent solubility of these compounds in common physiological media precluded us from doing traditional antimicrobial activities. To circumvent this problem, we incorporated these boron compounds into chitosan films. Only weak or moderate activities against Gram-negative and Gram-positive bacteria were observed in this study.