Resumo em Inglês:

MnCo2O4/Au was investigated as an electrocatalyst for the oxygen reduction and evolution in alkaline media. Polarization curves showed an unprecedented activity for the oxygen reduction due to a synergistic effect between MnCo2O4 and Au, involving CoII/CoIII-MnIII/MnIV, as revealed by in situ X-ray absorption near edge structure (XANES). Additionally, results showed favorable interaction between the oxide and Au, which enhanced the activity for the oxygen evolution reaction.

Resumo em Inglês:

Carbenoids are a class of highly reactive reagents that play an important role in modern organic synthesis. These species are very similar to singlet state carbenes since they have an ambiphilic character and react by a concerted mechanism allowing stereospecific transformations. Herein, we discuss these and other chemical aspects of zinc, lithium and magnesium carbenoids as well as relevant applications of these intermediates in organic synthesis.

Resumo em Inglês:

Volatile organic compounds (VOCs) from ten endophytic fungal species belonging to the Botryosphaeriaceae family were extracted by headspace-solid phase micro-extraction (HS-SPME) and analyzed by gas chromatography-mass spectrometry (GC-MS). Thirty-four VOCs were identified. Most of the compounds are sesquiterpenes (14 non-oxygenated and 10 oxygenated), and two linear ketones and eight alcohols were also identified. Multivariate data analysis (PCA and HCA) allowed the differentiation of all investigated species, and proved to be efficient for the differentiation of Neofusicocum parvum and N. ribis, which are considered very similar species. α-Bisabolol, α-selinene, α-cedrene epoxide and guaiol acetate were suggested as biomarkers.

Resumo em Inglês:

The non-commercial copolymers E45S8, E45S17 and their mixtures with Pluronic® P123 (E21P67E21) were studied as carriers of the model drug griseofulvin. Critical micelle concentration (cmc) (dye solubilisation method), drug solubilisation capacity (Scp and Sh) determined by ultraviolet-visible (UV-Vis) spectroscopy and 1H nuclear magnetic resonance (1H NMR) and cytotoxicity (LDH activity in human neutrophils) were studied. E45S17 1.0 wt.% dispersions presented colloidal aggregates limiting its Scp in comparison to E45S8, but in 0.1 wt.% solutions this phenomenon seemed to be absent and E45S17 presented a higher Scp. The mixtures that showed the best Scp results contained 50% of P123 and presented low cmc. An evaluation of literature data suggested a minimum Em content of 62% in EmSn copolymers below which the increase of Sn length does not lead to an increase of Sh. The results suggested no toxicity of the copolymers on human neutrophils, supporting the use of P123 and poly(styrene oxide) containing copolymers as drug carriers.

Resumo em Inglês:

A method using dispersive liquid-liquid microextraction (DLLME) based on low density solvent (LDS) combined with liquid chromatography with diode array detection (LC-DAD) has been developed for determination of parabens. Some DLLME parameters such as kind and volumes of extraction and disperser solvents, pH of the aqueous samples, ionic strength, extraction, centrifugation and speed time, were investigated. The method exhibits good linearity (0.9990 to 0.9993), limits of detection (0.5-0.8 µg L-1), and limits of quantification (1.3-2.4 µg L-1). In optimum conditions, enrichment factors and recoveries of studied parabens obtained were 38.9 to 88.4% and 30.3 to 68.0%, respectively. Surface water samples collected from Mogi Guaçu River (São Paulo state, Brazil) were analyzed, showing average contents of methyl-, ethyl-, propyl-, and n-butylparaben of 8.0, 5.8, 13.1 and 15.1 µg L-1, respectively. This is the first study on parabens in a Brazilian River, in a long stretch of river (ca. 300 km of extension).

Resumo em Inglês:

Nucleation and growth mechanism of iron oxide nanoparticles on zeolite template and their stability dependence are reported. Hyperfine field resulting from the variation of particle size indicates the effect of zeolite on particles growth; particle size decreases at lower concentration of zeolite. At higher concentration, a fraction of nano Fe3O4 experiences hyperfine field (45 and 49 T) similar to bulk particles. Effect of incubation and digestion time on the particles growth and the binding effect with zeolite are discussed. Annealing treatments show that the binding of nanoparticles with zeolite stabilizes the nanoparticles with regard to agglomeration and structural transformation. Thermogravimetry-differential thermal analysis (TG-DTA) shows that increase in dehydration temperature from 335.1 to 351.7 K results in zeolite content increasing from 0 to 1000 mg. Weight loss of the particles prepared in incubation time of 0.5 min is 9.46% and reaches 13.9% in 240 min. The weight loss remains practically constant at ca. 9% irrespective of the digestion method.

Resumo em Inglês:

Tris-heteroleptic ruthenium(II) cis-[Ru(Me4-phen)(dcbH2)(NCS)2], where Me4-phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, dcbH2 = 4,4'-dicarboxylic acid 2,2'-bipyridine, was synthesized, purified and characterized. Its characteristics were compared with those determined for cis-[Ru(Me2-phen)(dcbH2)(NCS)2] and cis-[Ru(phen)(dcbH2)(NCS)2] aiming to evaluate the effect of the number of methyl groups on the properties of the compounds. Changes in the Fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (NMR) spectra indicated a modification in the electronic distribution of the complex because of the presence of methyl groups at the 3 and 8 positions of 1,10-phenanthroline. These changes also modified the excited state properties and resulted in a blue shift of the absorption and emission spectra. The complex was incorporated onto TiO2 to prepare dye-sensitized solar cells, achieving up to JSC = 11.9 mA cm–2, VOC = 0.627 V, ff = 0.67 and η = 5.0%.

Resumo em Inglês:

The composition of essential oils from flowers of Solanum stipulaceum Roem & Schult collected in May and September was studied for the first time. Effects of g-radiation on volatile constituents were investigated by gas chromatography (GC) with flame ionization detector (FID). In addition, the antileukemic activity was studied by a 3-(4,5-dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide (MTT) colorimetric assay against human cell lines HL-60 and THP-1. The main constituents of the essential oil of flowers collected in May were β-caryophyllene (25.8%), γ-gurjunene (11.9%), and β-gurjunene (8.2%), whereas the essential oil of flowers collected in September was mainly composed of β-caryophyllene (26.5%), caryophyllene oxide (11.0%), and γ-gurjunene (10.0%). The main components of essential oil from flowers collected in September were not significantly affected by γ-radiation at lower doses than 10.0 kGy. No cytotoxic activity in leukemic cell lines was observed for non-irradiated samples. However, irradiated samples exhibited slightly cytotoxic activity.

Resumo em Inglês:

Species of the Annonaceae family are used in traditional medicine, and several antitumor acetogenins have been isolated from the leaves of Annona muricata and Rollinia mucosa. Leaves samples (self-shaded and sun-exposed) of these species were collected during winter and summer seasons. Extraction media were prepared from mixtures of five solvents according to a simplex centroid design. Plant extracts were analysed by injection into a high-performance liquid chromatography with diode array detection (HPLC-DAD) and evaluated after applying by multivariate curve resolution-alternating least-squares (MCR-ALS) and discriminant-unfolded partial least-squares (D-UPLS). The objective was to check whether the chemometric resolution of chromatographic profiles could help in the discrimination of samples according to taxonomic classification, sun exposition and/or harvest season. The results indicate that extraction media containing ethanol as main solvent achieved discrimination of self-shaded versus sun-exposed plants and harvest season of Annona muricata. Also, D-UPLS analysis allowed taxonomic discrimination between Annona muricata and Rollinia mucosa extract samples.

Resumo em Inglês:

In this work, a batch adsorption study was conducted to investigate the removal efficiency of lead, copper and zinc ions from aqueous solutions. Magnetic amine-functionalized mesoporous silica nanoparticles were synthesized by grafting amine groups within the channels of magnetic mesoporous silica nanocomposites. Morphological and structural characterizations were made by X-ray powder diffraction, N2 adsorption-desorption, scanning and transmission electron microscopy, Fourier transform infrared spectroscopy and elemental analysis. Among different factors influencing the sorption process, solution pH, shaking time and mass of adsorbent were investigated. The removal efficiencies were higher than 98% under optimized experimental conditions. Maximum adsorption capacities calculated by the Langmuir model were 268, 93 and 82 mg g-1, for lead(II), copper(II) and zinc(II) ions, respectively. Accuracy and applicability of the synthesized adsorbent was estimated by analyzing spiked natural water samples and good recoveries (> 95%) were obtained with no matrix interferences.

Resumo em Inglês:

The activity of the heterometallic alkoxide [FeCl{Ti2(OiPr)9}] (1) towards polymerization of rac-lactide (rac-LA) and ε-caprolactone (ε-CL) was investigated in toluene solution and in bulk at various temperatures, monomer/heterometallic alkoxide molar ratio and reaction times. The alkoxide 1 was active in solution for ε-CL and in bulk for both monomers. Polymers were obtained in good yields with molecular weights ranging from 3890 to 15000 g moL-1 and polydispersity indexes (PDI) values varying from 1.3 to 2.5. Based on the 1H nuclear magnetic resonance (NMR) end-group analysis of polymers, a coordination-insertion mechanism was suggested for both monomers. The average number of growing chains per molecule of initiator (4 to 5 for rac-LA and 7 to 8 for ε-CL) indicates that both bridging and terminal isopropoxides are active initiating groups. Kinetic studies with ε-CL indicated that the polymerization rate is first order with respect to monomer concentration. The catalytic properties of 1 were compared to those found for other titanium(IV) and iron(II) complexes using ε-CL as a model monomer.

Resumo em Inglês:

In this study, the monitoring of pesticide residues, which show potential for environmental contamination, in center-pivot irrigated areas in the Brazilian cerrado, was performed. The pesticides monitored were acephate, atrazine, azoxystrobin, buprofezin, carbofuran, cyproconazole, chlorpyrifos, difenoconazole, diuron, imidacloprid, malathion, methamidophos, metolachlor, metribuzin, monocrotophos, monuron, thiamethoxam, and triazophos. Surface water samples were collected upstream and downstream of Tijunqueiro dam. The subsurface water in piezometric wells was drilled in the surroundings of the irrigated area; fish and sediment were collected in the dam. The technique of solid phase extraction (SPE) was used for the extraction of water samples, the matrix solid phase dispersion (MSPD) for the sediment samples and QuEChERS (quick, easy, cheap, effective, rugged and safe) for the fish samples. The multiresidue methods used were accurate and precise for most pesticides monitored by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Atrazine was detected in two of the subsurface water samples.

Resumo em Inglês:

Ten 4,7-methanoisobenzofuran-1(3H)-ones were synthesized and their insecticidal activities against the insect pest Diaphania hyalinata were evaluated. The most active substances have been selected from the initial screening to find the dose to kill 50 (LD50) and 90% (LD90) of the melonworm. Time-mortality curves of the three selected formulations at the LD90 concentration have been made against D. hyalinata. From the time-mortality curves we found that the formulation (3aR,4R,5S,6S,7S,7aS)- and (3aS,4S,5R,6R,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aR,4R,5R,6R,7S,7aS)- and (3aS,4S,5S,6S,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 50% of the melonworm after 2 h, presenting the best knockdown effect. Bioassays against Solenopsis saevissima and Tetragonisca angustula were carried out for the lactones selected in the initial screening against D. hyalinata. The formulation (3aS,4R,5S,6S,7S,7aR)- and (3aR,4S,5R,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aS,4R,5R,6R,7S,7aR)- and (3aR,4S,5S,6S,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 31.25 and 68.30% of the pest natural enemy and the pollinator bee, respectively. At the same concentration this formulation killed 90% of D. hyalinata. The selectivity in favor of the non-target organisms has rendered this formulation a position as a promising agrochemical.

Resumo em Inglês:

The continuous search for antimicrobial candidates pushes the pursuit of compounds in the most diverse organisms. Amphibians are known as a prolific source of antibacterial peptides. Based on the rich biodiversity of the Amazon region the unexplored green-tree frog (Hypsiboas cinerascens) was studied for its skin secretion peptide content. Chromatographic separations and established tandem mass spectrometry (MS/MS) methods were used for sequencing the primary structures of the purified compounds. De novo sequencing lead to the identification of five new peptides related to hylaseptin P1, displaying an aminated C-terminal. Sequencing of the complementary deoxyribonucleic acid (cDNA) analysis allowed the disambiguation of isobaric amino-acids for C-01. Matrix assisted laser desorption ionization (MALDI) was carried out, demonstrating the in situ co-occurrence of the identified peptides in the dorsal skin. The major peptide C-01 was synthesized and assayed against a selection of microorganisms displaying minimal inhibitory concentrations (MICs) ranging from 4 to 16 µM.

Resumo em Inglês:

We present here our results in the synthesis of eleven new 3-(1H-1,2,3-triazol-1-yl)-2-(arylselanyl)pyridines by copper-catalyzed azide-alkyne cycloaddition reactions. The reactions were performed in the presence of catalytic amount of copper(II) acetate and sodium ascorbate using a mixture of tetrahydrofuran/water (1:1) as solvent at room temperature in air. The reaction is tolerant to different functional groups such as substituted-benzene rings, alcohol and ester and none electronic or steric influence was observed. All the products were obtained in good to excellent yields. Alternatively to the conventional oil bath heating, the use of microwave irradiation or ultrasound methods is also presented as alternative energy sources.

Resumo em Inglês:

As part of our ongoing search for bioactive constituents of natural Korean medicinal resources, a bioassay-guided fractionation and chemical investigation of the MeOH extract of Raphanus sativus (Brassicaceae) seeds resulted in the isolation and identification of fifteen compounds, including a new phenolic compound. The structure of the new compound was determined by extensive spectroscopic analysis and the Mosher's method. One of the compounds has been recently reported as a synthetic product. Some compounds showed moderate antiproliferative activities against the tumor cell lines A549, SK-OV-3, SK-MEL-2, and HCT-15 with IC50 values in the range of 5.62 to 28.88 μM. Moreover, the anti-neuroinflammatory activities of the isolates were determined by measuring the nitric oxide (NO) levels in the medium using murine microglia BV-2 cells. With exception of one specific compound, all the others inhibited the lipopolysaccharide (LPS)-stimulated NO production (IC50 values < 200 μM).

Resumo em Inglês:

Validating methodology formerly reported, polythiophene electrosynthesised as nanowires from the monomer and some of its oligomers is now described. The work is conducted on a platinum electrode previously modified with a template that tunes the polymer growth inside the confined space of the pores. In addition, it was confirmed that the use of larger chain-length oligomers as starting unit helps to obtain more homogeneous wires, although its adhesion to the supporting substrate works against. Characterisation allows to verify the morphology and to confirm higher levels of doping/undoping of the nanostructures as compared to the corresponding bulky deposits, which points to improved macroscopic properties. It is demonstrated that this strategy allows obtaining nanowires of very small diameter, ranging from 2.8 to 4.0 nm; thus demonstrating that the use of this approach enables the direct obtainment of nanowires upon the electrode surface, with the obvious advantage that this implies.

Resumo em Inglês:

The species Piper ottonoides Yuncker (Piperaceae), known as “joão-brandim”, is a shrub that occurs in the Brazilian Amazon rainforest. Its roots and leaves are used in traditional medicine as local anesthetic to treat toothache and sore throat. In this study, the structural characterization in mixture of isobutyl amides present in semi-purified fractions from fruits, leaves, stems and roots of P. ottonoides was achieved by employing gas chromatography-mass spectrometry (GC-MS) and a combination of nuclear magnetic resonance (NMR) techniques (1H, 1H-1H COSY, 1H-13C HSQC, 1H-13C HMBC, TOCSY and 1H-1H J-RES). The MS fragmentation patterns and the NMR chemical shifts, multiplicities, coupling constants and the signal correlations in the two-dimensional spectra were carefully analyzed also taking into account some key elements of differentiation among the compounds. The data set allowed identifying unequivocally the new amide N-isobutyl-7-(4’- methoxyphenyl)-2E,4E-heptadienamide, which we named ottonoidenamide as well as piperovatine and chingchengenamide A in all parts of the plant, the additional presence of pipercallosine and pipercallosidine in roots and of dihydropiperlonguminine in fruits and leaves. The presence of piperovatine and pipercallosine in P. ottonoides should be associated to its traditional use.

Resumo em Inglês:

Monolithic and core-shell columns were comparatively evaluated for separation of deisopropylatrazine (DIA), deethylatrazine (DEA), hydroxyatrazine (HAT), simazine (SIM) and atrazine (ATR) under similar conditions of elution, flow rate and sample volume. Although both columns provided separation of the analytes with resolution > 1.5, the core-shell column exhibited better efficiency, leading to narrower peaks. It has height equivalent to the theoretical plates (HETP) for DEA, DIA and HAT, eluted under isocratic elution, about 2.5 times smaller than those of the monolithic column. A soil sample was studied by ultrasound assisted extraction with 80:20 (v/v) acetonitrile:water, revealing the presence of HAT and ATR. This sample was enriched with 0.25, 0.50 and 1.0 mg kg-1 of the five triazine compounds and analyzed, leading to recovery percentages between 45 and 86%.

Resumo em Inglês:

This article discusses a simple approach for the microwave-assisted synthesis of good quality nanosized calcium titanate crystals doped with trivalent Tm and Yb lanthanide ions. The prepared nanoparticles had a microcube-like structure and a crystallite size of ca. 47 nm. The structure of the nanocrystals was analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and their spectroscopic behavior was examined at a laser excitation wavelength of 350.7 nm. It was found that doping CaTiO3 nanocrystals with Yb and Tm leads to about 250-fold brighter photoluminescence (PL) emissions in the blue and near-infrared regions than that emitted by pure CaTiO3 nanocrystals. The PL emission was correlated with the structural disorder.

Resumo em Inglês:

This paper describes an efficient approach for the synthesis of a novel series of sixteen 2-(5-trifluoromethyl-1H-pyrazol-1-yl)-5-(5-trihalomethyl-1H-pyrazol-1-yl-1-carbonyl) pyridines, for the first time with non-identical substituents in both pyrazole rings, through the cyclocondensation reaction of 4-methoxy-4-alkyl(aryl/heteroaryl-1,1,1-trihaloalk-3-en-2-ones [CX3C(O)CH=CR1OCH3, in which R1 = CH3, C6H5, 4-CH3C6H4, 4-OCH3C6H4, 2-furyl and X = F, Cl] or acetylacetone with some 6-[3-alkyl(aryl)-5-trifluoromethyl-1H-pyrazol-1-yl]nicotinohydrazides. Optimized yields of 67-91% were obtained when the reactions were performed in ethanol (green solvent) at reflux for 16 h. Subsequent antioxidant and antimicrobial evaluation revealed promising 1,1-diphenyl-2-picrylhydrazyl (DPPH) inhibition percentage and exhibited fungiostatic and fungicidal activities against yeasts, dermatophytes and filamentous, especially for the pyridine systems, when the both pyrazole rings attached to a pyridine ring contain CX3 groups (X = H, F, Cl) of different kinds. It is also observed the trichloromethyl substituted compounds presented higher antioxidant activity in comparison to their fluorinated analogous.

Resumo em Inglês:

Terpenes are the main constituents of hops essentiol oil and contribute to the singular sensory properties of beer. However, terpenes are sensitive to oxidation leading to quality loss during beer aging. Herein, the reactivity of terpenes towards 1-hydroxyethyl radical has been determined employing a competitive kinetic approach using the spin-trap α-(4-pyridyl-1-oxide)- N-tert-butylnitrone (4-POBN). The apparent rate constant (kapp) for the reaction of terpenes with 1-hydroxyethyl radical ranges from (3.9 ± 0.2) × 105 to (1.5 ± 0.2) × 107 L mol−1 s−1 for β-pinene and terpinolene, respectively. The reaction involves hydrogen atom transfer from the terpene to 1-hydroxyethyl radical rather than electron-transfer and the rate constant is shown to be dependent on the number of allylic and benzylic hydrogen atoms and on the value of the bond dissociation enthalpy for the weakest C−H bond. The results provide a better understanding on the mechanism behind terpene decomposition in beer brewing and aging process and may further contibute to improve the oxidative stability of the herb-flavored beverages.

Resumo em Inglês:

Avenanthramides play a role as phytoalexins in oat. Recently, various bioactivities have been found in avenanthramides as an antioxidant activity, anti-inflammatory, anti-atherogenic and anti‑proliferative effect. In this study, the optimal conditions for the extraction of avenanthramides 2c, 2p and 2f from oat grain, cultivar Avenuda, were determined using response surface methodology (RSM). The effects of three independent variables (methanol concentration, extraction temperature and time) on the yield of aventhramides were investigated. A second-order polynomial model adequately fitted the experimental data with the R2 values of 0.959, 0.970 and 0.984 for the response of avenanthramides 2c, 2p and 2f, respectively. The optimization method which combined RSM with desirability function was chosen to find the best extraction conditions. The optimal conditions for the highest yield of avenanthramides were a methanol concentration of 70%, extraction temperature 55 °C and time 165 min. Under these conditions, the yields of avenanthramides 2c, 2p and 2f were 9.70 ± 0.38 mg kg-1, 10.05 ± 0.44 mg kg-1 and 19.18 ± 0.80 mg kg-1 oat grain, respectively.

Resumo em Inglês:

In this work, a bulky Fe0/carbon matrix obtained by a low cost and simple reduction/carbonization of Fe3+ salt with sucrose was treated with CO2 to selectively oxidize the amorphous carbon to release the graphite like carbon coated magnetic Fe0 particles. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, X-ray diffraction (XRD), BET, thermogravimetric analysis (TG) (in CO2) and particle size analyses showed that the treatment with CO2 of the Fe/carbon bulky composite led to the selective oxidation of the more amorphous carbon with the formation of 125-132 nm Fe@C nanoparticles with surface areas of 217 m2 g−1.

Resumo em Inglês:

A spectrophotometric method for the determination of AlIII in hemodialysis water employing alizarin red S complexing agent in the presence of polyvinylpyrrolidone 40 surfactant is described. The complex, formed in pH 4.5 buffered media, is detected at 510 nm. Optimal concentrations of all reagents were investigated as well as the appropriate detection wavelength. A linear analytical curve in the range of 5.0-320 µg L-1 was obtained, providing a limit of detection (3s, n = 7) of 2 µg L-1 and quantification limit of 5 µg L-1. Results were compared with those generated using inductively coupled plasma mass spectrometry (ICP-MS) as an independent technique and method validation was also demonstrated by analysis of AccuStandard certified reference material QCS‑02-R1-5, appropriately diluted to 10 µg L-1. Equivalent results (t-test at a 95% confidence level) with a relative standard deviation of 4% were obtained. Real samples, spiked at a level of 10 µg L-1 to conforme to Brazilian legislated limits, showed recoveries between 90-110%. The procedure is simple and fit-for-purpose with sufficient detection power to screen for Al at trace levels in hemodialysis water without pre-concentration of the samples.