Resumo em Inglês:

Poly(4-vinylpyridine) (P4VP) and P4VP/pentacyanoferrate(II) metallopolymer were used to suspend up to 1 mg mL-1 of multi-walled carbon nanotubes (MWCNT) in ethanol/water mixtures, providing noncolavent decoration of MWCNT with electroactive iron complex. The major interaction between polymer side chains and nanotubes is via π-π stacking, rather than charge-transfer interaction reported for many nitrogenated interacting molecules. Preservation of structural integrity of the nanotubes after functionalization was attested by Raman, which was reflected in the semiconducting character of the dried nanocomposites. Proximity of pentacyanoferrate(II) to MWCNT walls was suggested by its solvatochromic shift of metal-to-ligand charge transfer band attributed to [Fe(CN)5]3− bound to P4VP pyridyl moieties. Electronic microscopy revealed smooth films and good adhesion between MWCNT bundles and the matrix. The procedure described herein can be used to combine unique properties of transition metal compounds able to coordinate to pyridyl groups, with the film-forming ability of P4VP and conductivity provided by MWCNT.

Resumo em Inglês:

A facile and highly efficient protocol for synthesis of new 5-substituted-1H-tetrazoles derivatives using copper-doped silica cuprous sulfate (CDSCS) is described. In this method, the cycloaddition reaction of sodium azide with structurally diverse nitriles involving bioactive N-heterocyclic cores exploiting CDSCS in refluxing H2O/i-PrOH (1:1, v/v) furnishes the corresponding 5-substituted-1H-tetrazoles in good to excellent yields (up to 93%). The influence of parameters effective in progress of reaction including solvent type, temperature and catalyst was studied and discussed. In this protocol, CDSCS was proved to be an efficient heterogeneous nano-catalyst to easily achieve the new tetrazole derivatives. The advantages of CDSCS in current protocol known are its cheapness, thermal and chemical stability, ease of recyclability and reusability for several consecutive runs without significant decline in its reactivity.

Resumo em Inglês:

Five sesquiterpenoid oxides, named nectandrene A, B, C, D, and E, were isolated from the essential oil of the leaves of Nectandra megapotamica. Their structures were elucidated by spectroscopic analysis, and the relative configurations were proposed by their nuclear Overhauser effect (NOESY) spectrum. Three of these isolated compounds displayed significant antimicrobial activity; the compound most active had minimal inhibitory concentration (MIC) values between 3.12 and 25.0 μg mL-1 against some tested bacteria, and antifungal activity with MIC values between 12.5 and 25.0 μg mL-1.

Resumo em Inglês:

Traditional tomatoes (Solanum lycopersicum L.) have been mainly selected for their fruit quality and maintained by local farmers in Andean areas of Cuyo and Northwestern Argentina. Volatile organic compounds (VOCs) in mature fruits of Andean tomato landraces were evaluated for the first time using headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) and combined with classical multivariate analysis. The data sets composed of 101 volatile metabolites were identified in 4 accessions of Andean landraces, one commercial variety and one wild tomato accession (Solanum pimpinellifolium L.). The metabolic profile showed typical VOCs of tomato and 21 new compounds never informed in S. lycopersicum. Andean traditional tomatoes have been shown to be metabolically different from wild species. In addition, some varieties of Andean tomatoes have a different profile of VOCs and are richer than the commercial variety. A different and original metabolic volatile composition found in fruits of Andean tomato landraces of Argentina, in comparison with commercial cultivars, might probably reveals selection based on quality attributes made by local farmers.

Resumo em Inglês:

Benzene, toluene and xylene (BTX) are a particular class of volatile organic compounds, which are highly toxic pollutants. In this study, samples of gallium-containing mesoporous silica (MS-Ga7% and MS-Ga11%) were synthesized and their catalytic activity in the oxidation of BTX was investigated. The physicochemical characterization shows that the inclusion of gallium in the mesoporous silica structure leads to an increase in the number of oxygen vacancies in the structure of the MS-Ga system, which can result in an increase in the total and surface oxygen mobility. The results show the highest conversion for benzene (65%), with > 40% for toluene and > 28% for o-xylene. The high catalytic activity observed was attributed to a combination of several factors including a higher number of active sites (gallium and gallium oxide) being exposed, with a greater mobility of the active oxygen species on the surface of the catalyst promoting the catalytic activity.

Resumo em Inglês:

The gold electrodeposition process from a glycerol solution on a carbon paste electrode (CPE) was investigated by voltammetry and the morphologies of the electrodeposits were analyzed by scanning electron microscopy (SEM). Voltammetric study indicated that AuCl4− was reduced to Au0 and the process was mixed controlled (mass transport and electron transfer), preceded probably by AuCl4− decomplexation. Glycerol affected the kinetic of gold electrodeposition in function of the AuCl4− concentration. SEM images indicated that the gold electrodeposit covered totally some of the graphite flake by a homogeneous morphology, regardless of the electrodeposition condition. Moreover, using a full factorial planning it was verified that the deposition charge and potential affected the modified CPE performance in a potassium ferrocyanide solution, while HAuCl4 and glycerol concentrations affected only by interactions with the other factors.

Resumo em Inglês:

We report on the synthesis of single-crystalline tellurium nanowires with different aspect-ratios prepared via facile surfactant-assisted synthesis under mild conditions. Short and long Te nanowires were synthesized by the reduction of tellurium dioxide by hypophosphorous acid with the assistance of polyoxyethylene (23) laurylether and cetyltrimethylammonium bromide, respectively. We obtained uniform single-crystal Te nanowires with diameter below 30 nm and tunable length from 600 nm to 5 µm. Short and long Te nanowires showed remarkable nonlinear absorption and their third-order nonlinear optical properties were investigated by the Z-scan technique with single 80 ps laser pulses at 532 nm. For the first time, it was observed a distinguished switching behavior from saturated absorption to reverse saturated absorption as a function of the laser intensity in one-dimensional Te nanostructures. Although both short and long Te nanowires display such interesting behavior, the short ones exhibited superior optical limiting performance.

Resumo em Inglês:

Facilitated transport of silver(I) cation across a bulk liquid membrane by two synthesized ligands, bis-β-enamino ester (BBEE) and bis(benzoic acid) trioxaheptane (BBAT), as carriers dissolved in dichloromethane has been investigated. BBEE was used as a specific ion carrier for the transport of silver(I) ion. The influence of experimental parameters affecting the transport efficiency of silver(I) ion have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the receiving phase and picrate ion as ion pairing agent in the source phase, the amount of silver(I) ion transported across the liquid membrane after 120 min was found to be 97%. Tolerance to the presence of different ions was investigated and it was found that silver(I) cation transport was not affected even in the presence of 10-fold concentration of these metal cations in solution. This system was applied for the recovery of silver(I) cation from silver plating and photographic waste solution.

Resumo em Inglês:

This work involved the validation of a multiresidue method according to the Normative Instruction 24/2009-MAPA for determining 25 analytes, among fluoroquinolones, sulfonamides and trimethoprim in samples of poultry and porcine kidney. The extraction procedure was based on a QuEChERS approach. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed using the selected reaction monitoring mode (SRM) and ESI+ ionization. All of the validated figures of merit were evaluated as satisfactory. Accuracy was assessed by recovery studies, varying from 82.7 to 115.5% for porcine kidney and from 91.5 to 110.4% for poultry kidney. Relative standard deviations were lower than 25.5% for porcine kidney, and 29.8% for poultry kidney. Decision limits (CCα) comprised values from 10.37 to 3298.43 µg kg-1 for porcine kidney and 10.08 to 3176.59 µg kg-1 for poultry kidney. Detection capabilities (CCβ) varied from 10.73 to 3396.86 µg kg-1 for porcine kidney and 10.67 to 3253.19 µg kg-1 for poultry kidney. The developed method has been successfully employed in the routine analysis of incurred samples.

Resumo em Inglês:

Copper(II) complexes of the Schiff base ligands 2-((5-nitrofuran-2-yl)methyleneamino)phenol (HL1) and 2-(4-nitrobenzylideneamino)phenol (HL2) were prepared and characterized using physicochemical and spectroscopic techniques. In these complexes the Schiff base ligands acted as a bidentate donor bound to Cu2+ through the oxygen and nitrogen atoms in the deprotonated form. The electron paramagnetic resonance spectra, carried out on [CuCl(L1)(phen)].0.5H2O and [CuCl(L2)(phen)].2H2O complexes, showed the presence of only mononuclear forms. The Cu2+ complexes and ligands were evaluated for their in vitro trypanocidal activity. The complex [CuCl(L1)(phen)].0.5H2O was more active than the free Schiff base and also presented a superior effect to benznidazole, the reference drug. The antiproliferative activity of the Schiff bases and Cu2+ complexes were evaluated for their effect on seven tumor cell lines and showed a cytostatic and in some cases a cytotoxic effect. These compounds also presented binding properties to deoxyribonucleic acid (DNA) and moderate ability to quench the intrinsic fluorescence of albumins.

Resumo em Inglês:

Inorganic elements present in pharmaceutical products were determined by inductively coupled plasma-mass spectrometer (ICP-MS), employing microwave acid digestion as a sample preparation method. The most abundant isotopes, 75As+, 65Cu+, 52Cr+, 58Ni+, 208Pb+, and 51V+, were determined in acyclovir ointment and its constituents. Elemental impurities in the pharmaceutical samples were determined using an inductively coupled plasma-universal cell technology-mass spectrometer (ICP-UCT-MS) operated in kinetic energy discrimination (KED) and standard mode. The accuracy of the method was assessed by means of addition and recovery experiments. Except for Cr, spiked recoveries of the elements added to the samples before microwave acid digestion (MW-AD) step were between 95.1 and 126%, and after MW-AD step ranged from 85.6 to 132%. Limits of detection (LOD) obtained by proposed method is in agreement to those required by the U.S. Pharmacopeia Convention (USP), showing that the ICP-MS technique is well suited for quantification of these elements. The LOD's (ng L-1) for 51V+, 52Cr+, 58Ni+, 65Cu+, 75As+ and 208Pb+ in 1% v v-1 HNO3 medium were: 2.2, 81.3, 91.9, 6.9, 0.2 and 3.1, respectively. The concentration of the analytes in these samples presented a wide range, varying from 2.3 ± 0.8 µg kg-1 for As to 3446 ± 47 µg kg-1 for Cr.

Resumo em Inglês:

Silver nanoparticles and zinc hydroxide-layered hybrid materials (AgNPs/ZHL) have been successfully developed as efficient catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with sodium borohydride. A facile and rapid visible-light assisted green route was used for the deposition of silver nanoparticles (AgNPs) on the external surface of ZHL material. The resulting AgNPs/ZHL hybrids contained AgNPs with spherical morphology and uniform size distribution. Moreover, the AgNPs/ZHL compounds exhibited excellent catalytic performance (the reduction reaction was finished within 4 min) and reusability (three cycles) toward the reduction of 4-NP to 4-AP in presence of sodium borohydride. The reduction reaction obeyed the pseudo-first-order kinetics. The rate constants increased with the increase of amount of the AgNPs deposited into the hybrid materials. These results suggest that the as-prepared catalysts (AgNPs/ZHL) have great potential for heterogeneous catalytic applications.

Resumo em Inglês:

This study aimed to prepare a complex of 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) and 6CN10, a poorly water soluble 2-aminothiophene derivative with antifungal properties, by freeze-drying technique. The complex was characterized by thermal analysis, infrared/Raman spectroscopy, X-ray diffraction and scanning electron microscopy. In addition, we used the data of the phase solubility study, 1H, and 2D NMR spectroscopy and molecular modeling in order to investigate the interactions between 6CN10 and HP-β-CD. The apparent solubility of 6CN10 with HP-β-CD increased more than 29 fold. The phase solubility assay in water at 25 ºC showed an AP-type curve, with an apparent stability constant K1:1 and K1:2 of 96 and 0.1989 M-1, respectively. The results of IR, NMR and docking indicate that 6CN10 is able to form complexes with HP-β-CD (1:1 and 1:2 stoichiometric ratios), generating the formation of inclusion and preferably, non-inclusion complexes. The antifungal activity against Cryptococcus neoformans demonstrated the superior performance of the complex (46.66 µg mL-1) when compared with the free drug (166.66-333.33 µg mL-1). The present study provides useful information for the potential application of complexation with low soluble compounds and about the type of complex formation between 6CN10 and HP-β-CD.

Resumo em Inglês:

Microcapsules of sugarcane bagasse lignin loaded with organic extracts of neem (Azadirachta indica) were prepared and evaluated as potential bioinsecticides. Lignins were extracted and modified by oxidation and acetylation reactions providing different biopolymers. Afterwards, they were characterized through several analytical techniques. The formulations were initially prepared as colloidal suspension of lignin nanoparticles, which were then spray-dried. The products were submitted to quality control protocols using high performance liquid chromatography (HPLC), thermal and photochemical degradation studies, followed by biological assays against Spodoptera frugiperda and Diatraea saccharalis. The formulations showed increases in both thermal and photo stability of approximately 40% compared with control samples. All the formulated microparticles were efficient against the insects evaluated and required a shorter time to achieve 100% mortality than the controls. The use of sugarcane bagasse lignins to prepare microparticles improved the resistance of neem extracts against abiotic factors, retaining the biological activity of this biopesticide.

Resumo em Inglês:

Correct interpretation of mass spectra is essential to our understanding of the ion chemistry occurring in the gas phase inside mass spectrometers and for constructing a solid knowledge from which mass spectrometry (MS) data of novel molecules will be interpreted. Assignments of product ions leading to incorrect dissociation mechanisms can also be dangerous in several disciplines such as in forensic chemistry and clinical diagnostics. Main fragmentation routes for rhodamines B and 6G were investigated by high accuracy Orbitrap tandem mass spectrometry (MS/MS). Isobars were properly resolved and molecular formulas were correctly attributed to all major product ions. This proper evaluation of ions composition and formula allowed us to propose a detailed mechanism for their dissociation. A comprehensive mechanistic fragmentation is proposed for rhodamine B and 6G using product ion assignments resulting from high resolution and accuracy tandem MS data, which should serve as a guide for MS and MS/MS data interpretation of homologues molecules.

Resumo em Inglês:

The acute toxicity of copper and cadmium in Oreochromis niloticus was evaluated through a 96 h static assay. Precipitation of Cu and co-precipitation of Cd in the presence of Cu were noted, being indicative of differences in nominal and actual concentrations of metals. Under these conditions, LC50-96h was determined as 3.53 mg L-1Cu, 20.1 mg L-1 Cd and 1.36 mg L-1 (Cu + Cd). Besides the quantitative determinations of total dissolved metals in water, considerations on Cd/Cu interactions in aquatic media were presented, allowing the assessment for metals speciation. Data revealed that alkalinity, hardness, dissolved organic carbon and formation of inorganic complexes reduce metal availabilities, mainly in relation to Cu. In spite of this, the LC50 for Cd was significantly reduced in the presence of Cu, matching environmental realistic values. Based on simulated fate of metals, hardness may impair a reduction of 18 and 2% in metal activities, respectively to Cu and Cd.

Resumo em Inglês:

The first Simira sampaioana (Rubiaceae) phytochemical study allowed the isolation and structural determination of a new erythroxylane diterpene named Angelocunhol, 11β,12α-dihydroxy-2,4(18),15-eritroxilatrien-1-one, together with 14 known compounds: simirane B, harman, maxonine, isomalindine, malindine, sitost-4-en-6-ol-3-one, estigmast-4,22-dien-6-ol-3-one, campest-4-en-6-ol-3-one, sitost-4-en-3-one, stigmast-4,22-dien-3-one, campest-4-en-3-one, β-sitosterol, stigmasterol, and stigmast-4,22-dien-3-ol from the wood of a specimen of the species. The structures of these compounds were elucidated on the spectroscopic-data analysis basis, mainly 1H and 13C nuclear magnetic resonance (NMR), including 2D experiments (1H-1H correlation spectroscopy (COSY), nuclear Overhauser spectroscopy (NOESY), heteronuclear multiple-bond correlation-HMBC and heteronuclear single-quantum correlation-HSQC), and high-resolution electrospray mass spectrometry (HRESI-MS).

Resumo em Inglês:

Sulfonamides are among the most widely employed antibacterial in veterinary medicine. Because a substantial proportion of sulfonamides are excreted unchanged as parent compounds after administration or are excreted as their metabolites through urine and feces, their presence in soils is a matter of concern. Adsorption and desorption are important processes that influence the transport, transformation and bioavailability of antimicrobials in soils, and data related to sorption capacity are therefore needed for environmental risk assessments. The sorption potential of sulfachloropyridazine (SCP) was assessed in four Brazilians soils using batch equilibrium experiments. The adsorption/desorption data fit well Freundlich isotherms. The sorption coefficients (KD) ranged from 1.00 to 4.48 cm3 g-1, and the Freundlich adsorption coefficient (KF) ranged from 1.89 to 5.63 µg1-1/n (cm3)1/n g-1 showing that SCP adsorption is generally low in the studied soils. The results were compared with previously published data obtained for the sorption of other sulfonamides in the same four soils.

Resumo em Inglês:

Direct and pulse current electrodeposition techniques were applied for preparation of novel electro-active manganese oxides. The influences of Ag doping and addition of cetyltrimethylammonium bromide (CTAB) on electrochemical properties were discussed. The morphology and structure of the electrodes are studied by different techniques including field emission scanning electron microscopy (FE-SEM), contact angle and X-ray photoelectron spectroscopy (XPS). Electrochemical behavior of the samples are investigated by cyclic voltammetry (CV), constant current charge-discharge (CC), and electrochemical impedance spectroscopy (EIS). The specific capacitances were measured to be 269, 315, 435, 442, 480 and 508 F g-1 for M-g, M-p, MC-g, MC-p, MCA-g and MCA-p (current density = 1 A g-1), respectively. The MCA-p exhibit high specific capacitance, excellent cycling stability (only 7.5% loss after 1000 cycles at 1 A g-1), and high energy densities (71 Wh kg-1). Ag doping and addition of CTAB which provides more active sites for the pseudocapacitive reactions.

Resumo em Inglês:

Sewage sludge is the residue produced by the wastewater treatment plants, which can be used as soil conditioner in agriculture. However, the current legislation recommends monitoring chemical contaminants such as polychlorinated biphenyls (PCBs). In this study, solid-liquid extraction with low temperature purification (SLE-LTP) was optimized and validated for monitoring six PCBs. The analyses were performed by gas chromatography and mass spectrometry. Sulfur interference was removed by 1.5 g of copper metal. The extraction was carried out using 6.50 mL isopropanol, 1.50 mL ethyl acetate, 0.1 g NaCl, 0.8 mL water and 15 min into ultrasound. Extraction percentages were between 82 and 94% and relative standard deviation ≤ 16% for low concentrations. Detection and quantification limits were 3.3 and 10 µg kg-1, respectively. The method was applied to sludge samples collected monthly in the wastewater treatment plant and PCB 52 was detected in six samples.

Resumo em Inglês:

The application of electrochemical technology for the degradation of organic pollutants often faces two main problems, related to the anode material and mass transport limitations. Although PbO2 electrode is inexpensive and provides satisfactory electrooxidation kinetics, in the form of plane electrodes it is unable to resolve the mass transfer problem that arises at low concentrations of organics. In this work, an electrochemical flow reactor was developed for the preparation of three-dimensional electrodes consisting of PbO2 films electrodeposited onto reticulated vitreous carbon. The electrodes were characterized in terms of the substrate coating, morphology, structure, and electrocatalytic activity in the decoloration reaction of Reactive Blue 19 dye. The results showed that it was possible to deposit a uniform film of PbO2 on the surface of the substrate after optimization of the current density and deposition time (0.7 mA cm-2 for 30 min). Comparison of the plane and three-dimensional electrodes revealed that the turbulence generated by the porous matrix significantly accelerated the dye decoloration kinetics, increasing 3.3-fold the first order kinetic constant (from 0.010 min-1 for VC/PbO2 to 0.033 min-1 for RVC/PbO2).

Resumo em Inglês:

This report describes the use of toner-based microzone plates for quantitative determination of glucose in artificial urine and human serum samples using colorimetric detection. The proposed approach has exhibited a linear response for glucose concentration levels from 0 to 10 mmol L-1 with determination coefficient (R2) of 0.996. The achieved values for sensitivity and limit of detection were 5.1 AU (mmol L-1)-1 and 0.6 mmol L-1, respectively. The glucose analysis in artificial serum samples revealed error lower than 5% in comparison with certified values provided by the supplier. Lastly, the proposed approach has also provided suitable accuracy (92-105%) for glucose measurements in artificial urine samples.