Resumo em Inglês:

Conventional methods to detect pathogenic microorganisms can be wasteful, expensive, and not very sensitive. Due to these limitations, approaches based on nanotechnology and the development of new diagnostic tests are emerging as alternative methods. Resulting from the unique electrical, magnetic, luminescent, and catalytic properties of nanomaterials, rapid and cost-effective diagnostic tests have been developed to recognize the presence of microbial pathogens or some of their components in different samples. The purpose of this review is to provide an overview and an update regarding the use of several nanomaterials as biosensors, among which are gold nanoparticles, carbon nanotubes, magnetic nanoparticles, and quantum dots. The application of these biosensors has opened a new interdisciplinary frontier between biological detection and materials science.

Resumo em Inglês:

The development of cost-effective molecular devices that efficiently capture and convert sunlight into other useful forms of energy is a promising approach to meet the world’s increasing energy demands. These devices are designed through a successful combination of materials and molecules that work synergistically to promote light-driven chemical reactions. Light absorption by a surface-bound chromophore triggers a sequence of interfacial electron transfer processes. The efficiencies of the devices are governed by the dynamic balance between the electron transfer reactions that promote energy conversion and undesirable side reactions. Therefore, it is necessary to understand and control these processes to optimize the design of the components of the devices and to achieve higher energy conversion efficiencies. In this context, this review discusses general aspects of interfacial electron transfer reactions in dye-sensitized TiO2 molecular devices for solar energy conversion. A theoretical background on the Marcus-Gerischer theory for interfacial electron transfer and theoretical models for electron transport within TiO2 films are provided. An overview of dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs) is presented, and the electron transfer and transport processes that occur in both classes of devices are emphasized and detailed. Finally, the main spectroscopic, electrochemical and photoelectrochemical experimental techniques that are employed to elucidate the kinetics of the electron transfer reactions discussed in this review are presented.

Resumo em Inglês:

In this study, an aluminosilicate residue from insulators of high voltage transformers was used for the adsorption of basic dyes. The absorbent was characterized by X-ray fluorescence analysis, X-ray diffraction analysis, scanning electron microscopy, multimolecular adsorption theory (Branauer-Emmet-Teller (BET)) and determination of the point of zero charge (pHPZC). The effect of solution pH and adsorbent mass, the kinetic and thermodynamic behavior at different temperatures and the application of non-linear isotherm models of Langmuir, Freundlich, Temkin and Dubinin-Radushevich were investigated. The pHPZC value for the aluminosilicate was 3.7. The best conditions for adsorption of methylene blue and crystal violet dyes were pH 8.0 and adsorbent mass of 1100 mg in 25 mL. The best fit for the experimental data was obtained applying the pseudo-second-order kinetic model, with an equilibrium time of 480 to 720 min, and the activation energy suggests a physical adsorption mechanism. Isothermal parameters suggest a heterogeneous, favorable and predominantly physical surface adsorption. The thermodynamic studies indicated that the adsorption process is not spontaneous and is exothermic and the Gibbs energy values (∆Gº) suggest physisorption.

Resumo em Inglês:

Ultrasonic pretreatment of cowpea bean pod biomass with addition of tripotassium phosphate (K3PO4) was used to induce the production of bio-oil enriched in phenolic compounds. An ultrasound bath operating at 40 kHz, 154 W power, and constant biomass:K3PO4 ratio of 5:1 (m/m) was used for pretreatments with different durations: 0.5, 1.5, 3, 6, 8, and 12 h. After the pretreatment, the biomass was pyrolyzed in a fixed bed reactor at 600 °C, under a flow of N2 at 5 mL min−1. The pyrolysis results indicated that the use of K3PO4 reduced the bio-oil yield, when compared to non-catalytic pyrolysis, and that the use of ultrasound caused increased biomass devolatilization, increasing the gas yield and reducing the formation of biochar. Gas chromatography mass spectrometry (GC-MS) analysis of the bio-oils indicated that pretreatment of the biomass led to significant increases of the phenolics contents, as well as alteration of the chemical profile of these compounds. The highest phenolics content of 8.12% m/m was obtained for the biomass submitted to 1.5 h of ultrasonic pretreatment, compared to 4.89% m/m for the untreated biomass.

Resumo em Inglês:

The Mundaú lagoon (Maceió, AL), besides being relevant socially, economically, and culturally, also in its surroundings, presents an intense anthropic occupation, characterized by a large population and the industrial activities presence. In this systematic environmental monitoring study (from 2017 to 2019), concentrations of Al, As, Bi, Cd, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, V, and Zn in surface waters, and total Hg content in the bivalve Mytella charruana (sururu) were recorded, using cold vapor atomic fluorescence spectrometry (or hydride generation) (HG/CV AFS), inductively coupled plasma mass spectrometry (ICP-MS), and chronopotentiometry. In the water samples, the following elements presented concentrations above the values recommended by the National Council for the Environment (CONAMA), in µg L−1: Al (24.4−2008), Cu (1.88-13.03), Fe (84.9-4107), Hg (<0.0069-2.92), Mn (10.65-200), Pb (192-1443) and Zn (121-997), and therefore, the water was classified following the water pollution index (WPI), as highly impure and polluted. The Hg content in sururu, the main food in Mundaú lagoon, ranged from 0.036-0.63 mg kg−1 (dry weight). Further, the chemometric evaluation of the data based on the principal component and correlation analysis suggested a chemical-defined profile at the different sampling points.

Resumo em Inglês:

A rapid and reproducible liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated to simultaneously determine sacubitril, valsartan and a metabolite of sacubitril (LBQ657) in human plasma using sacubitril-d4 and valsartan-d3 as the internal standards. Following protein precipitation, the analytes were operated on an Ultimate® XB-C18 column (2.1 × 50 mm, 3.5 μm, Welch) with a gradient elution with acetonitrile, and 5 mM ammonium acetate and 0.1% formic acid in water as the mobile phase. The detection was performed on a Triple Quad™ 4000 mass spectrometer coupled with an electrospray ionization source (ESI) under positive-ion multiple reaction monitoring mode. The linearities are 2.00-4000, 5.00-10000 and 5.00-10000 ng mL−1 for sacubitril, valsartan and LBQ657, respectively. The accuracy and precision of intra- and inter-day, dilution accuracy, recovery and stability of the method were all within the acceptable limits and no matrix effect or carryover was observed. The suitability of the method was successfully demonstrated in terms of the quantification of sacubitril, valsartan and LBQ657 in plasma samples collected from healthy Chinese volunteers in a clinical trial.

Resumo em Inglês:

A series of novel 2-(thiophen-2-yl)-4H-chromen-3-yl-sulfonate derivatives (4a-4n) were synthesized and investigated for their in vitro free radical scavenging potential as well as cytotoxic efficacies against selected cancer cell lines. The cytotoxicity of the 4H-chromene derivatives (4a-4n) was evaluated according to three human cancer cell lines (HepG2, A549, HeLa) by utilizing a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Accordingly, part of the results exhibited better cytotoxic activities than that of the positive controls (4H-chromen-4-one and apigenin). Among them, compounds 4c-4g exhibited better training to the positive control against the three human cancer cell lines (half maximal inhibitory concentration (IC50) = 3.87 ± 0.12 to 21.38 ± 0.52 μM). Moreover, the extract of the 4H-chromene derivatives (4a-4n) showed better activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2’-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) in antioxidant assays compared to that of the positive control ascorbic acid (IC50 = 12.72 ± 0.27, 5.09 ± 0.21 μg mL−1). Thus, it can be confirmed from the bioassay results that the overall structural design, as well as proper substitution, is crucial in delivering anticipated biological effects. In this regard, spectroscopic techniques such as 1H nuclear magnetic resonance (NMR), 13C NMR, and high-resolution mass spectrometry (HRMS) were also carried out to confirm the final structures.

Resumo em Inglês:

A hybrid imprinted polymer (HMIP) was synthetized via sol-gel technique in aqueous solution for caffeine separation from environmental waters samples. The optimal conditions of synthesis were stablished by application of a 23 full factorial experimental design with three factors: ratio of functional monomer and cross-linker reagent, and acid or basic catalyst (HCl or NH4OH). The HMIP obtained with the factorial designs was 22.5 times more selective for caffeine than control polymer, with an adsorption mechanism of pseudo-second order with two sorption sites. The maximum equilibrium adsorption capacity was 1.91 mg g−1 that was maintained until ten cycles of reuse, indicating their excellent stability. The material was 21 times more selective for caffeine than for its analogous molecules (theophylline and theobromine). HMIP was applied in solid phase extraction (SPE) procedure and caffeine extraction of surface water had good recoveries (93.0%). These results demonstrated that the factorial experimental design resulted in an efficient and selective sorbent for caffeine with a reduction of number of synthesis and problems of trial-and-error protocol as well as reagents consumption decrease.

Resumo em Inglês:

This work reports the synthesis, structure and catalytic activity of a novel ruthenium(II) complex, [RuCl(dppb)(44bipy)(4-pic)]PF6 (where dppb = 1,4-bis(diphenylphosphine)butane; 44bipy = 4,4’-dimethyl-2,2’-dipyridyl; 4-pic = 4-picoline). The molecular structure and catalytic activity were studied by Fourier transform infrared (FTIR), UV-Vis and nuclear magnetic resonance (NMR) spectroscopies, cyclic voltammetry, and X-ray crystallography, while the electronic structure was investigated by density-functional theory (DFT) and time dependent DFT (TD-DFT) methods. Electrochemical studies showed the substitution of the chlorido ligand from the precursor by the 4-pic ligand, exhibiting the RuII/RuIII process at 1.21 V. The structure of the compound was optimized using DFT simulations and showed data similar to the X-ray structure. The UV-Vis absorption spectrum showed a good agreement with TD-DFT simulations. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies were determined at the Becke, 3-parameter, Lee-Yang-Parr (B3LYP) level. The study of the catalytic activity in the transfer hydrogenation of ketones by the 1H NMR showed efficient transfer hydrogenation reaction at 60 ºC, employing acetophenone as substrate and resulting in a high conversion. The formation of two ruthenium-hydride species was observed.

Resumo em Inglês:

Chromone derivatives exhibiting high absorbance values in the UVA/UVB region were synthesized, and their photoprotective properties were evaluated. Chromones were prepared according to known literature procedures and characterized by high resolution mass spectrometry, infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The in vitro solar protection factor (SPF) was determined by the Mansur method and cytotoxicity was evaluated using the sulforhodamine B assay. Two of the chromones synthesized demonstrated suitable SPF values and displayed no cytotoxic effect towards MRC-5 human fibroblasts at the tested concentrations, indicating great potential for future in vivo assays and clinical trials. Finally, the lead compound was incorporated into a nanoemulsion. Nanoemulsions showed high droplet size homogeneity and excellent stability. Chromones bearing methoxy substituents were found to be the most promising compounds with ideal photoprotective properties desirable for utilization and incorporation in sunscreen formulations.

Resumo em Inglês:

In this work, we studied the formation of hierarchical porous cartridges by means of bacterial cellulose impregnation with the zeolites A and X. Cellulose was successfully produced by Komagataeibacter genus and the zeolites were obtained by hydrothermal route. The composites were formed using both oxidized and non-oxidized cellulose. Different characterization techniques were used to analyze the resulting materials like powder X-ray diffraction, spectroscopic techniques (infrared vibrational spectroscopy and nuclear magnetic resonance), electron microscopy, thermal analyses, as well as ionic exchange experiments. The results show that the composites present layers with large voids among them, formed by cellulose nanofibrils tangling the particles in the oxidized samples, and shiftings in the bands referent to the carboxilyc groups and hydrogen bondings. The oxidation step for the cellulose seems to be important for the hierarchization and a positive effect on the cartridges is found for Ca2+ ionic exchange tests. Thus, these components can be successfully mixed to form cartridges with potential use at gas and liquid adsorption technologies.

Resumo em Inglês:

The genus Penicillium is among the most promising alkaloid-producing fungal and therefore plays an important role in terms of producing molecules with biotechnological potential. Thus, in order to identify alkaloid-producing fungi, 25 endophytic Penicillium strains previously isolated from Amazon medicinal plants were subject to an integrative approach based on direct infusion positive electrospray ionization mass spectrometry (ESI-MS) and principal component analysis (PCA). The multivariate analysis pointed paxiline (1), glandicoline B (2), roquefortine C (3), and oxaline (5) as responsible for the segregation of three promising alkaloid-producing groups, been these groups constituted for P. chrysogenum, P. oxalicum, P. paxilli, and P. rubens strains. These alkaloids and the glandicoline A (4) were tentatively identified by multiple-stage mass spectrometry. In addition, compounds 1 and 2 were isolated and confirmed by using 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. Overall, the chemical profile analysis by ESI-MS along with PCA provided a simple and effective approach to screening alkaloid-producing Penicillium strains for biotechnological applications.

Resumo em Inglês:

Environmental factors can influence secondary plant metabolism, inducing seasonal variation in chemical composition. Few works report how the seasons of Brazilian savanna (Cerrado), rainy and dry, impacts plant metabolism. We investigated the seasonal effect on the production of secondary metabolites in Duguetia furfuracea. Leaves of three individuals were collected monthly for one year and analyzed by ultra-fast liquid chromatography coupled to diode array detector and mass spectrometry (UFLC-DAD-MS), partial least squares-discriminant analysis (PLS-DA), hierarchical cluster analysis (HCA), volcano plot, and Pearson correlation. The main chemical classes found were benzyltetrahydroisoquinoline derivatives and flavonoids. Alkaloids are virtually perennial, with qualitative variation during the year, and flavonoids accumulate during the rainy season. Dew point temperature seemed to be the most representative weather indicator in the metabolite change. These results showed for the first time the effect of the Cerrado environment on the levels of flavonoids and alkaloids in Duguetia furfuracea. They could be useful for exploring this species since it is used in popular medicine and accumulates valuable secondary metabolites.

Resumo em Inglês:

Nanocrystalline BiVO4 on monoclinic phase was obtained by a modified-solution combustion synthesis (SCS) using poly(ethylene glycol) (PEG 6000) and polyvinylpyrrolidone (PVP) as stabilizing and surfactant agents, respectively. An active photoanode was built using a simple procedure by dip-coating deposition process on fluorine-doped tin dioxide (FTO). The structure, morphology and optical properties of FTO/BiVO4 photoanode were evaluated by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and diffuse reflectance UV-Vis spectroscopy. The photoelectrochemical performance measurements were carried out by linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS) under InGaN blue light emitting diode (LED) illumination condition (about 450 nm). In Na2SO4 electrolyte solution, the electrode has presented better photoelectroactivity than in NaNO3 solution, as evidenced by photoelectrochemical parameters such as: the highest photocurrent density (js) value, cathodic shifts of the onset potential (OP) and lower charge-transfer resistence (Rct). In the methyl orange (MO) degradation reaction the FTO/BiVO4 electrode has presented high photoelectroactivity, where the estimated kinetic constant rate (kobs) is 4.74 × 10−3 and 7.54 × 10−3 min−1 in NaNO3 and Na2SO4 solutions, respectively. This remarkable performance of the as-prepared electrode is due to the morphological BiVO4 structure, with elongated-shape nano-sized domain particles, besides the considerable porosity and roughness levels on electrode surface.

Resumo em Inglês:

Due to the usual resistance of textile dyes to conventional biological treatment processes, the color removal of dyeing wastewaters remains a challenge for the textile industry. This work evaluates the capacity of advanced oxidation processes based on thermally-activated persulfate concerning textile dyes’ degradation in aqueous solution and the reuse of dyeing baths. Preliminary studies were carried out in a bench-scale jacketed reactor, using Reactive Black 5 (40 mg L−1) as a model dye. Almost complete dye degradation was observed in 60 min in this stage, using 300 mg L−1 of persulfate and activation temperatures of 80 ºC, basically due to the action of radical sulfate. The use of high concentrations of persulfate (1000 mg L−1) allowed efficient color removal of dyeing baths containing remazol dyes in processes activated at 80 and 90 ºC. However, the wastewaters treated under these conditions did not lead to high dyeing efficiency in reuse studies, probably due to residual persulfate presence. In contrast, low concentrations of persulfate (250 mg L−1) lead to partial color removal and a better dyeing quality. The results suggest a good potential for treating high-temperature dyeing baths, saving water and auxiliary agents used in textile dyeing processes.

Resumo em Inglês:

Polycyclic aromatic hydrocarbons (PAHs) are an important environmental issue and the identification of new biocatalysts for an efficient biodegradation of these compounds is essential for bioremediation. Therefore, fungi strains isolated for the first time from a tropical peat at Santo Amaro das Brotas (Brazil) were studied for fluoranthene biodegradation. Fusarium sp. AC-7, Penicillium sp. AC-1 and Penicillium sp. AC-6 were isolated using fluoranthene as sole carbon source. All strains were tested for biodegradation of 100 mg L−1 fluoranthene during 14 and 28 days. After 28 days of biodegradation, 64 ± 3, 60 ± 4 and 51 ± 2% biodegradation was observed for Penicillium sp. AC-1, Penicillium sp. AC-6 and Fusarium sp. AC-7, respectively. Analysis of the obtained compounds enabled the identification of four metabolites, which were common to the three employed strains: anthrone, anthraquinone, 9-methoxyanthracene and cyclopropa[1]phenanthrene. It is important to note that control experiments were performed. The obtained results clearly demonstrated the efficiency of tropical peat fungi in the transformation of fluoranthene. These findings showed the potential of tropical peats for isolation of fungi and indicated that these strains can be applied for bioremediation processes of areas contaminated with fluoranthene and other PAHs.

Resumo em Inglês:

The present work intends to obtain and characterize a milk by-product: the human whey (HW), in order to avoid the excessive disposal of human milk (HM). The characterization was performed through analyzes of the chemical composition and fatty acids (FAs) and the triacylglycerol (TAG) lipid profile. The results indicated that the chemical composition altered significantly after the HW obtained, except for the percentage of ash and carbohydrates. About the FA composition, it was observed that strictly essential FA, essential FA and other FAs found in HM remained present in HW. For the nutritional lipids quality, the atherogenicity and the thrombogenicity indices presented desirable values, and the TAGs lipid profile revealed a variation in the analyzed samples. Therefore, it can be concluded that the characterized HW has potential for application in isolated form or to be used as an ingredient in other foods.