Resumo em Inglês:

An estradiol templated core-shell magnetic molecularly imprinted cryogel (MMIC) was synthesized to selectively extract and analyze estradiol in milk powder. The microsphere of Fe3O4@SiO2 was firstly prepared on Fe3O4 with ethyl silicate and 3-methyl propyl trimethoxy silane. Then the polymerization of α-methacrylic acid and ethylene glycol dimethyl acrylate was carried out on Fe3O4@SiO2 at −20 ºC for 24 h with estradiol as template. The morphology and microstructure of MMIC were investigated by transmission electron microscopy and infrared spectrogram. When used as chromatographic stationary phase, MMIC showed good selectivity and chromatographic performance for the template. Spiked milk powder samples were used to examine the adsorption capacity and selectivity of MMIC, giving recoveries of 92-101% and limit of detection 0.8-1.2 ng g−1. Experimental results indicate good reproducibility with relative standard deviation from 2.2 to 4.5% (n = 3) at spiked levels of estradiol 10, 50, and 100 ng g-1.

Resumo em Inglês:

Five new withanolides, designated as 15-oxo-nicaphysalin B, 6β,7α-dihydroxynicandrenone 10, 24α,25β-dihydroxy-nicandrenone-2 and a mixture of the epimers 17-(1α/1β-methylpropanone)-nicandrenone, in addition to six known others, were isolated from the leaf acetone extract from Nicandra physalodes. The complete structures of the five new withanolides, particularly their relative stereochemistries, were established by extensive spectroscopic analyses, including 1D and 2D nuclear magnetic resonance (NMR) and high-resolution electrospray ionization mass spectrometry (HRESIMS). The main isolated withanolides were evaluated for their antibacterial, antifungal and larvicidal properties, but, except nicandrenone, which showed marginal larvicidal activity, none of them was active.

Resumo em Inglês:

Amino acids/ureides and carbohydrates are the main nutrients for the plants growth. These metabolites are continuously translocated through the plant organism via well-known transportation mechanisms. The well-established source-to-sink relationship involves the transfer of these nutrients from mature (source) to young (sink) leaves. Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) is used herein to determine the spatial distribution of amino acids/ureides and carbohydrates in the imprintings of Mentha × piperita L. leaves at three distinct maturation stages: young, expanding, and mature. Hence, chemical images of some typical carbohydrates (glucose, sucrose, sorbitol/mannitol) and free amino acids/ureides (phenylalanine, leucine, histidine, aspartate, asparagine, tyrosine, glutamate, allantoic acid) clearly point to a source-to-sink relationship, as the young leaves are the final destination for some of these key metabolites. These results therefore reveal the high potential of DESI-MSI to investigate biochemical processes in plants, a still underexplored area.

Resumo em Inglês:

A method for simultaneous analysis of ciprofloxacin (CIP), levofloxacin (LEV) and norfloxacin (NOR) in mangrove sediment was developed using aqueous ultrasound-assisted extraction (UAE), solid phase extraction (SPE) and high-performance liquid chromatography with fluorescence detection (HPLC-FD). The method showed excellent linear correlation coefficient for the three fluoroquinolones (r2 > 0.999) using external calibration curve and good recovery in real sediment samples ranging from 73.73 to 88.85%. The precision showed a relative standard deviation lower than 20% and detection limits of 1.10, 3.33 and 0.26 µg kg-1 to CIP, LEV and NOR, respectively. There was no presence of interfering. After validation, the method was applied in the determination of pharmaceuticals in mangrove sediment in the Paciência River, Maranhão Island, Brazil. Only the CIP antibiotic was found in three of six samples analyzed, with values ranging 56.55-70.45 µg kg-1.

Resumo em Inglês:

A hydrated kaolinite-methanol intercalation compound (Kaol-MeOH (hydrated)) was synthesized by utilizing kaolinite/dimethyl sulfoxide intercalation compound (Kaol-DMSO) as an intermediary, and further displacement intercalation with butyl trimethylammonium chloride (BTAC) was also carried out. The obtained samples were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results showed that the d001 value of the Kaol-MeOH (hydrated) could be arbitrary values between 0.86 and 1.08 nm, which could be caused by the hydrogen-bonded MeOH or water molecules between the interlayer spaces of methoxy-modified Kaol. Furthermore, this part of interlayer molecules could be removed by heating and have no obvious effect on the subsequent intercalation reaction. In addition, the time required for Kaol-MeOH (hydrated) preparation was drastically shortened to 3 days, which greatly reduces the time-consuming for the preparation of subsequent compounds.

Resumo em Inglês:

The objective was identifying three different anthocyanidins and to quantify them in six different berries. Results from the conventional method (using extraction with hydrochloric acid) were compared with data from the proposed method (without acid extraction). The following figures of merit were used: linearity, accuracy, linear range, limits of detection and quantification, using an ultra performance liquid chromatography (UPLC) coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionization source. The separation of anthocyanidins can be achieved in a much smaller period of time (1.30 min) and the cyanidin from Morus nigra L., Rubus idaeus L. and Vaccinium myrtillus L. was found in higher amounts in extracts obtained from the proposed method. Proposed mechanisms of mass spectrometry (MS/MS) collisional induced dissociation for pelargonidin, cyanidin and delphinidin were obtained and this is the first time that concentrations of anthocyanidins present in fruits of Solanum americanum Mill. were reported.

Resumo em Inglês:

The effects of low contents of acetonitrile (AN) or N,N-dimethylformamide (DMF) on the aggregation of sodium alkyl sulfate surfactants, in the absence and presence of poly(ethylene oxide) (PEO), were investigated using conductivity and isothermal titration calorimetry. The cosolvents slightly changed the critical micellar concentrations and did not alter the critical aggregation concentrations of the surfactants sodium decyl sulfate (DSS) and sodium dodecyl sulfate (SDS) with PEO. However, AN and DMF turned the micellization of the surfactants and their binding to the polymer enthalpically more favorable. For instance, for SDS, the micellization enthalpy, ΔHomic, decreased from close to 0 kJ mol-1 in water to -14.3 kJ mol-1 in the presence of 2.50 mol% AN, and the integral enthalpy change for aggregate formation with the polymer, ΔHagg(int), decreased from -1.1 kJ mol-1 in water to -15.5 kJ mol-1 in the same AN concentration. This was attributed to the modification of the solvation shells of both SDS and PEO by the cosolvent molecules, which reduced the entropic contribution to formation of the aggregates. Consequently, when SDS was replaced with DSS, the AN affected ΔHomic to a lesser extent, with a decrease of 9.1 kJ mol-1, while the ΔHagg(int) values were not altered, highlighting the influence of hydrophobic interactions in the surfactant aggregation process.

Resumo em Inglês:

4A Zeolite was synthesized using rice husk ash (RHA) as a raw material in a microwave-assisted hydrothermal synthesis. Two new procedures were proposed: procedure A, using RHA as the raw material, and procedure B, using the depolymerized RHA. Both procedures were performed using microwave-assisted hydrothermal synthesis, and neither synthesis required an aging time. Crystallinities of over 90 and 80% were reached at 100 ºC after 30 min of microwave heating for procedures A and B, respectively. The obtained zeolites were used as warm mix asphalt additives, and the performance of the zeolite obtained from procedure A was better. Additionally, the zeolite obtained from procedure A and commercial silane were used separately as asphalt-aggregate adhesion promoter. An increase in the adhesion percentage from 30% of a blank sample to 94% was observed.

Resumo em Inglês:

A series of HPW/Zn-Ti layered double hydroxides (LDHs) were prepared by immobilizing phosphotungstic acid (HPW) on the Zn-Ti LDHs. Systematically characterizations were performed to elucidate their structure. These HPW/Zn-Ti LDHs hybrids were used as heterogeneous catalysts in the epoxidation of fatty acid methyl ester (FAMEs) with H2O2. The HPW/Zn-Ti LDHs showed higher activity than bulk HPW and Zn-Ti LDHs. The conversion of FAMEs and the selectivity to epoxy fatty acid methyl ester (EFAME) were up to 90.6 and 86.0%, respectively. (PO4[WO2(O2)]4)3- was presumed to be the active site for the epoxidation in this work. The formed oxygen-donating intermediate Ti-OOH transferred oxygen free radicals to (PO4[WO2(O2)]4)3- in the catalytic process, accelerating the transfer of oxygen free radicals. Therefore, high catalytic activity of HPW/Zn-Ti LDHs is related to the potential synergistic interactions of Ti-OOH and PW anions.

Resumo em Inglês:

A convenient procedure for the synthesis and expansion of bicyclic rings has been developed for the production of probable precursors of non-racemic pyrenophorin, an antibiotic dilactone. The major highlight for this new synthetic methodology came from the use of a readily available reagent of easy manipulation, 9-oxabicyclo[3.3.1]nonane-2,6-diol, for the preparation of the bicyclic intermediate, which sequentially was subjected to oxidative cleavage with butyl nitrite resulted in an isomeric mixture, a dioximedilactone and diisoxazoledilactone.

Resumo em Inglês:

A series of iron-based catalysts supported on activated carbon (AC) and manganese-modified Fe2O3/AC catalysts with various Fe:Mn ratios were prepared for selective catalytic reduction (SCR) of NO by ammonia at low temperature. It was found that the addition of a small amount of MnOx into the Fe2O3/AC catalyst contributed to an improvement of the NO conversion. NO conversions of approximately 100% were obtained for the 10FexMn/AC (x = 1, 3, 5) catalysts at 180-240 ºC. The characterization results indicate that the addition of a certain amount of MnOx into the 10Fe/AC catalyst increased the dispersion of the amorphous state, increased the ratios of Fe3+/(Fe3+ + Fe2+) and Mn4+/Mn3+, and improved the surface area and pore volume.

Resumo em Inglês:

A series of metal oxide supported tungstophosphoric acid catalysts were prepared by impregnation. The physicochemical and acidic properties of these materials were characterized by a variety of different analytical and spectroscopic techniques, namely Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, and nuclear magnetic resonance (NMR), and exploited as heterogeneous catalysts for selective oxidation of benzyl alcohol (BzOH) with hydrogen peroxide (H2O2). Among them, 20 wt.% H3PW12O40/CeO2 catalyst exhibited the best oxidative activity. Further process optimization by response surface methodology (RSM) based on the Box-Behnken design model resulted in a benzyl alcohol conversion of 95.2% and a benzaldehyde yield of 94.2% with 98.9% selectivity, in good agreement with the experimental results. Kinetic studies based on an irreversible parallel reaction model led to an activation energy (Ea) of 44.73 kJ mol-1.

Resumo em Inglês:

In this paper, chemical functionalization of poly(lactic acid) (PLA) was carried out by using of salicyl aldehyde (SAl) and salicylic acid (SAc) as co-initiators of ring opening polymerization (ROP). Two factorial designs (22) were performed to evaluate the effects of the lactide/catalyst and co-initiator/catalyst molar ratios on the content of aldehyde or carboxylic acid end groups, thermal properties and molecular weight (Mw) of PLA. Tin(II) 2-ethylhexanoate was used as a catalyst. The co-initiator/catalyst molar ratio has a statistically significant influence on the polymer functionalization. The highest co-initiator/catalyst molar ratio of 12/1 allows the best aldehyde or carboxylic acid functionalization, independent on the lactide/catalyst molar ratio. On the other hand, the used lactide/catalyst and co-initiator/catalyst molar ratios did not show a statistically significant influence on the polymer thermal properties. Besides, co-initiator/catalyst molar ratio has a statistically significant influence on the polymer molecular weight. So, the highest co-initiator/catalyst molar ratio used (12/1) in combination with the highest lactide/catalyst ratio (125/1) produced functionalized PLA with higher molecular weights.

Resumo em Inglês:

We report herein the design and synthesis via click chemistry of twelve novel triazole retinoid analogues of tamibarotene (AM80) and the evaluation of their anticancer activities against six cancer cell lines: HL60, K562, 786, HT29, MCF7 and PC3. Among the synthesized compounds, two were more potent than tamibarotene against solid tumor cells, and one of them had similar potency to tamibarotene against HL60 cells. The bioisosteric exchange between the amide group and the 1,2,3-triazole core in the retinoid agent tamibarotene (AM80) reported in this work is a valid strategy for the generation of useful compounds against cancer.

Resumo em Inglês:

A new method using nonanoic acid-coated magnetic Fe3O4 nanoparticles as adsorbent has been developed for the single-step extraction and preconcentration of lead and copper in tobacco samples. Transmission electron microscopy and X-ray diffraction spectrometry were used to characterize the adsorbent. The experimental parameters affecting extraction efficiency, including amount of nanoparticles, volume of chelating reagents, sample pH, ultrasonic time and desorption conditions were investigated. The analytes desorbed from nanoparticles were determined by flame atomic absorption spectrometry. Under the optimum conditions, good linearity was obtained in the range of 2-400 µg L-1 for copper and 5-800 µg L-1 for lead (r > 0.998, p < 0.05). The limits of detection for copper and lead were 0.2 and 0.5 µg L-1, with enrichment factors of 45 and 52, respectively. The method was successfully employed to tobacco sample analysis and got excellent recoveries between 89.2 and 100.7% with relative standard deviations (n = 6) of 4.5-5.9%.

Resumo em Inglês:

A new series of 19-nor-clerodane diterpene derivatives was synthesized from the natural trans-dehydrocrotonin obtained from stem barks of Croton cajucara (Euphorbiaceae), a native medicinal plant of the Brazilian Amazon. The new derivatives were obtained by changes in the ketone moiety of trans-dehydrocrotonin leading to nitrogenated derivatives which are: three substituted hydrazine diterpenes, oxime, and methyloxime. The cytotoxic effect of the diterpene derivatives was evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay against Ehrlich carcinoma and K562 human leukemia cells. The cytotoxic activity of the hydrazine and oxime semi-synthetic derivatives was better than the one of the natural product trans-dehydrocrotonin. Moreover, all diterpenes were tested for their DNA topoisomerase I inhibitory activity, and the most effective one, in general, was observed to the phenyl-hydrazone derivative. Results indicated that the topoisomerase I inhibitory effect is correlated with the cytotoxic activity.

Resumo em Inglês:

The present study reports the synthesis and characterization of complexes formed among humic (HA) and fulvic acids (FA) derived from poultry wastes and ions Cu2+, Fe2+ and Zn2+. The release of such metals in a buffer solution simulating the soil solution was also evaluated. After complexation, the Fourier transform infrared (FTIR) spectra presented alterations in the absorption bands related to changes in the humic structure, thus indicating the complexation with phenolic and carboxylic groups. Thermogravimetric analyses demonstrated that complexed metals decreased the thermal stability of humic substances. Analyses by atomic absorption spectroscopy (AAS) demonstrated that the release of metals is directly related to the origin of the sample, type of interaction of metal and humic structure and conditions of the medium in which the complex is inserted.

Resumo em Inglês:

The invasive aquatic plants Eichhornia crassipes (water hyacinth), Eichhornia azurea, and Nymphaea spp. were evaluated as sources of lignocellulosic biomass for the production of bio-oil. These plants have high growth rates that can lead to various environmental problems and the production of large amounts of waste biomass. The materials were characterized in terms of their contents of moisture, oil, and ash, and by analysis using thermogravimetry, infrared spectroscopy (IR), elemental analysis, and energy dispersive X-ray fluorescence spectrometry (EDX). The in natura biomasses had moisture contents of around 90%. Micropyrolysis studies were performed at 500 ºC using the dried biomasses (ca. 8% moisture). The liquid product of pyrolysis (bio-oil) was trapped in an adsorbent and then eluted with different solvents. The best recovery was achieved using tetrahydrofuran. The bio-oil solutions were derivatized with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA) and analyzed by gas chromatography mass spectrometry (GC-MS). The main compounds found in the bio-oils were glycerol, o-benzenediol, p-benzenediol, arabinoic acid, levuglucosan, and hexadecanoic acid.

Resumo em Inglês:

In this research three series of substituted 1H-pyrazolo[3,4-b]pyridine phosphoramidates were synthesized and characterized by infrared, 1H, 13C, and 31P nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry. The products were obtained in good yields (67-83%) under mild conditions by nucleophilic aromatic substitution reaction of aminoalkylphosphoramidates over 4-chloro-1H-pyrazolo[3,4-b]pyridines. These compounds were evaluated as antileishmanials against Leishmania amazonensis promastigotes in vitro. Among all, compounds of a series showed expressive antileishmanial activity. Two of them emerged as the most active, with IC50 values of 6.44 ± 1.49 and 12.25 ± 0.68 µM. The cytotoxicity of this series was assessed on murine cells and presented values similar to the reference drug pentamidine.

Resumo em Inglês:

Coffee bean chemical compositions has been extensively studied. However, there is a small amount of research on other parts of the coffee plant, including leaves. Fourier transform infrared (FTIR) spectral profiles of Coffea arabica L. cv. IAPAR 59 leaf extracts from a simplex-centroid design were studied by principal component analysis (PCA) to evaluate the effect of solvent extractor on its metabolites. PCA indicated that the extractor solvents containing ethanol were the most suitable for this study. FTIR spectra in conjunction with orthogonal signal correction and partial least squares-discrimination analysis (OSC-PLS-DA) were used to classify and discriminate the leaves of irrigated and non-irrigated plants by bands related to carbohydrates, amino acids and lipids. Leaves receiving different intensities of solar radiation were also discriminated by bands corresponding to caffeine, carbohydrates and lipids. FTIR spectral profile analyzed with chemometric tools showed to be a useful, powerful and simple procedure to discriminate coffee leaves collected from different microclimate conditions.

Resumo em Inglês:

Herein we report the synthesis of a series of O-alkyl oximes of flavone and 6-hydroxyflavone using a simple experimental protocol under solvent free conditions with yields up to 87%. Cytotoxicity of all compounds was evaluated against MDA-MB-231, PC-3, A-549 and MRC-5 cells. IC50 values for two compounds were determined to be in the range 28.7-47.8 µM against all tested cell lines. Oxime ethers derivatives showed IC50 values between 28.7 and 49.5 µM against MDA-MB-231, while the best activity was obtained for 6-hydroxyflavone with an IC50 of 3.4 µM against this cell line. Compounds containing the substituent hydroxyl at the position six of flavone system displayed the best antiproliferative activity over MDA-MB-231 cells, being necessary this group to improve the sensibility on this type of cells. The antiproliferative activity of 6-hydroxyflavone is drastically diminished when the carbonyl group of flavone is changed by an oxime ether.

Resumo em Inglês:

This study proposes an optimized procedure for the determination of inorganic antimony species in natural waters using hydride generation atomic fluorescence spectrometry (HG AFS) and continuous flow system. The variables of the hydride generation system, such as pre-reduction time, hydrochloric acid concentration and sodium tetrahydroborate concentration, were evaluated using full factorial design at two levels and Doehlert design. After optimized experimental conditions, the method allowed the determination of antimony with limits of detection and quantification of 9 and 30 ng L-1, respectively. The precision (RSD) of the method was < 5% and the accuracy was confirmed by the analysis of certified reference material (SLRS-4, River water for trace metals). The method was successfully applied for inorganic antimony speciation in water samples collected in Salvador City, Bahia State, Brazil. In mineral water, total Sb concentrations ranged from 0.26 to 0.30 µg L-1, whereas the concentrations of SbIII were below 0.03 µg L-1. On the other hand, in natural surface waters, the quantifiable concentration of total Sb and SbIII ranged from 0.41 to 1.23 µg L-1 and 0.23 to 1.04 µg L-1, respectively. The highest average concentrations of Sb were obtained in regions with the largest urban influence, ratifying the anthropogenic impact in water bodies.

Resumo em Inglês:

Surfactants are molecular structures with remarkable physicochemical properties and applications. Most of their characteristics are due to their ability to promote aggregation and interactions with different interfaces. The scarcity of theoretical studies dedicated to evaluating the forces involved in these interactions prompted us to propose other models capable of reproducing the experimental data in better ways. We carried out molecular dynamics (MD) simulations to obtain a model for cetyltrimethylammonium bromide (CTAB), selected from gromos54a7 force field parameters, that better describes most of its behaviors in aqueous solution (micellar structure, counterion dissociation, etc.) and its adsorption pattern on a gold surface. The parameters adopted for one of the models were able to mimic several characteristics suggested by experimental measurements of the CTAB micelles, as well their adsorption pattern on a gold surface. Indeed, this model was able to obtain quasi-spherical micelles, as well as a pattern of adjacent cylindrical micelles with alkyl chain interactions on a gold surface.

Resumo em Inglês:

An electronic analytical balance was used to monitor a transesterification reaction through density variations. To test the proposed system, we studied how the transesterification reaction was influenced by: (i) the addition of methanol to the oil; (ii) the addition of the catalyst; (iii) stirring; and (iv) temperature.

Resumo em Inglês:

Carotenoid analysis in citrus is still a challenge due to their complex carotenoid profile and matrix acidity, which can promote isomerization and epoxide-furanoid rearrangements of these compounds. A new method for carotenoid extraction from freeze-dried citrus was developed. Extraction was carried out by magnetic stirring using ethyl acetate and methanol as solvents and Na2CO3 to neutralize organic acids. Liquid-liquid partition was achieved by centrifugation. Carotenoid quantification was accomplished by both UV-Vis and high-performance liquid chromatography-diode array detection (HPLC-DAD). Method repeatability (2.9 to 8.5%) and recovery (82 to 88%) were similar to reported values for procedures including all the carotenoid analysis steps. In 'Valencia' orange pulp, xanthophylls accounted for 98% of the total carotenoid content and the predominant carotenoids were (9Z)-violaxanthin, (all-E)-lutein and (9Z)-antheraxanthin. This method was further applied for carotenoid analysis in freeze-dried 'Tommy Atkins' mango pulp. The developed method is precise, accurate, fast and able to maintain epoxy-carotenoids stability during analysis.