Resumo em Inglês:

From the recent development of catalytically controlled C-H activation with amenable synthetic routes obviating many challenges, the demand for this strategy has raised significantly to perform complex organic transformations. The impact of the achieved results in both homogeneous and heterogeneous catalysis reflects its efficacy in modern synthetic chemistry. A consolidated report and guidance of the methodologies involved in the previous and ongoing research in this domain would be very useful for the researchers to focus on more specific and selective C-H activation reactions to access desired complex molecular scaffolds. The perspective of this review is to contribute to the scientific community with examples, tips and details of modern development in this field and with a complete illustration of the routes which may be effective for planning of the ubiquitous C-H bond activation and its use for synthesis of relevant organic molecules.

Resumo em Inglês:

Green Cavendish banana peel and pulp flours were obtained by three drying methods: oven dryer at 70 °C; air fryer at 180 °C and domestic oven at 180 °C, being the latter two new possibilities. Bioactive constituents using paper spray ionization mass spectrometry (PS-MS), phenolic identification and quantification by ultra-performance liquid chromatography with UV-Visible detection (UPLC/UV-Vis) and antioxidant capacity were evaluated. Phenolic acids showed distinct thermal stability between the treatments. Gallic acid was the predominant compound, ranging from (29.56 to 1211.74 mg 100 g-1) and had higher concentration than that found in other bananas described in literature. Green Cavendish banana flour is an advantageous source of bioactive compounds and antioxidant capacity, especially its peel. 26 compounds were identified by PS-MS: phenolics, organic acids, sugars, amino acid, phytosterol, iridoid and coumarin derivatives. Green Cavendish banana flour has great functional potential, and the air fryer can be a promising alternative for drying.

Resumo em Inglês:

In this work, we investigated the use of cotton scraps in natura and modified with iron nitrate, in the adsorption of one of the main water contaminants of the textile industries, the reactive black dye. Special attention was paid to the appropriate destination of the spent adsorbent, in compliance with the precepts of the circular economy. Cotton and polyester are excellent candidates for adsorbents and are produced on a large scale worldwide, but fabric wastes do not yet have a well-established method of application. We found that fabrics containing different types of fibers or colors maintain the ability to remove dye. The retention promoted by the cotton fabric in natura reached 18.8 mg g-1. After treatment with iron ions, there was an increase in the dye adsorption capacity to 31.0 mg g-1. In addition, the spent iron-containing adsorbent was pyrolyzed at 973 K, resulting in an activated magnetic carbon with a specific surface area ranging from 300 to 565 m2 g-1. Thus, it was possible to convert the used adsorbent into a new material with wide application possibilities.

Resumo em Inglês:

In this work, we report a method to quantify methylparaben, ethylparaben, propylparaben and butylparaben in urban waters of São Carlos (São Paulo State, Brazil) by online solid phase extraction-liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) system. The method achieved ng L-1 limits with good accuracy and precision (internal standards for each paraben were used). The total run cycle time takes 9.5 min per sample including the extraction, cleanup and columns conditioning cycles, lower collection volumes of urban water and solvent usage. The SPE cartridge applied showed robustness allowing over 500 sample injections (800 µL each) with good chromatographic performance. This study findings included the detection of parabens in samples in São Carlos.

Resumo em Inglês:

Herein, we present three new binuclear copper(II) complexes containing different polycyclic aromatic hydrocarbons, able to catalyze the oxidation of 3,5-di-tert-butylcathecol, a model substrate for catechol oxidase. The ligands and complexes were successful characterized in solid and solution states. The structure of C1 was determined by X-ray crystallography and it contains a [CuII2(L1-µ-phenoxo)(OAc)(H2O)2] unit, with two coppers in a pyramidal square geometry and a large distance of 3.715 Å between the copper(II) centers. All complexes (C1, C2 and C3) were found to be effective catalysts in the oxidation of 3,5-di-tert-butylcathecol to its quinone and C1 provided the highest catalytic constants at the three pH values studied. In addition to their potential use as a biomimetic catalyst in catechol oxidation, the interaction of these complexes with deoxyribonucleic acid from calf thymus (CT-DNA) was also studied, and C3 showed the greatest affinity with nucleic acids.

Resumo em Inglês:

Electrochemical procedures have emerged as a powerful tool for the synthesis of complex organic molecules including transformation of natural products. In this study, the electrosynthesis of biseugenol in MeOH afforded one new oxidized derivative, which was characterized as methoxyl-oxo-biseugenol (MOB) by nuclear magnetic resonance (NMR) and electrospray ionization-high resolution mass spectrometry (ESI-HRMS) analysis. Since biseugenol was previously described as a cytotoxic natural product, MOB was also tested against tumoral cells B16F10-Nex2 (murine metastatic melanoma) and SKMEL-25 (human metastatic melanoma) as well as against non-tumoral cells MØ Raw 264.7 (murine macrophage immortalized) and HUVEC (human umbilical endothelium). As results, MOB showed inhibitory concentration that affects 50% of cells (IC50) values of 9.5 ± 1.6 mg mL-1(B16F10Nex2), 13.2 ± 2.5 mg mL-1 (SKMEL-25), 19.9 ± 3.5 mg mL-1 (MØ Raw 264.7) and 36.3 ± 7.4 mg mL-1 (HUVEC). Therefore, selectivity index (SI) values of MOB to tumoral cells B16F10Nex2 and SKMEL-25 were calculated as 2.1 and 2.8, respectively, higher than biseugenol (1.4 and 1.7, respectively). Based on these results, the superior cytotoxic activity of MOB in comparison to biseugenol could be associated, at least in part, to the presence of a non-aromatic ring and a conjugated carbonyl system instead of a phenol moiety.

Resumo em Inglês:

This work describes a novel synthetic route for obtaining 2-amino-naphthoxazoles derived from β-lapachone, which consists of a condensation reaction between β-lapachone and thiourea in a basic medium. This synthetic approach can be seen as a potential route for obtaining 2-amino-oxazoles from quinones. The obtained amino-naphthoxazoles were characterized by spectroscopic techniques and the crystal structure of one of them was resolved by X-ray diffraction. The experimental results were compared to that obtained through density functional theory (DFT) calculations, revealing high correlation coefficients.

Resumo em Inglês:

Seventeen Schiff bases bearing 2-aminothiophene derivatives were designed and synthesized using molecular simplification. The resulting compounds (4a-4q) were evaluated for their in vitro antifungal activity against dermatophytes. Prediction of their druglikeness and pharmacokinetic properties, establishment of their structure-activity relationships (SAR), and cytotoxic evaluation of the most active compounds were performed. Using an eco-friendly procedure, microwave assisted synthesis resulted in compounds in good yields (35-85%). Compounds 4a-4q presented good druglikeness and pharmacokinetic profiles and no cytotoxicity for any cell line tested up to 100 µM. The compounds presenting the best antifungal profiles were 4e, 4f, 4g, 4k, 4l, 4m, 4o and 4p with more than one minimum inhibitory concentration (MIC) value occurring between 16-64 µg mL-1, thus, in some cases better than the reference drug (fluconazole). SAR testing indicated that the presence of halogens and nitro substituents increases antifungal activity. Taken together, the results demonstrate that 2-aminothiophene derivatives are promising lead compounds for the development of antifungal drugs.

Resumo em Inglês:

The present study investigated the use of choline chloride:glycerol deep eutectic solvent as an adjuvant for tuning the ethanol extraction of astaxanthin from Litopenaeus vannamei processing residues. The adjuvant concentration did not show a clear trend on the total carotenoid, however, the addition of adjuvant proved to be advantageous in the ultrasound-assisted experiments. In order to establish a balance between total carotenoid and productivity, an operational condition with ultrasound, 5% (m/v) choline chloride:glycerol and 10 min of incubation was selected, which provided 737.69 µg g-1 total carotenoids and 32.71 µg g-1 astaxanthin. When compared to the astaxanthin standard, the shrimp residue extract obtained greater antioxidant activity in free radical scavenging tests. In addition, the shrimp residue extract dramatically reduced the dosage of norfloxacin (up to 87.5%) and gentamicin (up to 75.0%) antibiotics in tests to inhibit the growth of Gram-negative bacteria.

Resumo em Inglês:

Polymeric films have been increasingly investigated due to the ease of miniaturization and integration in several sensor devices. Films obtained from the electrospinning technique have a controlled diameter and homogeneity, and substances can be incorporated into the polymeric network. Electrospinning fiber of chitosan (Ch) and poly(ethylene oxide) (PEO) was obtained from solutions prepared at different concentrations in acetic acid, and varying the distance and the voltage applied. The obtained films were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and UV-Visible specular reflectance spectra (UV-SRS). The best conditions for electrospinning were obtained for a 2% m/v (Ch + PEO) solution in the ratio 90:10% m/m (Ch:PEO), applied voltage of 18 kV, and 18 cm distance between the capillary tube and collector. Acridine orange, sodium fluorescein, and erythrosine fluorescence dyes were successfully incorporated into Ch:PEO films. The spectrofluorometric spectra of the films showed excitation and emission processes and the acridine orange film showed evidence of excimer formation by the presence of an excitation peak at 569 nm. Ch-PEO films with the incorporation of fluorescent dyes may well be used as flexible probes or sensors in colorimetric devices in biochemical applications.

Resumo em Inglês:

The pore size of the chabazite structure is exceptionally suitable for the methanol to olefins (MTO) reaction. The reaction has an induction period required for the formation of a hydrocarbon pool (HP), usually composed of aromatic compounds of different sizes. HP is alkylated by methanol and afterward cracked, leading to the formation of olefins. Despite the importance of HP, its formation and growth in size are exceedingly dependent on the porosity of the catalyst. The ideal is that the formed HP remains stable throughout the reaction because the growth in its size causes blockage of the small catalyst pores, decreasing its capacity. Herein we studied chabazite zeolites with different porosity and structure, caused by variation in the particle size and pores’ volume. Porosity influenced the formation of HP species in quantity (as revealed by thermogravimetric analysis (TGA)) and polymerization degree (gas chromatography coupled with mass spectrometer (GC-MS) analysis) and, consequently, the MTO reaction’s performance.

Resumo em Inglês:

Rhinella jimi toads (Stevaux, 2002) belong to the Bufonidae family, are endemic in the Brazilian Northeast and are commonly found during rainy periods. In general, amphibians of this family have in their poisons different metabolites that show a diversity of pharmacological activities. The isolation and identification of these compounds are of great importance, and techniques such as high-performance liquid chromatography coupled to mass spectrometry are widely used for the discovery of novel and known compounds in these poisons. For R. jimi poison, the ethyl acetate and methanolic extracts were obtained and thirty compounds were identified by combining ultra-performance liquid chromatography coupled to mass spectrometry (UPLC-MS) with direct infusion atmospheric pressure chemical ionization mass spectrometry (DI-APCI-MS/MS) and direct infusion electrospray mass spectrometry (DI-ESI-MS/MS) for each extract, respectively. Marinobufagin (2) and marinobufotoxin (19) were the majorities of each extract, respectively. In addition, other bufadienolides mainly present in the ethyl acetate extract, such other bufotoxins, alkaloids and arginine diacid derivatives were identified in the methanol extract. In a cytotoxic assay by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), the extracts and compound 2 demonstrated half-maximal inhibitory concentration (IC50) values better than the positive control doxorubicin, evidencing excellent cytotoxic. This is the most complete study of the chemical composition of R. jimi toad poison and its respective cytotoxic activity, promoting the enrichment of knowledge about this family and species.

Resumo em Inglês:

In this work, three complexes were synthesized from the trivalent europium ion (EuIII), using the picrate anion (pic), and delta-valerolactam (DVL), epsilon-caprolactam (EPK), and oenantholactam (OEN). The synthesized complexes [Eu(pic)3·(DVL)3], [Eu(pic)3·(EPK)3], and [Eu(pic)3·(OEN)3] were studied as luminescent markers for application as security elements in Brazilian banknotes. All complexes showed red color emission with absorption at 397 nm and emission at 614 nm. Qualitative luminescence tests were performed on R$10, R$20, R$50, and R$100 Brazilian banknotes. The complexes were applied on the surface of the banknotes and were exposed to different wavelengths of 254, 312, 365, and 320-400 nm. The chemical profiles of the complexes were identified on the banknotes employing the laser desorption ionization mass spectrometry (LDI (±) MS) technique. Generally, tests were promising, and can thus provide a simple, fast, and easy method to identify the authenticity of questioned documents, with an average cost of R$0.65 per mg.

Resumo em Inglês:

N-Phthalimido β-amino acid derivatives, 3-phthalimido-3(2-hydroxyphenyl) propanoic acid (P2HPA) and 3-phthalimido-3(2-nitrophenyl) propanoic acid (P2NPA) with new series of di- and triorganotin(IV) complexes (1-12) have been designed and synthesized. All the ligands and organotin(IV) complexes were characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H, 13C, 119Sn) spectroscopy and electron ionization mass spectrometry (EI-MS). Synthesized ligands and complexes were screened to determine the antibacterial activity and results showed that the triorganotin(IV) complexes have better activity compared to diorganotin(IV) complexes and ligands. In addition, molecular docking analysis of ligands on the catalytic pocket of sortase A (PDB ID 1T2W) showed that the ligands can bind the active amino acid residues in the pocket. The antioxidant activity was also performed by the DPPH (1,1-diphenyl-2-picrylhydrazyl radical) method and complexes showed better results than ligands. The compounds were also tested in vivo to determine the hypoglycemic activities on different groups of alloxan induced diabetic rabbits. The complexes (1-6) were found better hypoglycemic agents as they stabilized the glucose level to about 175-105 mg dL-1 as compared to ligand P2HPA.

Resumo em Inglês:

The key step in the chemoenzymatic synthesis of apremilast was to produce the chiral alcohol (R)-1-(3-ethoxy-4-methoxyphenyl)-2-(methylsulfonyl)ethanol, (R)-3. Two enzymatic approaches were evaluated to obtain (R)-3, one using ketoreductases and the other lipases. Bioreduction of 1-(3-ethoxy-4-methoxyphenyl)-2-(methylsulfonyl)ethanone (2), using ketoreductase KRED-P2-D12, led to (R)-3 with 48% conversion and 93% enantiomeric excess (ee). Kinetic resolution of rac-1-(3-ethoxy-4-methoxyphenyl)-2-(methylsulfonyl)ethyl acetate (rac-4), via hydrolysis reaction, with 20% of n-butanol, catalyzed by lipase from Aspergillus niger yielded (R)-3 with > 99% ee, 50% conversion and E-value (enantiomeric ratio) > 200. The reaction between enantiomerically pure (R)-3 and 4-acetylamino-isoindol-1,3-dione (8) afforded apremilast in 65% yield and 67% ee.

Resumo em Inglês:

Xylopia aromatica (Lam.) Mart. (Annonaceae) is a typical species from the Brazilian cerrado that presents medicinal properties. The plant is distinguished by its large white flowers which produce a pleasant fragrance. X. aromatica is characterized by a wide range of medicinal application. These characteristics have motivated us to investigate the flowers volatile organic compounds (VOCs) via in vivo and in vitro protocols by a headspace solid-phase microextraction (HS-SPME) technique combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS). Four different fibers, extraction times and temperatures were the parameters changed to lead to the maximum profiling of the volatile constituents. Data were analyzed using principal component analysis (PCA). A total of 77 VOCs were extracted from the floral scent, with 52 and 68 extracted from in vivo and in vitro sampling, respectively, of which 48 were reported for the first time in the literature as volatile constituents from X. aromatica flowers. The extraction and identification of VOCs were successfully performed through HS-SPME/GC-MS. The PCA data allowed the identification of parameters that led to the maximum number of VOCs, which were polyacrylate (PA) and carboxen/polydimethylsiloxane (CAR/PDMS) fibers, 60 min extraction time and temperature of 29.0 °C. Among the volatile constituents identified, sesquiterpenes predominated, comprising about 61.04%.

Resumo em Inglês:

Thallium (Tl) is a rare metal with toxic effects notably harmful to human health and the environment. In this article, the natural occurrence of Tl was evaluated in a deactivated manganese mine located in the western region of Bahia, Brazil. The extraction procedure with aqua regia was used to dissolve the soil, sediment, and tailings samples. The Tl content was determined by differential pulse anodic stripping voltammetry (DPASV) and manganese (Mn) and iron (Fe) by flame atomic absorption spectroscopy (FAAS). The Tl levels ranged from 0.64 to 473 mg kg-1, triggering an alert since most of the samples (soil and sediment) analyzed presented Tl concentrations above 1.0 mg kg-1, recognized as the maximum limit recommended by environmental agencies in North America and Europe.

Resumo em Inglês:

This work shows an alternative methodology based on a portable near-infrared (NIR) spectroscopy coupled to independent components analysis (ICA) in a pseudo-univariate calibration way to determine total anthocyanins (TA) concentration and antioxidant activity (AA) in whole grape juice. To this, the scores proportions more related to TA and AA were plotted against TA and AA obtained by its respective references methodology to build pseudo-univariate calibration models with correlation coefficients of 0.9699 and 0.9814, respectively. From the results, it is possible the suggestion that NIR spectra coupled to ICA enable to overcome interferences using first-order data and work properly when there is enough selectivity for the analyte profile in the sample data.