Resumo em Inglês:

Corrosion of carbon steel pipelines in sweet environments has been extensively researched on oil and natural gas exploration and production in order to obtain efficient corrosion mitigation methods. Although the consequences of corrosion are known, the cause and mechanism by which a certain phenomenon occurs are still not well understood. Sweet corrosion is mainly caused by the carbon dioxide dissolved in the water contained in the oil. It can manifest itself in different ways and one of which is the formation of a scale on the inner walls of the pipelines, which determines the evolution of corrosion process. This paper discusses the effects of partial pressure of carbon dioxide, dissolved hydrogen sulfide, dissolved oxygen and water chemistry on scale formation. Particular attention is paid to the nature and stability of the aqueous species formed during the corrosion process, as well as the thermodynamic and kinetic aspects lead to the scale formation on the carbon steel surface. The main objective is to enhance the understanding of the conditions of formation and precipitation of siderite and mackinawite and their effects on corrosion processes involving low carbon steels.

Resumo em Inglês:

The developed method (DM) allows to perform experiments in shorter time with reduced amount of sample and reagent for fatty acids (FA) determination in fermented milk samples. Design Expert software was employed to discover the greatest sonication time (7 and 20 min) and concentration for alkaline and acidic reactions (0.70 and 1.5 mol L-1). Validation procedures were applied in yogurt samples with diverse fat content, ranging from 1.22 to 2.83%, being in agreement with acceptable values. Besides, the intraday relative standard deviation (RSD) (1.86%) and interday RSD (4.23%) values confirmed the good accuracy of the proposed method for FA derivatization.

Resumo em Inglês:

Effects of grape maturity, maceration length during winemaking and interaction of both of them on physicochemical parameters, phenolic and volatile composition were investigated in tropical Syrah wines with the aim of finding the best conditions to produce wines that are rich in phenols and positive aroma active compounds. A headspace solid phase micro extraction and gas chromatography with mass spectrometry (HS-SPME-GC-MS) method was improved and validated for the analysis of 41 volatiles. Principal component analysis (PCA) and analysis of variance (ANOVA)-PCA coupled with inspection of statistically significant loadings were important to access the effects of maturation and maceration on wine composition. Wines made from riper grapes (21-23 ºBrix) stood out in relation to color intensity, total phenolic compounds, and presented high levels of anthocyanins, flavonols, procyanidin A2, and linalool (floral). Thirty days of maceration were linked to higher levels of some flavan-3-ols, gallic acid, a few esters (fruity) and alcohols, (E)-nerolidol (floral), while nonanoic acid (unpleasant aroma) reduced its concentration with prolonged maceration.

Resumo em Inglês:

Chagas disease is a neglected tropical disease caused by the hemoflagellated parasite Trypanosoma cruzi (Kinetoplastida). The only available drug to treat chagasic patients in Brazil, the nitroheterocycle benznidazole, is effective solely during the acute phase of the infection. There is accordingly a need to develop new therapeutic tools for the treatment of Chagas disease. This work reports the synthesis, trypanocidal evaluation and human serum albumin (HSA) interactions of a novel series of 1,2,4-triazoles. The new derivatives were synthesized via microwave irradiation in good yields. Most compounds showed toxic effects against T. cruzi with low toxicity to host cells. Three S-alkylated-triazoles showed the best activity profile against amastigotes, with half maximal inhibitory concentration (IC50) values of 3.95 ± 1.41, 4.15 ± 0.92 and 3.61 ± 0.65 µmol L-1, respectively. The interaction between HSA and 3-[(1E,3E)-4-(1,3-benzodioxol-5-yl)buta-1,3-dien-1-yl]-5-(butylthio)-4-cyclohexyl-4,5-dihydro-1H-1,2,4-triazole was investigated using multiple spectroscopic techniques and molecular docking, revealing that serum albumin is a potential endogenous carrier to this compound in the human bloodstream.

Resumo em Inglês:

Meliaceae representatives are economically important in several aspects including the production of highly prized woods (mahogany, cedar, etc.), constituents for cosmetics, and insecticides. The present study aimed to verify the chemical composition as well as leishmanicidal and cytotoxic potential of essential oils from leaves of two different populations of Guarea macrophylla collected at cities of São Paulo (population I) and Cubatão (population II), São Paulo State, Brazil. Chemically, the oils showed the predominance of sesquiterpenes: cis-β-guaiene, bicyclogermacrene, viridiflorol, and isolongifolan-7α-ol from population I and α-copaene, E-caryophyllene, cis-β-guaiene, and γ-amorphene from population II. In vitro antileishmanial activity against promastigote forms of Leishmania (L.) amazonensis of essential oils was evaluated and displayed 50% effective concentration (EC50) values ranging from 11.8 to 20.5 µg mL-1. Furthermore, toxicity against peritoneal macrophages of BALB/c mice was observed, with 50% cytotoxic concentration (CC50) ranging from 17.7 to > 100 µg mL-1. Multivariate statistical analysis revealed the influence of each constituent of the oils against L. amazonensis being 1,10-di-epi-cubenol, α-amorphene, E-caryophyllene, isopimara-7,15-diene, and β-elemene associated with the antileishmanial potential.

Resumo em Inglês:

This work aimed to compare the methods for the determination of twenty plant growth regulators (PGRs) from Chinese herbal medicines by applying liquid and solid extraction methods simultaneously. Quick, easy, cheap, effective, rugged and safe (QuEChERS) and matrix solid-phase dispersion (MSPD) were chosen as the liquid and solid extraction methods, respectively. Due to the complex matrix of herbal medicine, carbon nanotubes were selected as the solutions/sorbents for the extraction and purification. The extracts were analyzed by ultra-performance liquid chromatography-triple quadrupole-mass spectrometry (UPLC-MS/MS). Both methods resulted in good efficiency for the extraction and purification. The recoveries fell in the range of 71-117% with relative standard deviations (RSDs) less than 19%. The limits of detection were in the range of 0.01 to 3 μg kg-1 with the two methods. The standards were prepared using the matrix matched standards due to the considerable matrix effects of the herbal medicines. Compared to the liquid method, the solid method required a smaller amount of sample, which is critical for PGR analysis of rare valuable herbal medicines. The two methods were applied for the determination of the twenty PGRs in different Chinese herbal medicine successfully.

Resumo em Inglês:

Currently, the pharmaceutical industry devotes great attention to drug degradation products because these compounds can offer risks to patients. A previous degradation study of betahistine (N-α-methyl-2-pyridylethylamine) conducted under different stress conditions detected three main impurities named A, B and C. Degradation products were analyzed by high-resolution mass spectrometry in electrospray source and time of flight analyzer (ESI-TOF) and nuclear magnetic resonance (NMR). Impurity mutagenicity was evaluated by Derek Nexus and Sarah Nexus softwares. Liquid chromatography hyphenate with tandem mass spectrometry (LC-MS/MS) analysis of the betahistine forced degradation sample indicated the presence of a new impurity, which was named impurity C1. 2D NMR experiments allowed the complete structural characterization of the new entity. The active pharmaceutical ingredient and degradation impurities were classified as inactive in the in silico mutagenic studies. Systematic investigation of a forced degradation sample led to the characterization of a new betahistine impurity. The in silico mutagenicity study of the betahistine degradation impurities may be useful in the risk assessment of the drug products.

Resumo em Inglês:

Eugenol has diverse biological properties including antimycobacterial activity, and the triazole ring is an important heterocycle in antimycobacterial compounds. Therefore, this research aimed to synthesize novel eugenol-derived 1,2,3-triazole as antimycobacterial agents with interesting cytotoxic profile and pharmacological assets. Sixteen compounds were obtained and characterized by nuclear magnetic resonance (NMR), infrared (IR), and high-resolution mass spectrometry (HRMS). Among them, the best growth inhibition properties from a microdilution assay were observed for three derivatives: a benzylic ether (minimum inhibitory concentration (MIC) = 48.89 µM) against Mycobacterium abscessus (ATCC 19977), an O-galactosyde (MIC = 31.76 µM) against Mycobacterium massiliense (ATCC 48898) and a sulfonate (MIC = 88.64 µM) against Mycobacterium fortuitum (ATCC 6841). They can form biofilms, and the infection progression is challenging to control due to multi-drug resistance profiles against diverse antibiotics. In conclusion, the above-mentioned compounds represent starting points in the search of bioactive molecules against mycobacteria with low cytotoxicity and better pharmacological profiles.

Resumo em Inglês:

Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) was used to assess the spatial distribution of some key flavonoids in peppermint (Mentha × piperita L.) leaves. The chemical images were generated by applying DESI-MSI on the peppermint leaves imprinting while acquiring the spectra in the negative ion mode. The following key flavonoids were detected and grouped within well-known biosynthetic routes in plants: naringenin route [naringenin, sakuranetin, hesperetin, hesperidin, luteolin, and apigenin]; luteolin route [luteolin, chrysoeriol, luteolin-7-O-D-glucuronide, luteolin-7-O-D-glucoside, luteolin-7-O-neohesperidoside]; apigenin route [apigenin, apigenin-7-O-gentiobioside, apigenin-7-O-neohesperidoside, thymusin/pilosin, pebrellin, acacetin/genkwanin, ladanein, xanthomicrol/pedunculin/nevadensin]. Maps of the spatial distribution of these flavonoids throughout the peppermint leaves within each route were then displayed. The results described herein comprise an important (although still underexplored) subject that certainly will experience a remarkable growth in the next years.

Resumo em Inglês:

Fluoroquinolones antimicrobials are partially excreted in natura after administration. Their occurrence was investigated in hospital raw sewage (HRS) and treated wastewater (TW) using an online solid phase extraction-ultra high-performance liquid chromatography-tandem mass spectrometry method (SPE-UHPLC-MS/MS). The analytical curves ranged from 0.25 to 46 ng mL-1 and the matrix effect, assessed for marbofloxacin and lomefloxacin, ranged from –63 to +1%. All HRS samples contained ciprofloxacin (1-34 ng mL-1) and ofloxacin (0.9-27 ng mL-1), while norfloxacin was detected in 17% of the samples (0.8-4.4 ng mL-1). Only ciprofloxacin (0.5-5.6 ng mL-1) was detected in TW samples. The antimicrobial activity of the HRS samples for E. coli was higher than a ciprofloxacin solution of 1 mg L-1, due to the presence of other antimicrobial agents. Ozonation (10 mg O3 L-1 min-1 ; 10 min) degraded up to 84% of the fluoroquinolones and removed the antimicrobial activity of HRS samples.

Resumo em Inglês:

Density functional theory (DFT) calculations have been performed to develop a systematic structural analysis of Au13L83+, where L = SCH3, SeCH3, SCH2OCH3 and S(CH2)2NH2, in order to examine the influence of different ligands. Binding energy calculations indicate that the gold core is more stabilized by the ligand in the following sequence S(CH2)2NH2 > SCH2OCH3 > SeCH3 > SCH3. Natural bond orbital (NBO) analysis describes the interaction between the gold and the ligands, showing that the strongest electron donation occurs from a lone pair orbital on the sulfur and selenium atoms to the antibonding acceptor σ* (Au-S) and σ* (Au-Se) orbitals, respectively. The NBO analysis allowed to understand the origin of enhanced stability of the [Au13(S(CH2)2NH2)8]3+. Time-dependent DFT (TDDFT) calculations have been performed to simulate the optical absorption spectra of Au13L83+ in gas phase and under the effect of solvents with different polarities. The absorption spectrum of [Au13(S(CH2)2NH2)8]3+ shows a spectral profile that differs considerably from the others in gas phase and which is strongly affected by the solvent.

Resumo em Inglês:

Coconut oil has several domestic uses and health benefits, which can be used in food, pharmaceuticals and cosmetics products. However, it has been the target of adulteration with lower price oils and fats, such as soybean oil. In this study, a fast, easy and simple methodology was used to detect low quantities of intentionally adulterated coconut oil with soybean oil by direct infusion electrospray ionization mass spectrometry (ESI-MS) at different levels (0, 2, 5, 10, 15, 20, 30, 50, 70 and 100%). In the oil industry, intentional adulterations usually occur with the addition of low quantities of soybean oil to coconut oil. Therefore, the suggested ESI-MS method is promising for routine analysis to guarantee the quality control of coconut oil since it is possible to detect adulteration with a minimal of 2% soybean oil addition.

Resumo em Inglês:

Herein, we present the serendipitous obtaining of 7-chloro-2,3-dihydro-5H-thiazolo [3,2-a]pyrimidin-5-one in 40% yield by using POCl3 and a thiobarbituric acid derivative. The thiazolopyrimidine derivative was characterized by 1H nuclear magnetic resonance (NMR), UV-Vis, and Fourier transform infrared (FTIR) spectroscopy. Additionally, the structure was confirmed by single crystal X-ray diffraction, where it was found that the compound crystallizes in the P-1 triclinic space group with two conformeric molecules of 7-chloro-2,3-dihydro-5H-thiazolo [3,2-a] pyrimidin-5-one by asymmetric unit. Also, from the structural data was studied the supramolecular interactions using Hirshfeld surface analysis and 2D fingerprint plots.

Resumo em Inglês:

A series of N-aryl-5,6,7,8-tetra-hydrobenzo[4,5]thieno[2,3-d ]pyrimidin-4-amines were synthesized in moderate to good yield by using a microwave-enhanced conditions. The selected compounds were evaluated for their cytotoxic effects (IC50 values) on human pulmonary carcinoma (A549), murine BALB/c spontaneous colon adenocarcinoma (CT26) and human hepatocellular liver carcinoma (HepG2) cell lines in vitro. Amongst these compounds, one compound was found to have the better cytotoxic activity with reference to the standard Erlotinib hydrochloride (Tarceva™) against A549 (IC50 = 16.06 ± 0.09 µM) and HepG2 (IC50 = 15.01 ± 0.31 µM) cell lines. Especially, two compounds showed best cytotoxic effects against CT26 (IC50 = 11.38 ± 0.44 µM) and HepG2 (IC50 = 8.51 ± 0.52 µM) cell lines, respectively. The preliminary structure-activity relationships were disclosed and the thieno[2,3-d] pyrimidine skeleton could be exploited to potential antitumor agents in the future.

Resumo em Inglês:

This study evaluated different methods of extraction based on quick, easy, cheap, effective, rugged and safe (QuEChERS) method for analysis of the antibiotics ceftiofur, cloxacillin and enrofloxacin in milk using ultra-performance liquid chromatography-tandem mass spectrometry. The QuEChERS acetate method has been shown to be inefficient for extracting such antibiotics. The optimized QuEChERS method presented excellent recoveries, from 95 to 99%. A complete factorial design was used to evaluate the effects of variables of the clean-up step: anhydrous octadecylsilane (C18), primary secondary amine (PSA) and sodium acetate (NaAc). Linearity (R2) above 0.96 was achieved for all compounds. Accuracy and precision were assessed by recovery. Accuracy was 91-99%. Intraday precision with relative standard deviations (RSD) lower than 12.3% and interday precision lower than 12.4% were obtained. Limits of detection (LOD) and quantification (LOQ) were obtained between 1.4-6.8 and 1.5-8.7 µg L-1, respectively. The applicability was evaluated using 91 real milk samples.

Resumo em Inglês:

Total phenolic compounds (TPC) extraction from the seed and total monomeric anthocyanins (TMA) extraction from the skin of “Sabará” jabuticaba were optimized with simplex lattice designs for solvent mixing, and the extraction time was optimized by univariate design. The optimum conditions for the extraction method were ethanol:water (60:40 v/v) solvent for TPC (seed) and methanol:water:acetic acid (80:20:0.5 v/v/v) solvent for TMA (skin). For both compound groups, the optimum extraction time was 30 min. The TMA yield for the skin of the “Sabará” variety was 1172.16 mg cyanidin-3-glycoside equivalents per 100 g freeze-dried sample, and for TPC in the seed, it was 86.50 mg gallic acid equivalents per 1 g freeze-dried sample. Both optimized extraction protocols proved to be extremely fast, simple, inexpensive and to have excellent extraction performance. The optimized protocols were compared with two other methods described in the literature and they were also applied to study the TMA contents in skin and the TPC contents in seed of five other varieties of jabuticaba, harvested in 2014 and 2015.

Resumo em Inglês:

This work reports the remediation of a liquid residue derived from the thermal treatment of petrochemical residues by advanced oxidation processes. Firstly, degradation studies of phenol aqueous solutions by heterogeneous photocatalysis, Fenton, and photo-Fenton were conducted. Fenton processes showed a higher efficiency, mainly in the UVA photo-assisted mode (94% in 3 min), and henceforward it was chosen for the remediation of the residue. However, the high organic load of the raw residue (6,000 mg L-1 of chemical oxygen demand (COD)) limited the efficiency of the Fenton processes. Hence, the raw liquid residue was diluted with the scrubber residue, produced during the thermal treatment of the petrochemical residues, reducing the COD to values close to 2,000 mg L-1. The photo-Fenton treatment allowed the removal of approximately 95% of the COD load, decreasing the residual concentration of phenolic compounds from 213 to 0.5 mg L-1. At the same time, the concentration of BTEXs (benzene, toluene, ethylbenzene and xylene) were reduced to values lower than the limit of quantification (LOQ) of the chromatographic technique. Therefore, the photo-Fenton process is an efficient alternative to the remediation of residues with high complexity and with high COD values, like the ones obtained in the petrochemical industry.

Resumo em Inglês:

Sugarcane waste ash, a Si-rich waste product, is generated in large quantities and creates a serious disposal problem in the Brazilian ethanol-sugar industry, affecting the environment and public health. Here, a simple method capable of generating bare silica nanoparticles utilizing this residue is demonstrated. Firstly, the crystalline silica present in sugarcane waste ash (SWA) was converted into amorphous by melting a mixture of sodium hydroxide and SWA at 550 ºC for 1 h. The silica nanoparticles (SiO2NPs) were formed by lowing pH. This production process of SiO2NPs from SWA was optimized varying the ash:NaOH mass ratio, increasing the silica extraction up to 96%. The sample’s composition was characterized by total X-ray fluorescence spectroscopy, morphology and physical-chemical properties were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, specific surface area measurements, Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analyses (TGA), followed by use as adsorbent for the removal of methylene blue dye. With this process of extraction, nanoparticles smaller than 100 nm were generated, with a surface area of 63 m2 g-1 and a maximum adsorption capacity of 37 mg g-1 for methylene blue. The results indicate a successful process for obtaining an adsorbent from an industrial waste product using a cost effective and rapid synthesis procedure rendering renewable product.

Resumo em Inglês:

The present work aims at studying the preconcentration of Cu2+ ions by solid phase extraction using SiO2/Al2O3/TiO2 ternary oxide as adsorbent material. This methodology consists of the affinity of the analyte for the adsorbent material and its subsequent elution with the least amount of solvent. Subsequently, the aqueous phase containing the extracted analyte was collected and analyzed by square wave anodic stripping voltammetry (SW-ASV). For the applied solid phase extraction (SPE) methodology, a complete factorial design was carried out with 3 variables at 2 levels (pH, elution flow rate and analyte concentration) to optimize the extraction conditions. The results showed that at pH 9, the SiO2/Al2O3/TiO2 oxide presents excellent Cu2+ adsorption capacity with recovery values between 81.0 and 104% for this pH range. The limit of detection (LOD) and limit of quantification (LOQ) values were determined to be 1.71 and 5.64 µg L-1, respectively. The study of recovery for SPE method revealed results of 102 and 103%.

Resumo em Inglês:

Boron doped diamond films (BDD) are the most studied electrocatalytic materials and their efficiency for removing organic compounds is attributed to their ability to produce a large amount of hydroxyl radicals by the electrolysis of water. However, some organic compounds are easy to degrade than others, as well as they also interact with BDD surface. Thus, it is necessary to understand the chemical/electrochemical process at the molecular level. In this frame, this work aims to study the electrochemical oxidation (EO) of oxalic acid (OA) at BDD anode, understanding the reaction mechanism, formation of hydroxyl radicals, the effect of supporting electrolyte concentration, and the role of oxidants in solution taking into consideration the cyclic and linear voltammetric measurements. Voltammetric results clearly reveal that a direct electron transfer is achieved as the main mechanistic behavior suffered by OA on BDD surface before oxygen reaction. However, the concentration of sulfates in solution plays an important role in the solvation, diffusion and adsorption species at BDD surface, promoting parallel mechanisms. From the information provided by experimental measurements, the preferential mechanism on BDD surface at low or high overpotential regions was elucidated.

Resumo em Inglês:

Prostate cancer is one of the most common form of cancer among men, and its incidence has been increasing progressively. Since the prostate depends on androgenic hormones to regulate its growth and development, interference with androgenic biosynthesis are important to control the disease. Thus, in this work, a 4D-quantitative structure-activity relationship (QSAR) receptor independent study was carried out using the Laboratório de Quimiometria Teórica e Aplicada (LQTA)-QSAR approach and the new tool Web-4D-QSAR with a set of benzylidene oxazolidinedione and thiazolidinedione inhibitor of the 17β-hydroxysteroid dehydrogenase type 3. The obtained model is robust, free from chance correlation, and with good predictability in all tests performed. In addition to this result, a good mecanistic interpretation related to the binding with the biological target could be traced, which strengthens its potential application in virtual screening and design of new inhibitors of the studied enzyme with the possibility of use in the pharmacological treatment of prostate cancer.

Resumo em Inglês:

Two new compounds, caryopristimerin and 2α,3α,22β-trihydroxy-21-oxo-29-nor-friedelan-24-oic acid, were isolated from the hexane/ethyl ether extract of Salacia crassifolia roots. Caryopristimerin represents the first example of a homo Diels-Alder adduct of a sesquiterpene and a triterpene, and the new 29-nor-friedelane displays a highly oxygenated A ring with a carboxylic group at the unusual C-5 position. The new compounds were elucidated by infrared (IR), high-resolution-atmospheric pressure chemical ionization-mass spectrometry (HR-APCI-MS), 1D/2D nuclear magnetic resonance (NMR) and single crystal X-ray diffraction analysis. Additionally, the known compounds 3-oxo-29-hydroxyfriedelane, pristimerin, tingenone and netzahualcoyonol are herein reported for the first time as constituents of S. crassifolia. Their structures were established by spectroscopic analysis.