Scielo RSS <![CDATA[Química Nova]]> http://www.scielo.br/rss.php?pid=0100-404220180005&lang=es vol. 41 num. 5 lang. es <![CDATA[SciELO Logo]]> http://www.scielo.br/img/en/fbpelogp.gif http://www.scielo.br <![CDATA[CHEMICAL COMPOSITIONS AND ANTIOXIDANT AND ANTIMICROBIAL ACTIVITIES OF PROPOLIS PRODUCED BY <em>Frieseomelitta longipes</em> AND <em>Apis mellifera</em> BEES]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500485&lng=es&nrm=iso&tlng=es In this study, we investigated the chemical compositions and antioxidant and antimicrobial activities of propolis produced by the stingless bee Frieseomelitta longipes and the honeybee Apis mellifera collected from colonies in North Brazil. In terms of volatile composition, both mono- and sesquiterpenes were detected in the propolis of F. longipes while only sesquiterpenes were detected in that of A. mellifera. Out of 50 volatiles identified in all samples, 26 were found exclusively in F. longipes propolis and 8 were found exclusively in A. mellifera propolis. The chemical profiles of the propolis extracts were determined by atmospheric pressure chemical ionization-mass spectrometry and liquid chromatography-electrospray ionization-tandem mass spectrometry allowed to identify several prenylated benzophenones. A. mellifera extracts exhibited major antioxidant activity as assessed by the 2,2-diphenyl-1-picrylhydrazyl method and all extracts exhibited antioxidant activity as assessed by the β-carotene/linoleic acid method. The ethanolic extracts of the propolis showed promisor activity against all tested microorganisms. <![CDATA[THERMOGRAVIMETRIC APPROACH FOR ASSESSING THE OXIDATION LEVEL OF A BIODIESEL SAMPLE]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500492&lng=es&nrm=iso&tlng=es Biodiesel, unlike diesel, is highly susceptible to autoxidation. This autoxidation is a major concern for a biodiesel producer. Various methods have been developed to estimate the degree of oxidative stability of biodiesel. These methods are useful to compare and estimate the oxidative stability between different biodiesel samples. However, an absolute value of the oxidative state will be more useful. In this study, we describe a method of estimating a figure that can be used as an indicator of the oxidation level. This indicator was determined from the thermal decomposition curve of biodiesel, as obtained from the thermogravimetric test. Biodiesel from waste cooking oil was oxidized at 80, 100 and 120 ºC using different exposure areas (19.6, 63.6, and 153.9 cm2). The percentage of oxidation, measured from low (80 ºC, 19.6 cm2) to highly aggressive conditions (120 ºC, 153.9 cm2), was in the range of 0.4 ± 0.1 and 23.5 ± 3.3. Kinematic viscosity was also measured for the oxidized samples, and a strong correlation (R2=0.96) was observed between the percentage of oxidation products and kinematic viscosity. In addition, the oxidative effect of temperature and area of exposure on the biodiesel samples was confirmed by ultraviolet spectroscopy. <![CDATA[SYNTHESIS AND CYTOTOXIC ACTIVITY OF 1,2,3-TRIAZOLE DERIVATIVES OF EUGENOL]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500497&lng=es&nrm=iso&tlng=es Eugenol is an aromatic compound found in several plant species. It presents important biological activities including cytotoxicity. In this paper, it is described the synthesis and the evaluation of the cytotoxic activity of eugenol derivatives bearing 1,2,3-triazole functionalities. Eugenol, extracted via hydrodistillation from dried flower buds of Eugenia caryophyllata (=Syzygium aromaticum), was submitted to alkylation reactions to afford two terminal alkynes in good yields. The key reaction involved in the preparation of eugenol derivatives corresponded to the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC), between alkynylated eugenol derivatives and different benzyl azides. The evaluation of the cytotoxicity of twenty seven synthesized derivatives against HL60 leukemia cell line revealed that at 100 µmol L-1, five of them, namely 4-((4-allyl-2-methoxyphenoxy)methyl)-1-(3-bromobenzyl)-1H-1,2,3-triazole (6n), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-benzyl-1H-1,2,3-triazole (7a), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(4-chlorobenzyl)-1H-1,2,3-triazole (7c), 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(4-iodobenzyl)-1H-1,2,3-triazole (7e) and 4-(3-(4-allyl-2-methoxyphenoxy)propyl)-1-(3-bromobenzyl)-1H-1,2,3-triazole (7m), were capable of significantly decreasing cell viability. These most active triazolic derivatives were also evaluated against B16F10 melanoma and Nalm6 leukemia cell lines. While only compound 7a was active against the former, compounds 6n, 7a, and 7m displayed activity against the latter. Derivative 7a was active against all cell lines. It is believed that eugenol derivatives bearing triazole functionalities may represent a scaffold to be explored toward the development of new agents against cancer. <![CDATA[REACTIVE MOLECULAR DYNAMICS SIMULATION AND CHEMICAL KINETIC EVALUATION OF COMBUSTION OF TRIETHYLALUMINIUM (TEA)]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500507&lng=es&nrm=iso&tlng=es The combustion process of triethylaluminum is investigated by means of reactive molecular dynamics simulations using the ReaxFF force field. The behavior of the system in five different temperatures ranging from 2000-4000 K was evaluated. As a pyrophoric material, TEA reacts also with water, generating gaseous hydrogen, whose content increases with the system temperature. Rapid water formation and O2 depletion were observed and, using Arrhenius equation, the preexponential factor and activation energy were found to be 9.67E+09 s-1 and 1.242 kJ mol-1, respectively. The results obtained are in accordance to the expected for pyrophoric materials and the simulation in question can help elucidating and analyzing the complex reaction mechanism of TEA combustion. <![CDATA[EVALUATION OF ADSORPTION AND ELECTROCHEMICAL STUDY OF SOLAR CELLS PRODUCED WITH TiO<sub>2</sub> AND DYE EXTRACTED FROM <em>HIBISCUS</em>]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500512&lng=es&nrm=iso&tlng=es Dye-sensitized solar cells using natural dyes have lower cost when compared to ruthenium-based dyes. This paper aims to evaluate, electrochemically, solar cells composed of TiO2 with dye extracted from the Hibiscus(var. Sabdariffa) and propose an adsorption model capable of predicting the adsorption mechanism of the dye on the semiconductor surface. The characterization techniques used were: Fourier Transform Infrared Spectroscopy, UV-VIS Spectroscopy, Measurement of the Open Circuit Potential, Photocronoamperometry, and Current Density Curves vs. Potential. The infrared spectroscopy confirmed there was adsorption of dye on the TiO2 surface. The adsorption isotherm with the better value of linear coefficient (R= 0.9874) was the Langmuir isotherm. The electrochemical techniques showed that the best cell prepared from a solution with a concentration of 5.27 mg L-1 of the natural dye, had an Eca= 516 mV, j = 0.15 mA cm-2 and an energy efficiency (η) of 0.15%. <![CDATA[YTTRIUM ALUMINUM OXIDE DOPED WITH Yb<sup>3+</sup>AND Er<sup>3+</sup> INCORPORATED INTO POLYAMIDE MEMBRANE]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500519&lng=es&nrm=iso&tlng=es Lanthanide ions have special light emission, which can occur through descending and ascending energy conversion. Ascending energy conversion is especially interesting for bioapplications because excitation in the infrared region does not excite biomolecules and therefore does not interfere in detection, not to mention that it penetrates deeper in the skin. Here, we synthesized yttrium and aluminum oxide doped with Yb3+and Er3+ions via the non-hydrolytic sol-gel methodology. The doped matrix was incorporated and dispersed over a polyamide membrane obtained by Additive Manufacturing. X-ray diffraction revealed that a mixture of yttrium aluminum monoclinic and garnet phases emerged. Upon excitation at 980 nm in the Yb3+ion, the Er3+ presented more intense emission as a function of the laser power, which favored red emission. The intensities of the bands corresponding to the 4S3/2 → 4I15/2 (563 nm) and 5F9/2 → 4I15/2 (660 nm) transitions involved the absorption of two photons. The oxide incorporated into the polyamide membrane presented the same behavior. After coating with polyetherimide, the latter system was resistant to 5.1 W laser, which paves the way for new applications. <![CDATA[SELF-ASSEMBLY AND HOST-GUEST BEHAVIORS OF A SUPRAMOLECULAR HELICATE FE<sup>II</sup> <sub>2</sub>L<sub>3</sub>]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500528&lng=es&nrm=iso&tlng=es A novel helicate complex [FeII2L3]4+ resulted from subcomponent self-assembly of a C3-symmetric triamine, 2-formylpyridine and octahedral iron(II) in CH3CN, which was confirmed by ESI-MS measurement. After the addition of selected planar aromatic molecules in CD3CN solution, shifts of 1H NMR signals of the helicate were investigated. The results revealed that the size, functional group and symmetry of guest molecules remarkably influence the interaction patterns. <![CDATA[HOW TO OBTAIN GOLD NANOPARTICLES FROM LEMON JUICE?]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500533&lng=es&nrm=iso&tlng=es This article refers about a green method for the preparation of gold nanoparticles using juice from four types of lemon (Tahiti, Key lime, Sicilian and Rangpur). The approach is based on a classic synthesis of nanoparticles using sodium citrate as reducing agent, since all these lemon varieties have citric acid in their compositions. Several characterization techniques demonstrated the efficacy of the method for obtaining red colloidal solutions (nanoparticles in the order of 5-25 nm). The importance of this attempt to make environmentally friendly synthesis of gold nanoparticles is linked to the several applications of these nanomaterials, the most important being biomedicine, catalysis, electronics, biochemical sensing and imaging. <![CDATA[NEW ALKYL PHENOLS AND FATTY ACID PROFILE FROM OILS OF PULPED <em>Spondias mombin</em> L. SEED WASTES]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500540&lng=es&nrm=iso&tlng=es Spondias mombin L. is a Brazilian tree belonging to the family Anacardiaceae and popularly known as “cajá”, the genus is well known by the various exotic fruit species such as “siriguela” (S. purpurea), “umbu” (S. tuberosa) and “umbu-cajá” (S. bahiensis). It presents commercial importance to the locals especially due the small juice fruit industries and the seeds are often discarded as waste after pulping. Despite the regional importance, even today there is little information on the chemical composition of these fruits. Thus, the dichloromethane extract of the waste seeds of S. mombin was subjected to different chromatographic fractionation allowing the isolation of a main triglyceride identified as 1,3-dioleoyl-2-linoleoyl glycerol, two new alkyl phenols named 1-hydroxyl-3-[(Z)-10’-octadecenyl]-benzene and 1-hydroxyl-3-[(Z)-10’-docosenyl] benzene, and a mixture of phytosteroids. The seed’s fatty acid profile and the cytotoxicity of the oils and isolated compounds were also determinated employing BST. The alkenylphenol mixture present some toxicity (CL50 215,4 µg mL-1) in this test. <![CDATA[PREPARATION, PHYSICOCHEMICAL CHARACTERIZATION AND CONTROLLED RELEASE OF GALACTOMANNAN MICROPARTICLES CONTAINING ALLANTOIN]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500544&lng=es&nrm=iso&tlng=es In this work, the allantoin was encapsulated with galactomannan extruded from Delonyx regia, by the spray drying technique. The microparticles obtained were structurally characterized by infrared spectroscopy (IR), thermal analysis, scanning electron microscopy (SEM) and the controlled release profile was evaluated. The results of IR suggested the formation of the polymeric wall of the microcapsules and SEM revealed spherical particles with an average size range of 2.84 ± 0.41 µm. X-ray diffraction showed the loss of crystallinity of the active after encapsulation and differential explanatory calorimetry exhibited the loss of its peak melt. The encapsulation efficiency for the microparticles was approximately 84% for the different environmental conditions. The coating of allantoin with the biopolymer promoted a gradual release of the drug over a period of 6 hours and these results are in accordance with the Brazilian Pharmacopoeia. The set of results obtained in this work is relevant and accredits the system developed as a possible alternative for the formation of encapsulated natural drugs destined to possible treatments of cutaneous cellular regeneration. <![CDATA[2,3-UNSATURATED <em>O</em>-GLYCOSIDES: APPLICATIONS, FERRIER REARRANGEMENT AND REACTIONS]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500550&lng=es&nrm=iso&tlng=es In carbohydrate chemistry, the O-glycoside is an organic molecule in which sugar is bound to another functional group via a glycosidic bond. In the last few years, considerable progress has been made in the synthesis and applications of O-glycosides. Despite their challenging chemistry, due to their versatility, O-glycosides play a pivotal role the development of the chemistry of novel materials and bioactive molecules. This review summarizes recent developments, in the last twenty years, about the Ferrier rearrangement reaction involving synthesis, mechanistic proposal and application of 2,3-unsaturated O-glycosides. <![CDATA[BIOGENIC SYNTHESIS OF IMPORTANT ENVIRONMENTAL MINERALS: MAGNESIUM PHOSPHATE COMPOUNDS AND PERSPECTIVES]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500567&lng=es&nrm=iso&tlng=es The ecological processes in which metabolites with industrial or medical applications are produced are of great importance. Magnesium plays many important roles in environmental and medical applications. Phosphorus is obtained by mining. It is estimated to have a very limited half-life and expected to be depleted as a resource in 100 years. Its recovery by mining and subsequent marketing as phosphate has important environmental implications. These processes are part of an important recovery technology. Bacteria have contributed to the formation of minerals since the advent of life on Earth. Bacterial and/or fungal biomineralizations play a critical role in biogeochemical cycles. These processes have important technological and environmental applications. In many past publications dealing with bacterial and fungal recovery of phosphates as insoluble products, magnesium played an important role. This is a review of recent progress in the microbial recovery of biogenic magnesium phosphate compounds, their importance, and their roles in treatment of several human diseases. <![CDATA[ENVIRONMENTAL FRIENDLY METHODS FOR REGIOSELECTIVE IODINATION OF THE 3,7,3’,4’-TETRAMETHOXY-QUERCETIN]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500577&lng=es&nrm=iso&tlng=es Halogenated compounds are valuable substrates for the field of organic synthesis and more specifically as reagents for coupling reactions. Environmental friendly procedures for regioselective iodination is the aim of this study, using four different methods previously described in the literature, that embrace green chemistry concepts, to obtain the 6- and 8-iodo-isomers of 3,7,3’,4’-tetramethoxy-quercetin. As traditional column chromatography does not resolve the mixture of isomers, the regioselectivity for iodination was quantified by use of HPLC. The use of a protic polar solvent improves selectivity for formation of the 8-iodo- isomers (tipically, I2, LiOH, MeOH, 3 h, 54% yield), while the use of a polar aprotic solvent or in the absence of a solvent favors formation of the 6-iodo- isomer (typically, I2, K2CO3, without solvent, 5 min, 60% yield). Twenty-one reaction procedures were investigated, five of which selectively gave the 6,8-diiodo-derivative. To the best of our knowledge, selective methods for the synthesis of this compound have not been described in the literature. The best condition was the neat reaction with N-iodo-succinimide with 68% yield in just a few minutes. All product yields are after column chromatography using silica gel, and characterized by usual methods, including 1H-NMR, 13C-NMR, IR and MS-TOF. <![CDATA[ACIDIC LEACHING OF Li-ION BATTERIES]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500581&lng=es&nrm=iso&tlng=es This paper describes a route for recovering cobalt and lithium from spent Li-ion batteries via acidic leaching. Sulfuric, hydrochloric, hydrofluoric and formic acids were used as leachants. Hydrogen peroxide was added as reductant, except for formic acid since it is itself a reductant. Experiments were run at 25-40 ºC for 1-3 h. Under the best optimal conditions, the leaching efficiency order was HCl ≈ HF &gt; H2SO4 &gt; HCOOH. Over 90 wt.% of cobalt and lithium were leached by the inorganic acids. The insoluble matter corresponds mainly to the carbon from the cathode. Co(II) was extracted with D2EHPA 16 vol.% diluted in n-hexane at pH ~5 (A/O ratio 1/1 vol/vol, one stage, 25 ºC). Co(II) striping was possible using a dilute leachant (1-2 mol L-1 HCl or H2SO4, 4-5 mol L-1 HF or HCOOH). Lithium was isolated from the raffinate by precipitation as carbonate or phosphate. <![CDATA[EXPLAINING THE GEOMETRY OF SIMPLE MOLECULES USING MOLECULAR ORBITAL ENERGY-LEVEL DIAGRAMS BUILT BY USING SYMMETRY PRINCIPLES]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500587&lng=es&nrm=iso&tlng=es The built of qualitative energy-level molecular diagrams for different geometries of simple molecules allow to explain the preferred geometry. The diagrams are built using simple symmetry principles and explain, on basis of the number of nonbonding electrons, for example, why the molecule of water is bent and not linear and ammonia is pyramidal and not planar. This simple energy principle does not need to consider the Valence Shell Electron-Pair Repulsion theory (VSEPR theory) neither hybrid orbitals to explain the geometry of simple molecules. This discussion is more appropriate to inorganic chemistry courses where symmetry is a common topic. <![CDATA[A THERMODINAMIC CORROSION STUDY OF CARBON STEELS IN HYDROGEN SULFIDE - EXPLORING CHEMICAL EQUILIBRIUM CONCEPTS]]> http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000500594&lng=es&nrm=iso&tlng=es This study addresses an inherent problem to the oil and natural gas exploration and production industry, the corrosion of pipes and tanks by H2S. H2S with water emulsified in the oil or H2S with the water vapor mixed in the gas, they make the acid environment leading to corrosion. This is commonly manifested by the formation of insoluble sulfides on the surface of the carbon steels destined for this purpose. The evolution of the corrosion process depends on the composition and physicochemical characteristics of sulfide film. In this context, we intend to interpret the conditions of formation and precipitation of iron sulfides as a function of pH, using concepts of chemical equilibrium, electrode potential and electrochemical cell that are part of the subjects of chemistry.