Scielo RSS <![CDATA[Química Nova]]> vol. 37 num. 9 lang. en <![CDATA[SciELO Logo]]> <![CDATA[<b>Particulate matter in the indoor environment of museums in the megacity of São Paulo</b>]]> Atmospheric pollutants can have serious impacts on the preservation of São Paulo's tangible cultural heritage. The purpose of this paper is to report the results of a monitoring campaign focussed on particulate matter (PM) that was conducted in three of the most important museums of the São Paulo megacity (Brazil): the Museu de Arqueologia e Etnologia (MAE-USP), the Museu Paulista (MP-USP), and the Pinacoteca do Estado de São Paulo (PE). These museums exhibit indoor PM and black carbon (BC) concentrations consistent with their urban locations and their specific methods for managing the indoor environment. <![CDATA[<b>Preconcentration of copper from natural water samples using ligand-less <i>in situ</i> surfactant-based solid phase extraction prior to FAAS determination</b>]]> In the present work, a simple and rapid ligand-less, in situ, surfactant-based solid phase extraction for the preconcentration of copper in water samples was developed. In this method, a cationic surfactant (n-dodecyltrimethylammonium bromide) was dissolved in an aqueous sample followed by the addition of an appropriate ion-pairing agent (ClO4-). Due to the interaction between the surfactant and ion-pairing agent, solid particles were formed and subsequently used for the adsorption of Cu(OH)2 and CuI. After centrifugation, the sediment was dissolved in 1.0 mL of 1 mol L-1 HNO3 in ethanol and aspirated directly into the flame atomic absorption spectrometer. In order to obtain the optimum conditions, several parameters affecting the performance of the LL-ISS-SPE, including the volumes of DTAB, KClO4, and KI, pH, and potentially interfering ions, were optimized. It was found that KI and phosphate buffer solution (pH = 9) could extract more than 95% of copper ions. The amount of copper ions in the water samples varied from 3.2 to 4.8 ng mL-1, with relative standard deviations of 98.5%-103%. The determination of copper in water samples was linear over a concentration range of 0.5-200.0 ng mL-1. The limit of detection (3Sb/m) was 0.1 ng mL-1 with an enrichment factor of 38.7. The accuracy of the developed method was verified by the determination of copper in two certified reference materials, producing satisfactory results. <![CDATA[<b>Polyurethane networks from pentaerythritol-modified castor oil and lysine polyisocyanates</b>: <b>synthesis, mechanical, and thermal properties and in vitro degradation</b>]]> Biodegradable polyurethanes (PUR) were prepared from polyols derived from castor oil by transesterification of pentaerythritol-modified castor oil and lysine polyisocyanates (LDI and LTI). The polyurethanes obtained were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The mechanical behavior of the polyurethanes was measured by Shore A hardness and tensile testing (stress-strain curves). The biodegradable nature of the material was determined by contact angle, water absorption tests, and in vitro degradation in PBS solution. This study aims to examine the effect of the structure and functionality of diisocyanate on the mechanical properties and in vitro degradation of the material. The results were compared with homologous materials obtained from isophorone diisocyanate (IPDI) used in previous works. The objective was to evaluate candidate materials that can be potentially used in tissue engineering. <![CDATA[<b>Modulating the electronic structure of amino acids</b>: <b>interaction of model lewis acids with anthranilic acid</b>]]> On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form. <![CDATA[<b>Isoquinoline alkaloids and investigation of the antibacterial and antiplasmodial activities of <i>Guatteria citriodora</i> (Annonaceae)</b>]]> Phytochemical investigations of the stem bark, leaves and twigs of Guatteria citriodora resulted in the isolation of eight alkaloids: liriodenine, lysicamine, O-methylmoschatoline, 3-methoxyoxoputerine, palmatine, 3-methoxyguadiscidine, guattescidine and oxoputerine. The structures of the isolated substances were established by extensive spectroscopic techniques (1D and 2D NMR) and mass spectrometry (MS), as well as by comparison with data reported in the literature. The in vitro antimalarial activity of the alkaloidal fractions of the leaves and twigs against Plasmodium falciparum FCR3 showed significant results, with IC50 = 1.07 and 0.33 mg mL-1, respectively. The alkaloidal fraction of the leaves showed moderate activity against Enterococcus faecalis, with IC50 = 125.0 mg mL-1. Antiplasmodial and antibacterial activities are attributed to alkaloidal constituents. <![CDATA[<b>Modification of the conducting polymer polyaniline for enabling cation exchange</b>]]> This article reports the use of polyaniline (PAni), chemically and electrochemically synthesized, for copper removal from aqueous solutions. PAni films were electrodeposited on reticulated vitreous carbon (RVC). In all cases, p-toluenesulfonate anion (PTS-) was used as the dopant to obtain cation exchange properties. RVC/PAni showed no expressive copper removal due to the small amount of polymer in the film. Chemically synthesized PAni-PTS- was obtained in its reduced form (leucoesmeraldine). PAni degraded at neutral pH but remained stable at low pH, showing a very high ion-exchange capacity, which is superior to those observed for commercial resins. <![CDATA[<b>Separation and purification of three stilbenes from the radix of <i>Polygonum cillinerve</i> (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography</b>]]> An effective method for the rapid separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was successfully established. In the present study, a two-phase solvent system composed of chloroform-n-butanol-methanol-water (4:1:4:2, v/v/v/v) was used for HSCCC separation. A one-step separation in 4 h from 150 mg of crude extract produced 26.3 mg of trans-resveratrol-3-O-glucoside, 42.0 mg of pieceid-2"-O-gallate, and 17.9 mg of trans-resveratrol with purities of 99.1%, 97.8%, and 99.4%, respectively, as determined by high-performance liquid chromatography (HPLC). The chemical structures of these compounds were identified by nuclear magnetic resonance (NMR) spectroscopy. <![CDATA[<b>Electrochemical behavior and evaluation of diffusion in vitro of active α</b><b>-tocopherol associated with iontophoresis</b>]]> Iontophoresis is a method of administering substances through the skin, which uses electrical current or potential to promote transdermal delivery. We focused on α-tocopherol (vitamin E), a natural antioxidant able to reduce or block the oxidation reactions induced by free radicals in biological membranes. The aim of this study was to perform electrochemical evaluation and analysis of vertical diffusion of gel + α-tocopherol undergoing iontophoresis. The results showed a reduction in peak current at 0.78 V of α-tocopherol molecules when subjected to iontophoresis, increasing the diffusion and degradation of the system. <![CDATA[<b>Phytochemical study, antioxidant and antibacterial activities of <i>Stemodia maritima</i></b>]]> Stemodinol, a new natural compound, together with known compounds including jaceidin, stemodin, stemodinoside B, isocrenatoside, verbascoside, crenatoside, and isoverbascoside, were isolated from Stemodia maritima Linn. The antioxidant (DPPH method) and antimicrobial activities of stemodin, stemodinoside B, and crenatoside were investigated. Among the components tested, only crenatoside isolated from the roots showed a high antioxidant power. Stemodin and stemodinoside B exhibited antibacterial activities. <![CDATA[<b>Evaluation of aluminum lability in yerba mate infusions by adsorptive cathodic stripping voltammetry</b>]]> Infusions of yerba mate obtained at different stages of industrialization were evaluated to determine the bioavailable fraction of Al. Adsorptive Cathodic Stripping Voltammetry using DASA (complexing agent) was applied to determine the labile fraction of Al at pH 5.0 and pH 8.0 for the total fraction of dissolved Al. The results indicate that on average 60% of Al is complexed with organic compounds, minimizing their bioavailability; however, the labile fraction exceeds by up to 4 times the maximum weekly intake recommended by the World Health Organization. <![CDATA[<b>Chemical study of leaves of <i>Trichilia silvatica</i> Meliaceae</b>]]> From the leaves of a specimen of Trichilia silvatica Meliaceae, eight known compounds were isolated, namely, two pregnanes, 2α,3β,4β-trihydroxypregnan-16-one (1) and 2β,3β,4β-trihydroxypregnan-16-one (2), three diterpenes, cneorubine X (3), kolavelool (4) and kolavenol (5), in addition to γ-tocopherol, 3-O-β-D-glucopyranosyl-β-sitosterol and 3-O-β-D-glucopyranosyl-stigmasterol. This is the first reported occurrence of pregnane 1, diterpenes 3-5 and µ-tocopherol in the genus Trichilia. The structures of the isolated compounds were determined on the basis of their spectral data. <![CDATA[<b>Phytochemical investigation of <i>Wissadula periplocifolia</i> (L.) C. Presl and evaluation of its antibacterial activity</b>]]> A phytochemical study on the aerial parts of Wissadula periplocifolia using chromatographic techniques has led to the isolation of sitosterol (1a), stigmasterol (1b), sitosterol 3-O-β-D-glucopyranoside (2a), stigmasterol 3-O-β-D-glucopyranoside (2b), phaeophytin A (3), 13²-hydroxy-(13²-S)-phaeophytin A (4), phaeophytin B (5), 17³-ethoxyphaeophorbide (6), 3,4-seco-urs-4(23),20(30)-dien-3-oic acid (7), 3-oxo-21β-H-hop-22(29)-ene (8), dammaradienone (9a), and taraxastenone (9b). The isolated compounds were characterised by spectroscopic analysis. A preliminary assay to evaluate the antibacterial activity of W. periplocifolia extracts and fractions showed that the dichloromethane, ethyl acetate, and n-butanol fractions were active against Enterococcus faecalis. <![CDATA[<b>Voltammetric determination of amitriptyline in pharmaceutical formulation with boron-doped diamond electrode exploiting measures in acid medium</b>]]> A simple and reliable voltammetric method is presented for the determination of amitriptyline using a boron-doped diamond electrode in 0.1 mol L-1 sulfuric acid solution as the support electrolyte. Under optimized differential pulse voltammetry conditions (modulation time 5 ms, scan rate 70 mV s-1, and pulse amplitude 120 mV), the electrode provides linear responses to amitriptyline in the concentration range 1.05 to 92.60 µmol L-1 and at a detection limit of 0.52 µmol L-1. The proposed method was successfully applied in pharmaceutical formulations, with results similar to those obtained using UV-vis spectrophotometric method as reference (at 95% confidence level), as recommended by the Brazilian Pharmacopoeia. <![CDATA[<b>Interactions of chitosan/genipin hydrogels during drug delivery</b>: <b>a QSPR approach</b>]]> A hydrogel comprised of chitosan crosslinked using the low-toxicity crosslinker genipin was prepared, and the absorption of glibenclamide by the hydrogel was investigated. Optimized structures and their molecular electrostatic potentials were calculated using the AM1 method, and the results were used to evaluate the molecular interactions between the three compounds. The quantitative structure-property relationship model was also used to estimate the activity of the chemicals on the basis their molecular structures. In addition, theoretical Fourier transform infrared spectra were calculated to analyze the intermolecular interactions in the proposed system. Finally, the hydrophilicity of the hydrogel and its influence on the absorption process were also estimated. <![CDATA[<b>Simultaneous determination of four phenolic compounds in extracts of aerial parts of <i>Ipomoea pes-caprae</i> (L.) R. Br. (Convolvulaceae) by HPLC-UV</b>]]> Among other applications, Ipomoea pes-caprae is popularly used to treat jellyfish stings, supporting the development of a product for dermatological use. Hydroethanolic spray-dried extract was chosen for the further development of phytomedicines, and a stability-indicative HPLC-UV method was developed and validated for the determination of isoquercitrin and isochlorogenic acids A, B and C. The method was developed using a C18 column (250 x 4.6 mm, 5 µm) with an acetonitrile:water mobile phase at pH 3.0 in a gradient run. The four constituents and other unidentified components of the extract were appropriately resolved without interference of degradation products after stress tests (acid, alkali, neutral, oxidant, photolysis). The method showed linearity in the isoquercitrin concentration range from 5.0-50.0 µg mL-1, with adequate precision (RSD% < 2.5% for the intra- and inter-day studies), accuracy (recovery of 100.0 ± 2.0%), and robustness. Both the herbal drug and spray-dried extract of I. pes-caprae were subjected to stability studies in accelerated and long-term conditions over four months. The samples maintained their characteristics and marker contents (< 10% of variation). <![CDATA[<b>Seed-assisted behavior of zeolite crystallization</b>]]> Seed-assisted synthesis of zeolites diminishes crystallization time and enables the industrial use of certain zeolites, which was conventionally unfeasible due to the complexity of synthesis and the cost of organic structure-directing agents. This study reports the primary results of zeolite crystallization in the presence of seeds, which are used as a substitute for organic compounds. <![CDATA[<b>Multivariate curve resolution with alternating least squares</b>: <b>description, operation and aplications</b>]]> Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) is a resolution method that has been efficiently applied in many different fields, such as process analysis, environmental data and, more recently, hyperspectral image analysis. When applied to second order data (or to three-way data) arrays, recovery of the underlying basis vectors in both measurement orders (i.e. signal and concentration orders) from the data matrix can be achieved without ambiguities if the trilinear model constraint is considered during the ALS optimization. This work summarizes different protocols of MCR-ALS application, presenting a case study: near-infrared image spectroscopy. <![CDATA[<b>Effects of surface roughness on properties of passivation of self-assembled organic monolayers</b>]]> Precise surface area is needed for accurate characterization of self-assembled monolayers (SAMs) on metallic surfaces. The aim of this manuscript was to emphasize that miscalculation of surface area is the major source of errors in SAM electrochemical characterization. Limitations are discussed and recommendations given for beginners in analyses of SAM functionalized electrodes. The electrochemical measurements and examples were based on bare gold electrode immobilized with dodecanethiol. The degree of compression of the monolayer properties of formation and reproducibility of the electrochemical response depends on roughness factor, with values closer to the unit being better. <![CDATA[<b>Study of Scott test using spectroscopic techniques</b>: <b>an alternative method for detecting cocaine hydrochloride and its addulterants in street drugs</b>]]> Cocaine is usually seized mixed with a wide variety of adulterants such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these street drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences, producing false-positive results. Here, we describe the use of analytical techniques including attenuated total reflection Fourier transform infrared (ATR-FTIR) and ultraviolet-visible (UV-VIS) spectroscopies to distinguish between cocaine and other adulterants (lidocaine, promethazine, powdered milk and yeast) that yield positive results on the Scott test using the thiocyanate cobalt reagent. A further 13 substances were also analyzed using the Scott test. <![CDATA[<b>Experiment using grains to explore calibration in chemical analyses</b>]]> The conventional curriculum of Analytical Chemistry undergraduate courses emphasizes the introduction of techniques, methods and procedures used for instrumental analysis. All these concepts must be integrated into a sound conceptual framework to allow students to make appropriate decisions. Method calibration is one of the most critical parameters that has to be grasped since most analytical techniques depend on it for quantitative analysis. The conceptual understanding of calibration is not trivial for undergraduate students. External calibration is widely discussed during instrumental analysis courses. However, the understanding of the limitations of external calibration to correct some systematic errors is not directly derived from laboratory examples. The conceptual understanding of other calibration methods (standard addition, matrix matching, and internal standard) is imperative. The aim of this work is to present a simple experiment using grains (beans, corn and chickpeas) to explore different types of calibration methods. <![CDATA[<b>Automatic evaluation and data generation for analytical chemistry instrumental analysis exercises</b>]]> In general, laboratory activities are costly in terms of time, space, and money. As such, the ability to provide realistically simulated laboratory data that enables students to practice data analysis techniques as a complementary activity would be expected to reduce these costs while opening up very interesting possibilities. In the present work, a novel methodology is presented for design of analytical chemistry instrumental analysis exercises that can be automatically personalized for each student and the results evaluated immediately. The proposed system provides each student with a different set of experimental data generated randomly while satisfying a set of constraints, rather than using data obtained from actual laboratory work. This allows the instructor to provide students with a set of practical problems to complement their regular laboratory work along with the corresponding feedback provided by the system's automatic evaluation process. To this end, the Goodle Grading Management System (GMS), an innovative web-based educational tool for automating the collection and assessment of practical exercises for engineering and scientific courses, was developed. The proposed methodology takes full advantage of the Goodle GMS fusion code architecture. The design of a particular exercise is provided ad hoc by the instructor and requires basic Matlab knowledge. The system has been employed with satisfactory results in several university courses. To demonstrate the automatic evaluation process, three exercises are presented in detail. The first exercise involves a linear regression analysis of data and the calculation of the quality parameters of an instrumental analysis method. The second and third exercises address two different comparison tests, a comparison test of the mean and a t-paired test. <![CDATA[<b>Scientific texts written by undergraduate chemistry students</b>: <b>professors' analysis</b>]]> This study aimed to analyze the aspects of scientific language considered by chemistry professors in the evaluation of scientific texts authored by undergraduate chemistry students. Interviews were conducted with four professors who had evaluated reports and scientific articles written by students enrolled in undergraduate chemistry courses. The professors highlighted aspects pertaining to the structure and general organization of scientific texts typically adopted by the scientific community, and mentioned the importance of certain rhetoric elements in scientific language. This study can be an impetus for further investigation into the importance of language in chemistry education. <![CDATA[<b>Development of a flow injection analysis system employng alternative and low-cost materials for didactic purposes</b>]]> This work describes a simple and inexpensive flow injection analysis system in which gravity force provides fluid propulsion while needles for insulin administration or metallic wires act as electrodes for amperometric detection. The proposed system was able to demonstrate the influence of several operational parameters on the transient signals. Moreover, this system was successfully used to evaluate both the stoichiometry of Cu2+-EDTA complex and the effect of pH on the kinetics of the reaction between ferricyanide and ascorbic acid. Therefore, the proposed system can be regarded as an efficient and accessible didactic tool for the teaching of FIA principles. <![CDATA[<b>Inquiry dynamics in the study of perturbations to a state of chemical equilibrium</b>]]> Educational institutions are not being effective, because they do not give individuals what they need to integrate into postmodern society, nor produce citizens that postmodern society needs. Shortcomings include the scientific literacy and cognitive domain levels attained, with an aggravating waning interest in science among pre-university students. We present an inquiry module, an inquiry dynamic, as an education resource for the study of perturbations of a chemical equilibrium state by pre-university or university students of basic chemistry, to contribute to the relevance and popularity of science, potentiation of science literacy and development of cognition. Here we describe an investigation with pre-university students.