Biblioteca Digital

Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for die isolated pterin by quantum mechanical second-order Moller-Plesset Perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier, The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case...

Cinza leve de carvão, resíduo gerado em usina termelétrica, foi usada para sintetizar zeólita por meio de tratamento hidrotérmico com solução de NaOH. A cinza leve (CL-2) e a zeólita sintética (ZM-2) que foi predominantemente identificada como hidroxi-sodalita foram utilizadas como adsorventes dos corantes aniônicos índigo carmina (IC) e reativo laranja 16 (RL16) de soluções aquosas. Nos processos de adsorção, os efeitos de tempo de contato, concentração inicial de corantes, pH, massa de adsorventes e temperatura foram avaliados. O estudo cinético de adsorção demonstrou que os resultados apresentaram melhor ajuste ao modelo de pseudo-segunda ordem e que adsorção de superfície e difusão intrapartícula participaram no mecanismo de adsorção. Os parâmetros termodinâmicos demonstraram que a adsorção foi espontânea em todos os processos de adsorção. Os processos de adsorção foram de natureza endotérmica para todos os sistemas, com exceção do sistema IC/ZM-2, em que foi exotérmico. Os dados de entropia mostraram a ocorrência do aumento da desordem na interface sólido/solução durante a adsorção em todos os sistemas, exceto novamente no IC/ZM-2, no qual se verificou a diminuição da desordem na interface. As isotermas de adsorção ajustaram-se à equação linear de Langmuir. As capacidades máximas de adsorção foram 1...

Os aços inoxidáveis austeníticos são os mais utilizados em situações onde é indispensável resistência à corrosão e excelentes propriedades mecânicas. O níquel costuma ser o principal elemento de liga utilizado na estabilização da fase austenítica, e nos últimos anos seu valor, de acordo com a London Metal Exchange, sofreu variações abruptas de preço, desestabilizando o mercado do aço inoxidável. Nesse contexto os aços da série 200, também conhecidos como aços Cr-Mn-Ni, que substituem parte do níquel por manganês para manter a estabilidade da fase austenítica, tiveram sua produção incrementada. O objetivo do presente trabalho foi comparar a resistência à corrosão por pite de dois aços inoxidáveis austeníticos, aço 17Cr-6Mn-5Ni (designado como aço 298, não normalizado) e o aço UNS S30403. Para tanto, foram estudadas duas variáveis: o efeito da temperatura de solubilização e da composição química do eletrólito, a qual foi constituída por soluções aquosas com teor fixo de 0,6M NaCl e adições progressivas de Na2SO4 visando verificar o efeito inibidor do íon sulfato nos diferentes aços com os diferentes tratamentos de solubilização (1010°C, 1040°C, 1070°C e 1100°C). A corrosão por pite foi determinada através de ensaios de polarização potenciodinâmica cíclica e os resultados obtidos foram discutidos através das variações microestruturais encontradas. Foram empregadas técnicas de microscopia ótica e eletrônica de varredura...

Foi estudada a cristalização de suspensões aquosas de esferas de poliestireno (850Å, 910Å e 1090Å de diâmetro) no limite de baixas concentrações -1011 a 1013 esferas / cm3. A dependência do parâmetro de rede com a concentração original (n) da suspensão aquosa apresenta uma transição de fase da fase bcc para fcc, conforme já foi observada por outros autores. Observamos também que durante a cristalização a concentração de esferas no cristal Ra sistematicamente maior do que na solução original, portanto a água estaria sendo expelida para a solução durante a cristalização. Baseado nestas observações nós propomos um modelo de cristalização onde os cristalites (concentração n1) estão em equilíbrio termodinâmico com uma solução com concentração n2 (n1> n > n2), dando para cada concentração inicial um diferente parâmetro de rede determinado por este equilíbrio. Nossos resultados mostraram que o coeficiente de expulsão da água durante a cristalização é dependente do raio da esfera. Para realizar as medidas de parâmetro de rede nós adaptamos para as nossas condições particulares o método de Debye-Scherrer usado em difração de raios-X por cristais. O equivalente à fonte de raios-X era um laser de Argônio com comprimentos de onda variáveis. Diversas experiências novas são sugeridas.; The crystallization of aqueous suspensions of polystyrene spheres 850Å...

SnO2 supported membranes, presenting 3.0 nm average pore size, have been produced by sol casting on alumina tubular substrate using aqueous colloidal suspensions prepared by sol-gel route. The selectivity and flux throughout SnO2 membrane were analyzed by permeation experiments, using a laboratory tangential filtration pilot equipped with a monotubular membrane. To evaluate the effect of the surface charge at the membrane-solution interface, aqueous salt solutions (NaCl, Na2SO4, CaCl, and CaSO4) of different ionic strength have been filtered and the results correlated with the values of zeta potential measured at several pH. The results show that the retention coefficient is dependent on the electrolyte present in aqueous solution decreasing as: (dication, monoanion) > (monocation, monoanion) approximate to (monocation, dianion) > (dication, dianion). The surface charge and the cation adsorption capacity play a determinant role in these selectivity sequences. (C) 2001 Elsevier B.V. B.V. All rights reserved.

The aim of the present work is to characterize the vegetal raw material of the Calycophyllum spruceanum (Benth.) Hook. f. ex K. Schum., Rubiaceae, known as "mulateiro", and to evaluate the influence of extractive parameters for attainment of standardized aqueous extractive solutions. The physical-chemical characterization of the samples was performed using pharmacopoeic and not pharmacopoeic methodologies. A 2³ factorial design was used to evaluate the influence of extraction techniques (infusion/decoction), drug: solvent ratio (2.5 and 7.5%), and extraction time (5 and 15 min) on the total tannin content of aqueous extractive solutions from C. spruceanum. The extractive solution that showed higher total tannin and dry residue content had their physical-chemical characteristics determined. The results suggest that an aqueous extractive solution from rinds of C. spruceanum barks with higher tanning yield (9.9 g%), must be standardized using decoction as extraction methodology, with 2.5% of vegetal drug for an extraction time of 15 min. The results of the physical-chemical characterization suggest that environmental factors modify the properties of this species and, therefore, they can influence the quality and security of a product derived from this medicinal plant.

It is studied the extraction of cadmium(II) ions from acidic aqueous solutions using a stirred transfer cell-type emulsion liquid membrane (ELM) prepared by dissolving in kerosene, with D2EHPA (an alkylphosphoric acid) as mobile carrier and Span-80 as surfactant. The ELM allowed efficient metal transport from the feed solution to the stripping liquor in experiments carried out at 25 ºC. The significant variables on cadmium transport through the membrane were extractant concentration and metal content in the feed metal-donor solution. Concentration of HCl as stripping agent affected only the initial metal extraction rate but not the extraction extent. The surfactant content used in this study stabilized the membrane adequately, but the use of a higher content produced a smaller initial extraction rate due to higher interfacial resistance. The experimental results suggest the possibility of recovering or removing valuable or toxic metals from dilute aqueous solution in an extractor based on emulsified liquid membranes.

Structural and morphological characteristics of the electrodeposited Cr and Ni-Cr-P coatings and their corresponding electrochemical behaviors in chloride aqueous medium were investigated here. All coatings were electrodeposited on copper. Cr coatings were obtained from an industrial plating solution and amorphous Ni-Cr-P coatings were successfully obtained at 60ºC in the range of 100 to 400 mA cm-2, using a plating solution at pH 2 containing 40 g L-1 NiCl2.6H2O; 102 g L-1 CrCl3; 14 g L-1 NaPH2O2; 30 g L-1 H3BO3; 15 g L-1 NaBr; 50 g L-1 NH4Cl, 80 g L-1 Na3C6H5O7 .2H2O and 40 mL L-1 HCOOH. The coatings were obtained using constant charges of 500 and 1600 Coulombs. The characterization of the coatings was carried out by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC) and Energy Dispersive X-ray Analysis (EDX) techniques. The electrochemical behavior of both coatings was evaluated by potentiodynamic polarization curves, at room temperature, in 0.1 mol L-1 NaCl aqueous solution. It was not observed cracks on the electrodeposited Ni-Cr-P coatings and the surface morphology was characterized by the presence of spherical nodules. The crystallization of these coatings occurred at 325 °C with the formation of Ni and Ni3P phases. All the annealed Cr coatings showed cracked surfaces. The presence of cracks impairs the mechanical and corrosion resistance properties of Cr coatings. The hardness of the Ni-Cr-P was increased with the increase of the annealing temperature. Spherical noodles were absent in the surface of as-annealed Ni-Cr-P coating which it was associated with the diffusion of Cr to the surface and cracks were not observed in any annealing temperature. Among the various electrodeposited Ni-Cr-P coatings studied here...

The ozonolysis of ethinylestradiol (1), a synthetic steroidal estrogen, in an aqueous-methanolic solution was investigated. HPLC-UV analyses revealed that 1 was completely consumed after a 20 min reaction time either at pH 5 or 8. ESI(-)-MS (electrospray ionization mass spectrometry in the negative ion mode) monitoring also revealed the continuous consumption of 1 (detected as [1 – H]- of m/z 295) concomitantly with the emergence of oxidation products. Chemical structures were proposed for these products based on the data of MS and MS/MS (the m/z values and fragmentation profiles of the anionic specie, respectively). These data, in conjunction with the well-established knowledge about the reactivity of organic molecules toward ozone in aqueous solution, were evaluated and an unprecedented reaction route for the ozonation of 1 could thus be suggested. Hence, the first step in this reaction sequence was ascribed to involve a 1,3-dipolar cycloaddition of ozone at the phenolic ring of 1 yielding the di-hydroxylated product 2 (detected as [2 – H]- of m/z 311). The loss of acetylene as the unique dissociation channel for [2 – H]- thus confirmed that such hydroxylation occurred at the phenolic ring rather than the acetylenic moiety of 1. Subsequent oxidations were proposed to be the origin of a number of other products...

The ability of nano-silversol-coated activated carbon (NSSCAC) to adsorb Pb2+ from aqueous solution has been investigated through batch experiments. The adsorption of lead onto NSSCAC has been found to depend on adsorbent dose, initial concentration and contact time. The experiments were carried out at natural solution pH. Equilibrium data fitted well with the Langmuir model and Freundlich model with a maximum adsorption capacity of 23.81 mg of Pb/g of NSSCAC. The experiments showed that the highest removal rate was 92.42% for Pb2+ under optimal conditions. The sorption of Pb2+ on NSSCAC was rapid during the first 30 min and the equilibrium attained within 60 min. The kinetic processes of Pb2+ adsorption on NSSCAC were described by applying pseudo-first-order and pseudo-second-order kinetic models. The kinetic data for the adsorption process obeyed a pseudo-second-order kinetic model, suggesting that the adsorption process is chemisorption. The NSSCAC investigated in this study showed good potential for the removal of Pb2+ from aqueous solution.

The adsorption behavior of rice husk for cadmium ions from aqueous solutions has been investigated as a function of appropriate equilibrium time, adsorbent dose, temperature, adsorbate concentrations and pH in a batch system. Studies showed that the pH of aqueous solutions affected cadmium removal with the result that removal efficiency increased with increasing solution pH. The maximum adsorption was 98.65% at solution pH 6, contact time 60 min and initial concentration of 25 mg/L. The experimental data were analysed by the Langmuir, Freundlich and Temkin models of adsorption. The characteristic parameters for each isotherm and related correlation coefficients have been determined.  Thermodynamic parameters such as,  and have also been evaluated and it has been found that the sorption process was feasible, spontaneous and exothermic in nature. The kinetics of the sorption were analysed using the pseudo-first order and pseudo-second order kinetic models. Kinetic parameters, rate constants, equilibrium sorption capacities and related correlation coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption of cadmium could be described by the pseudo-second order equation...

A water-soluble triacetic acid cryptophane-A derivative (TAAC) was synthesized and determined by isothermal titration calorimetry (ITC) and fluorescence quenching assay to have a xenon association constant of 33,000 M−1 at 293 K, which is the largest value measured for any host molecule to date. Fluorescence lifetime measurements of TAAC in the presence of varying amounts of xenon indicated static quenching by the encapsulated xenon and the presence of a second non-xenon-binding conformer in solution. Acid-base titrations and aqueous NMR spectroscopy of TAAC and a previously synthesized tri-(triazole propionic acid) cryptophane-A derivative (TTPC) showed how solvation of the carboxylate anions can affect the aqueous behavior of the large, nonpolar cryptophane. Specifically, whereas only the crown-crown (CC) conformer of TTPC was observed, a crown-saddle (CS) conformer of TAAC was also detected in aqueous solution.

Single crystal ZnO nanotube arrays were synthesized at low temperature in an aqueous solution containing zinc nitrate and hexamethylenetetramine. It was found that the pH value of the reaction solution played an important role in mediating the growth of ZnO nanostructures. A change in the growth temperature might change the pH value of the solution and bring about the structure conversion of ZnO from nanorods to nanotubes. It was proposed that the ZnO nanorods were initially formed while the reaction solution was at a relatively high temperature (~90 °C) and therefore enriched with colloidal Zn(OH)2, which allowed a fast growth of ZnO nanocrystals along the [001] orientation to form nanorods. A decrease in the reaction temperature yielded a supersaturated solution, resulting in an increase in the concentration of OH− ions as well as the pH value of the solution. Colloidal Zn(OH)2 in the supersaturated solution trended to precipitate. However, because of a slow diffusion process in view of the low temperature and low concentration of the colloidal Zn(OH)2, the growth of the (001) plane of ZnO nanorods was limited and only occurred at the edge of the nanorods, eventually leading to the formation of a nanotube shape. In addition, it was demonstrated that the pH might impact the surface energy difference between the polar and non-polar faces of the ZnO crystal. Such a surface energy difference became small at high pH and hereby the prioritized growth of ZnO crystal along the [001] orientation was suppressed...

Human defensin 5 (HD5) is a 32-residue host-defense peptide expressed in the gastrointestinal, reproductive, and urinary tracts that has antimicrobial activity. It exhibits six cysteine residues that are regiospecifically oxidized to form three disulfide bonds (Cys3—Cys31, Cys5—Cys20, and Cys10—Cys30) in the oxidized form (HD5ox). To probe the solution structure and oligomerization properties of HD5ox, and select mutant peptides lacking one or more disulfide bonds, NMR solution studies and analytical ultracentrifugation experiments are reported in addition to in vitro peptide stability assays. The NMR solution structure of HD5ox, solved at pH 4 in 90:10 H2O/D2O, is presented (PDB: 2LXZ). Relaxation T1/T2 measurements and the rotational correlation time (Tc) estimated from a [15N,1H]-TRACT experiment demonstrate that HD5ox is dimeric under these experimental conditions. Exchange broadening of the Hα signals in the NMR spectra suggests that residues 19-21 (Val19-Cys20-Glu21) contribute to the dimer interface in solution. Exchange broadening is also observed for residues 7-14 comprising the loop. Sedimentation velocity and equilibrium studies conducted in buffered aqueous solution reveal that the oligomerization state of HD5ox is pH-dependent. Sedimentation coefficients of ca. 1.8 S and a molecular weight of 14...

Entre los productos que se pueden obtener de la colmena se encuentran la cera, la miel, la jalea real y el prop??leo. Este ??ltimo es una mezcla de composici??n qu??mica compleja que contiene b??lsamos, aceites et??reos, polen, vitaminas, algunos minerales y prote??nas, sustancias que le confieren una variedad de propiedades biol??gicas de gran inter??s para fines terap??uticos. Por esta raz??n en el presente estudio se obtuvieron y caracterizaron extractos etan??licos y acuosos de prop??leos de diferentes localidades del estado de Campeche, M??xico, probando posteriormente su efectividad antimicrobiana sobre las bacterias Staphylococcus aureus, Salmonella typhi, Pseudomonas aeruginosa y Streptococcus pyogenes. Los extractos presentaron colores que variaron del ??mbar claro al caf?? oscuro, encontr??ndose un rendimiento en s??lidos solubles totales superior en los etan??licos que en los acuosos. Se identificaron como metabolitos: lactonas, saponinas, fenoles, triterpenos, taninos, alcaloides, flavonoides, sustancias aminadas y leucoantocianidinas, estas ??ltimas s??lo en los extractos acuosos. La efectividad antimicrobiana de los extractos depende del solvente empleado, la procedencia del prop??leo y de la especie bacteriana evaluada...

The lithiated nickel–cobalt oxide LiNi0.5Co0.5O2 used as cathode material was grown at low-temperature using different aqueous solution methods. The wet chemistry involved the mixture of metal salts (acetates or nitrates) with various carboxylic acid-based aqueous solutions. Physicochemical and electrochemical properties of LiNi0.5Co0.5O2 products calcined at 400–600°C were extensively investigated. The four methods used involved complexing agents such as either citric, oxalic, aminoacetic (glycine), or succinic acid in aqueous medium which functioned as a fuel, decomposed the metal complexes at low temperature, and yielded the free impurity LiNi0.5Co0.5O2 compounds. Thermal (TG–DTA) analyses and XRD data show that powders grown with a layered structure ( space group) have been obtained at temperatures below 400°C by the acidification reaction of the aqueous solutions. The local structure of synthesized products was characterized by Fourier transform infrared (FTIR) spectroscopy. The electrochemical properties of the synthesized products were evaluated in rechargeable Li cells using a non-aqueous organic electrolyte (1 M LiClO4 in propylene carbonate, PC). The LiNi0.5Co0.5O2 positive electrodes fired at 600°C exhibited good cycling behavior.

La nature des acides dans un environnement aqueux est primordiale dans de nombreux aspects de la chimie et de la biologie. La caractéristique principale d'un acide est sa capacité à transférer un proton vers une molécule d'eau ou vers n'importe quelle base, mais ce procédé n'est pas aussi simple qu'il y paraît. Il peut au contraire être extrêmement complexe et dépendre de manière cruciale de la solvatation des différents intermédiaires de réaction impliqués. Cette thèse décrit les études computationnelles basées sur des simulations de dynamique moléculaire ab initio qui ont pour but d'obtenir une description à l'échelle moléculaire des divers procédés de transferts de proton entre acide et bases dans un milieu aqueux. Pour cela, nous avons étudié une serie de système, dont l'acide hydrofluorique aqueux, l'acide trifluoroacétique aqueux, et un système modèle constitué d'un phénol et d'une entité carboxylate reliés entre eux par une molécule d'eau en solution aqueuse. Deux états intermédiaires ont été identifiés pour le transfert d'un proton depuis un acide. Ces intermédiaires apparaissent stabilisés par un motif local de solvatation via des ponts H. Leurs signatures spectroscopiques ont été caractérisées au moyen de la spectroscopie infrarouge...

The photocatalytic removal of arsenite [As(III)] and monomethylarsonic acid [MMA(V)] was investigated in the presence of UV light (350 nm) and aqueous suspensions of ZnO synthesized by the sol–gel technique. Photocatalytic removal of these potent arsenic compounds results in the effective and rapid mineralization to less toxic inorganic arsenate [As(V)]. The effect of ZnO loading and solution pH on the treatment efficiency of the UV/ZnO photocatalytic process was evaluated. The optimal conditions for the removal of 5 mg L−1 [As(III)] and [MMA(V)] aqueous solutions were observed at catalyst loadings of 0.25 and 0.50 g L−1 with solution pH values of 7 and 8, respectively. Under these conditions, the activity of photocatalyst sol–gel ZnO was compared with TiO2 Degussa P25 and commercial ZnO catalyst. The results demonstrate that the high adsorption capacity of ZnO synthesized by sol–gel gives enhanced removal of arsenic species from water samples, indicating that this catalyst is a promising material for treatment of arsenic contaminated groundwater.

We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation–π interactions between Na+ ions in the aqueous solution and aromatic rings on the graphite surface, promoting the adsorption of water molecules together with cations onto the graphite surface; i.e., Na+ ions as a medium adsorbed to the graphite surface through cation–π interactions on one side while at the same time bonding to water molecules through hydration interaction on the other side at a molecular scale. These findings suggest that actual interactions regarding carbon-based graphitic surfaces including those of graphene, carbon nanotubes, and biochar may be significantly different from existing theory and they provide new insight into the control of surface wettability...

We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation-{\pi} interactions between Na+ ions in the aqueous solution and aromatic rings on the graphite surface, promoting the adsorption of water molecules together with cations onto the graphite surface; i.e., Na+ ions as a medium adsorbed to the graphite surface through cation-{\pi} interactions on one side while at the same time bonding to water molecules through hydration interaction on the other side at a molecular scale. These findings suggest that actual interactions regarding carbon-based graphitic surfaces including those of graphene, carbon nanotubes, and biochar may be significantly different from existing theory and they provide new insight into the control of surface wettability...