RESUMO
The capacity of an anaerobic sediment to achieve the simultaneous biodegradation of phenol and carbon tetrachloride (CT) was evaluated, using humic acids (HA) as redox mediator. The presence of HA in sediment incubations increased the rate of biodegradation of phenol and the rate of dehalogenation (2.5-fold) of CT compared to controls lacking HA. Further experiments revealed that the electron-accepting capacity of HA derived from different organic-rich environments was not associated with their reducing capacity to achieve CT dechlorination. The collected kinetic data suggest that the reduction of CT by reduced HA was the rate-limiting step during the simultaneous biodegradation of phenol and CT. To our knowledge, the present study constitutes the first demonstration of the simultaneous biodegradation of two priority pollutants mediated by HA.
Assuntos
Tetracloreto de Carbono/metabolismo , Substâncias Húmicas/análise , Fenol/metabolismo , Anaerobiose , Biodegradação Ambiental , Tetracloreto de Carbono/química , Elétrons , Halogenação , Cinética , Fenol/química , Poluentes do Solo/isolamento & purificação , Fatores de TempoRESUMO
We present a study of crystalline CCl(4) spanning up to 10 orders of magnitude in time at temperatures ranging from 160 K to 190 K using molecular dynamics simulations. The relaxation process is studied using angular self correlation functions. The results show that each of the four nonequivalent molecules of the monoclinic phase have a particular relaxation time. Two of the molecules relax in an exponential way and the two other molecules have a more complex behavior, especially at the lower temperatures. In all cases, the molecular rotations correspond to quick jumps between equivalent tetrahedral equilibrium positions. Most of these rotations are about the C(3) symmetry axes, however at high temperatures, rotations about the C(2) symmetry axes are observed as well. The waiting time between rotations follows a Poisson distribution. The calculated relaxation times show an Arrhenius behavior with different activation energy for different nonequivalent molecules, in line with recently published findings of nuclear quadrupole resonance experiments.
Assuntos
Tetracloreto de Carbono/química , Cristalização , Simulação de Dinâmica Molecular , TemperaturaRESUMO
A new helical dimeric copper(I) complex [Cu(2)(mphenpr)(2)](ClO(4))(2) where mphenpr is 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane has been prepared and characterized by X-ray crystallography and NMR. In the solid state, the metal centers are 6.42 A apart, and the electronic structure has been investigated with use of density functional theory (DFT) calculations. In solution the dimer equilibrates with a monomeric form [Cu(mphenpr)](ClO(4)), and the mechanism of unfolding of the dimer into monomer has been studied. In the presence of CCl(4), formation of the monomer is coupled to the reductive dehalogenation of the halocarbon. The mechanism of this process has been probed by the study of short-lived potential reaction intermediates using fast kinetic pulse radiolysis techniques and comparisons with DFT calculations. The copper(II) product [Cu(mphenpr)Cl](ClO(4)) and an analogue [Cu(mphenpr)](ClO(4))(2) have been isolated and characterized by X-ray crystallography.
Assuntos
Tetracloreto de Carbono/química , Compostos Organometálicos/química , Simulação por Computador , Cristalografia por Raios X , Dimerização , Halogenação , Modelos Químicos , Modelos Moleculares , Compostos Organometálicos/síntese químicaRESUMO
Adsorption isotherms of chlorobenzene, chloroform and carbon tetrachloride vapors on undoped SiO(2), and metal-doped Ag/SiO(2), Cu/SiO(2) and Fe/SiO(2) substrates were measured in the temperature range of 398-593K. These substrates were prepared from a typical sol-gel technique in the presence of metal dopants that rendered an assortment of microporous-mesoporous solids. The relevant characteristic of these materials was the different porosities and micropore to mesopore volume ratios that were displayed; this was due to the effect that the cationic metal valence exerts on the size of the sol-gel globules that compose the porous solid. The texture of these SiO(2) materials was analyzed by X-ray diffraction (XRD), FTIR, and diverse adsorption methods. The pore-size distributions of the adsorbents confirmed the existence of mesopores and supermicropores, while ultramicropores were absent. The Freundlich adsorption model approximately fitted the chlorinated compounds adsorption data on the silica substrates by reason of a heterogeneous energy distribution of adsorption sites. The intensity of the interaction between these organic vapors and the surface of the SiO(2) samples was analyzed through evaluation of the isosteric heat of adsorption and standard adsorption energy; from these last results it was evident that the presence of metal species within the silica structure greatly affected the values of both the amounts adsorbed as well as of the isosteric heats of adsorption.
Assuntos
Tetracloreto de Carbono/química , Clorobenzenos/química , Clorofórmio/química , Metais/química , Adsorção , Algoritmos , Cromatografia Gasosa , Cobre/química , Géis , Ferro/química , Nitrogênio/química , Porosidade , Dióxido de Silício/química , Prata/química , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica , Difração de Raios XRESUMO
A comparative study between the sonolytic, photocatalytic and sonophotocatalytic oxidation processes of aqueous solutions of malachite green was carried out in the presence of carbon tetrachloride, under a low power ultrasonic field (<15 W) and using titanium dioxide as a photocatalyst. The effect of a number of parameters such as ultrasonic intensity, TiO2 crystalline structure and the presence of CCl4 were studied using an inexpensive reactor. Enhanced rates of sonolytic degradation of malachite green in the presence of CCl4 were demonstrated. On the other hand, the simultaneous use of sonolysis and photocatalysis in the presence of CCl4 does not improve the degradation rate of malachite green in comparison with the one obtained using only sonolysis, but it makes possible a faster oxidative degradation of some reaction intermediaries. Finally, in air saturated solutions both processes, the sonolytic and the photocatalytic one, follow a first-order rate law.
Assuntos
Tetracloreto de Carbono/química , Corantes de Rosanilina/química , Catálise , Concentração de Íons de Hidrogênio , Fotoquímica , Iodeto de Potássio/química , Soluções , Espectrofotometria Ultravioleta , Ultrassom , ÁguaRESUMO
The immobilization and properties of the nitric oxide donor trans-[Ru(NO)Cl(cyclam)](PF(6))(2), RuNO, entrapped in a silica matrix by the sol-gel process is reported herein. The entrapped nitrosyl complex was characterized by spectroscopic (UV-vis, infrared (IR), X-ray photoelectron, and (13)C and (29)Si MAS NMR) and electrochemical techniques. The entrapped species exhibit one characteristic absorption band in the UV-vis region of the electronic spectrum at 354 nm and one IR nu(NO) stretching band at 1865 cm(-1), as does the RuNO species in aqueous solution. Our results show that trans-[Ru(NO)Cl(cyclam)](PF(6))(2) can be entrapped in a SiO(2) matrix with preservation of the molecular structure. However, in a SiO(2)/SiNH(2) matrix, the complex undergoes a nucleophilic attack by the amine group at the nitrosonium. Irradiation of the complex, entrapped in the SiO(2) matrix, with light of 334 nm, resulted in NO release. The material was regenerated to its initial nitrosyl form by reaction with nitric oxide.
Assuntos
Géis/química , Espectroscopia de Ressonância Magnética/métodos , Doadores de Óxido Nítrico/farmacologia , Óxido Nítrico/química , Compostos Organometálicos/química , Dióxido de Silício/química , Espectrofotometria Infravermelho/métodos , Aminas/química , Tetracloreto de Carbono/química , Desenho de Fármacos , Eletroquímica/métodos , Luz , Microscopia Eletrônica de Varredura , Doadores de Óxido Nítrico/química , Nitrogênio/química , Rutênio/química , Raios XRESUMO
Conformational preferences and orbital interactions of methyl chloroacetate (1), methyl bromoacetate (2) and methyl iodo-acetate (3) were analyzed using experimental infra-red data, theoretical calculations and NBO analyses. The conformational equilibria of compounds 1-3 can be represented by their cis and gauche rotamers. The gauche form of 1 is stable in the vapour phase and in a non-polar solvent, but the cis is predominant in a polar solvent. For 2 the gauche form is more stable than the cis, in both the vapour and liquid phases, but for compound 3 only the gauche form was observed both in vapour phase as in solution. These conformational preferences were attributed to the orbital interaction between two antibonding orbitals pi(C=O)(*)-->sigma(C-X)(*). This unexpected interaction was possibly due to the high (0.2) electron density on pi(C=O)(*), which results from the interaction between ether oxygen lone pair and pi(C=O)(*).
Assuntos
Acetatos/química , Espectroscopia de Ressonância Magnética/métodos , Carbono/química , Tetracloreto de Carbono/química , Modelos Químicos , Modelos Moleculares , Conformação Molecular , Estrutura Molecular , Solventes , Espectrofotometria/métodos , Espectrofotometria Infravermelho , EstereoisomerismoRESUMO
Two new amphipathy scales elaborated from molecular dynamics data are presented. Their applications contribute for the identification of the hydrophobic or hydrophilic regions in proteins solely from the primary structure. The new amphipathy coefficients (AC) reflect the side chain/solvent molecules configurational energies. A polar (water) and an apolar solvent, CCl4, were used resulting in the two ACwater and ACCCl4 scales. These solvents were chosen to simulate the aqueous phases and the transmembrane ambients of cellular membranes where the membrane proteins act. The new amphipathy scales were compared with some previous scales determined by different methods, which were also compared between them, indicating more than 90% of the correlation coefficients are less than 0.9: the scales are strictly dependent on the methodologies used in their determination. The ACCCl4 scale is related with the size of side chain amino acids while ACwater is related with the hydrophobicity of side chain amino acids. The quality of the scales was confirmed by an example of application where ACwater was able to identify correctly the transmembrane, hydrophobic regions of a membrane protein. These results also indicate that water is an important factor responsible for the tertiary structure of membrane proteins.
Assuntos
Proteínas de Membrana/química , Aminoácidos/química , Tetracloreto de Carbono/química , Interações Hidrofóbicas e Hidrofílicas , Conformação Molecular , Peptídeos/química , Complexo de Proteínas do Centro de Reação Fotossintética/química , Estrutura Secundária de Proteína , Estrutura Terciária de Proteína , Análise de Sequência de Proteína , Solventes/química , Termodinâmica , Água/química , Difração de Raios XRESUMO
The biological activity of radiosensitizers is associated to their electron affinity (EA), which can be divided in two main processes: vertical and adiabatic. In this work, we calculated the EAs of nitrofurans and nitroimidazoles (Fig. 2) using Hartree-Fock (HF) and density functional theory (DFT) methods and evaluated solvent effects (water and carbon tetrachloride) on EAs. For water, we combined the polarized continuum model (PCM) and free energy perturbation (FEP) (finite difference thermodynamic integration, FDTI) methods. For carbon tetrachloride, we used the FDTI method. The values of adiabatic EA obtained are in agreement with experimental data (deviations of 0.013 eV). The vertical EAs were calculated according to Cederbaum's outer valence Green function (OVGF) method. This methodology, which relies on theoretical aspects of free energy calculations on charged molecules in solution, was used to select potential selective radiosensitizers from recently reported compounds and could be helpful in the rational design of new and more selective bioreductive anticancer drugs.
Assuntos
Elétrons , Modelos Químicos , Radiossensibilizantes/química , Tetracloreto de Carbono/química , Eletroquímica , Estrutura Molecular , Nitrofuranos/química , Nitroimidazóis/química , Radiossensibilizantes/farmacologia , Reprodutibilidade dos Testes , Soluções/química , Termodinâmica , Água/químicaRESUMO
Oxidation of Cr(III) during sonication in carbonated aqueous solutions saturated with CCl4 leads to the quantitative formation of Cr(VI) and provides a simple and rapid method for spectrophotometric chromium determination with 1,5-diphenylcarbazide. The key to this method is the production of chlorine radicals when aqueous solution saturated with CCl4 is exposed to ultrasonic waves of 40 kHz. The effects of sonication period, CCl4 solution volume, acidity, and interferences were discussed. The time required for a single determination is lower than 2 min. The relative standard deviation obtained for aqueous solutions with 1 microg of Cr was < 2% (N = 10) and the calculated detection limit (3sigma) was 5 ng of Cr.