Kinetic study of the 2-methyl-3-methoxy-4-phenylbutanoic acid produced by oxidation of microcystin in aqueous solutions

Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.

Photodegradation of 2-naphthol in aqueous solutions in the presence of humic acid and ferric ions

In this work, the photodegradation of the carcinogenic pollutant 2-naphthol in aqueous solution containing Aldrich humic acid (HA) and ferric ions (Fe(III)) under 125 W and 250 W high pressure mercury lamp (HPML, lambda >= 365 nm) irradiation was investigated. The photooxidation efficiencies were dependent on the pH values, light intensities and Fe(III)/HA concentration in the water, with higher efficiency at pHs 3-4, and 50 mu mol l(-1) Fe(III) with 20 mg l(-1) HA under 250 W HPML. The initial rate of photooxidation increases with increasing, the initial concentration of 2-naphthol from 10 mu mol l(-1) to 100 mu mol l(-1), while do not change at 50 and 100 mu mol l(-1). However, higher removal efficiency of 2-naphthol is achieved at its lower initial concentration of 10 mu mol l(-1), and initial rate of photooxidation is 0.193 mu mol l(-1) min(-1). Dissolved oxygen (DO) plays an important role in the system containing Fe(III)-HA complexes in which Fenton and photo-Fenton reactions were enhanced in the environment. Hydroxyl radicals produced in HA solution with or without ferric ions were determined by using benzene as free radical scavenger and phenol as scavenging products proportional to hydroxyl radicals. By using UV-Vis and excited fluorescence spectrum techniques, the main photooxidation products, which have higher absorption in the region of 240-340 nm, were found, and the mechanisms for the oxidative degradation is proposed.

Degradation of 17 alpha-ethinylestradiol in aqueous solution by ozonation

This study investigates the ozonation of 17 alpha-ethinylestradiol (EE2) in aqueous solution. The affecting factors on the degradation of EE2 were studied and described in details, such as initial EE2 concentration, initial pH value and ozone concentration. In addition, some parameters such as pH. electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE2 could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the fort-nation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GUMS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE2 degradation. Then a possible reaction pathway for EE2 degradation involving all intermediates detected is proposed. During the ozonation process EE2 was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore. these organic acids are easily oxidized by ozone into carbon dioxide (CO2). This work shows that ozonation process is promising for the removal of EE2. The results can provide some useful information for the potential treatment of EE2 by ozonation in aqueous solution. (c) 2005 Elsevier B.V. All rights reserved.

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals ((OH)-O-.) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that (OH)-O-. photoproduction increased from 1.80 to 2.74 muM by increasing the HA concentration from 10 to 40 mg L-1 at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of (OH)-O-. in the HA solution with Fe(111) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of (OH)-O-. in HA solution with algae with or without Fe(111) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of (OH)-O-. in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest (OH)-O-. photoproduction at pH 4.0.

Water solubility enhancement of phthalates by cetyltrimethylammonium bromide and beta-cyclodextrin

Water solubility enhancements of six phthalates (five aliphatic phthalates and one phenyl phthalate) by cetyltrimethylammonium bromide (CTAB) and beta-cyclodextrin (beta-CD) were studied at 25 degreesC. The solubilities of these plithalates are remarkably enhanced by CTAB solutions above the critical micelle concentration (cmc). Only marginal enhancement of phthalate solubility was observed in solutions containing CTAB below its cmc and beta-CD at low concentrations (less than 5 mM). The solubility enhancements of the plithalates are proportional to the added amount of CTAB and beta-CD. Partition coefficients of the plithalates between monomeric CTAB surfactant and water (K-MN) and between CTAB micelle and water K-MC) were estimated from the experimental data. The mechanisms of solubility enhancements by CTAB and beta-CD were discussed. A log-linear equation was proposed and evaluated for the solubilization by CTAB below cmc, while the previously proposed linear partitioning model was questioned. The structures of the complexes formed between plithalates and beta-CD were proposed, and the formation constants were estimated. The values of log K-MC, log K-MN, and log Kbeta-CD of the plithalates were found to correlate linearly with the log K-OW of plithalates, with the exception of the solid phenyl phthalate.

Electrolyte electroreflectance spectroscopy studies on the interfacial behavior of the near-surface In0.15Ga0.85As/GaAs quantum well electrode vertical bar non-aqueous electrolyte

Electrolyte electroreflectance spectra of the near-surface strained-layer In0.15Ga0.85As/GaAs double single-quantum-well electrode have been studied at different biases in non-aqueous solutions of ferrocene and acetylferrocene. The optical transitions, the Franz-Keldysh oscillations (FKOs) and the quantum confined Stark effects (QCSE) of In0.15Ga0.85As/GaAs quantum well electrodes are analyzed. Electric field strengths at the In0.15Ga0.85As/GaAs interface are calculated in both solutions by a fast Fourier transform analysis of FKOs. A dip is exhibited in the electric field strength versus bias (from 0 to 1.2 V) curve in ferrocene solution. A model concerning the interfacial tunneling transfer of electrons is used to explain the behavior of the electric field. (C) 2001 Elsevier Science B.V. All rights reserved.

Characterization of CdSe and CdSe/CdS core/shell nanoclusters synthesized in aqueous solution

CdSe nanoclusters overcoated with CdS shell were prepared with macapoacetic acid as stabilizer. The optical properties of CdSe nanoclusters and the influence of CdS shell on the electronic structures of CdSe cores were studied by optical absorption, photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies. Based on PL and PLE results and the theoretical calculation on fine structure of bandedge exciton, a model of formation of excimer within the small clusters was proposed to explain the large Stokes shift of luminescence from absorption edge observed in PL results. (C) 2000 Elsevier Science B.V. All rights reserved.

Interfacial behaviour of a quantum well electrode/electrolyte: EER spectra of an SQW GaAs/AlxGa1-xAs electrode in HQ+BQ non-aqueous electrolyte

The quantum-confined Stark effect and the Franz-Keldysh oscillation of a single quantum well (SQW) GaAs/AlxGa1-xAs electrode were studied in non-aqueous hydroquinone + benzoquinone solution with electrolyte electroreflectance spectroscopy. By investigation of the relation of the quantum-confined Stark effect and the Franz-Keldysh oscillation with applied external bias, the interfacial behaviour of an SQW electrode was analysed. (C) 1997 Elsevier Science S.A.

Corrosion inhibition of carbon steel in tetra-n-butylammonium bromide aqueous solution by benzotriazole and Na3PO4

The corrosion inhibition behavior of benzotriazole, Na3PO4 and their mixture on carbon steel in 20 wt.% (0.628 mol l(-1)) tetra-n-butylammonium bromide aerated aqueous solution was investigated by weight-loss test, potentiodynamic polarization measurement, electrochemical impedance spectroscopy and scanning electron microscope/energy dispersive X-ray techniques. The inhibition action of BTA or SP or inhibitors mixture on the corrosion of carbon steel is mainly due to the inhibition of anodic process of corrosion. The results revealed that inhibitors mixtures have shown synergistic effects at lower concentration of inhibitors. At 2 g l(-1) BTA and 2 g l(-1) SP showed optimum enhanced inhibition compared with their individual effects.

Investigation of Interfacial Tensions for Carbon Dioxide Aqueous Solutions by Perturbed-Chain Statistical Associating Fluid Theory Combined with Density-Gradient Theory

The perturbed-chain statistical associating fluid theory and density-gradient theory are used to construct an equation of state (EOS) applicable for the phase behaviors of carbon dioxide aqueous solutions. With the molecular parameters and influence parameters respectively regressed from bulk properties and surface tensions of pure fluids as input, both the bulk and interfacial properties of carbon dioxide aqueous solutions are satisfactorily correlated by adjusting the binary interaction parameter (k(ij)). Our results show that the constructed EOS is able to describe the interfacial properties of carbon dioxide aqueous solutions in a wide temperature range, and illustrate the influences of temperature, pressure, and densities in each phase on the interfacial properties.

Characterization of CdSe and CdSe/CdS core/shell nanoclusters synthesized in aqueous solution

CdSe nanoclusters overcoated with CdS shell were prepared with macapoacetic acid as stabilizer. The optical properties of CdSe nanoclusters and the influence of CdS shell on the electronic structures of CdSe cores were studied by optical absorption, photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies. Based on PL and PLE results and the theoretical calculation on fine structure of bandedge exciton, a model of formation of excimer within the small clusters was proposed to explain the large Stokes shift of luminescence from absorption edge observed in PL results. (C) 2000 Elsevier Science B.V. All rights reserved.