Yuji Kimura

Clay–Alcohol–Water Dispersions: Anomalous Viscosity Changes Due to Network Formation of Clay Nanosheets Induced by Alcohol Clustering

Clay-alcohol-water ternary dispersions were compared with alcohol-water binary mixtures in terms of viscosity and optical absorbance. Aqueous clay dispersions to which lower alcohols (ethanol, 1-propanol, 2-propanol, and tert-butanol) were added exhibited significant viscosity anomalies (maxima) when the alcohol content was 30-55 wt %, as well as optical absorbance anomalies (maxima). The maximum viscosity (ηmax) depended strongly on the clay content and varied between 300 and 8000 mPa·s, making it remarkably high compared with the viscosity anomalies (2 mPa·s) observed in alcohol-water binary mixtures. The alcohol content at ηmax decreased as the hydrophobicity of the alcohol increased. The ternary dispersions with viscosity anomalies exhibited thixotropic behaviors. The effects of other hydrophilic solvents (glycols) and other kinds of clays were also clarified. Based on these findings and the average particle size changes, the viscosity anomalies in the ternary dispersions were explained by alcohol-clustering-induced network formation of the clay nanosheets. It was estimated that 0.9, 1.7, and 2.5 H2O molecules per alcohol molecule were required to stabilize the ethanol, 2-propanol, and tert-butanol, respectively, in the clay-alcohol-water dispersions.

Removal of bisphenol A and its derivatives from aqueous medium through laccase-catalyzed treatment enhanced by addition of polyethylene glycol

ABSTRACT In this study, enzymatic removal of bisphenol A (BPA) from the aqueous medium was investigated through the generation of water-insoluble oligomers, and this procedure was applied to removal of bisphenol derivatives. The experimental parameters, such as the temperature, pH value, enzyme concentration, and concentration and molecular weight of polyethylene glycol (PEG), were determined for the laccase-catalyzed treatment of BPA. The optimum conditions were determined to be pH 7.0 and 40°C in the absence of PEG. Water-insoluble oligomers generated under these conditions were readily removed by filtration or centrifugation. The optimum pH value was decreased to 5.0 in the presence of PEG and the laccase dose was reduced to one-fiftieth of that in the absence of PEG. This indicates that the addition of PEG protects the enzymatic activity and prevents capture of laccase molecules in the oligomers. The oligomers generated in the presence of PEG were removed from the aqueous medium by filtration with a membrane filter or by centrifugation. The oligomers were completely filtrated out with a filter paper by decreasing the pH value to 3.0. In addition, several bisphenol derivatives were also treated and subsequently removed by adjusting the laccase dose in the presence of PEG using the above procedure.

Removal of bisphenol derivatives through quinone oxidation by polyphenol oxidase and subsequent quinone adsorption on chitosan in the heterogeneous system.

In this study, the combined use of a biopolymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was systematically investigated for the removal of bisphenol derivatives from aqueous medium. The process parameters, such as the pH value, temperature, and PPO concentration, were estimated to conduct the enzymatic quinone oxidation of bisphenol derivatives by as little enzyme as possible. Bisphenol derivatives effectively underwent PPO-catalysed quinone oxidation without H2O2 unlike other oxidoreductases, such as peroxidase and tyrosinase, and the optimum conditions were determined to be pH 7.0 and 40°C for bisphenol B, bisphenol E, bisphenol O, and bisphenol Z; pH 7.0 and 30°C for bisphenol C and bisphenol F; and pH 8.0 and 40°C for bisphenol T. They were completely removed through adsorption of enzymatically generated quinone derivatives on chitosan beads or chitosan powders. Quinone adsorption on chitosan beads or chitosan powders in the heterogeneous system was found to be a more effective procedure than generation of aggregates in the homogeneous system with chitosan solution. The removal time was shortened by increasing the amount of chitosan beads or decreasing the size of the chitosan powders.

Removal of naphthols and analogues by the combined use of an oxidoreductase polyphenol oxidase and a biopolymer chitosan from aqueous solutions

In this study, the combined use of an amino group-containing polymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was applied to the removal of naphthols and dihydroxynaphthalenes (DHNs) from aqueous solutions. The process parameters, such as the pH value, temperature and enzyme dose, were discussed for PPO-catalysed oxidation of 1-naphthol. The optimum conditions of enzymatic oxidation of 1-naphthol were determined to be pH 8.0 and 40 °C. Under the optimum conditions, PPO-catalysed oxidation of 1-naphthol increased with an increase in the enzyme dose. Quinone derivatives enzymatically generated were chemisorbed on chitosan beads and the initial velocity of PPO-catalysed oxidation increased with an increase in the amount of added chitosan beads. A specific initial velocity of 0.0675 μmol/U·min was obtained in the PPO concentration range below 200 U/cm3 and 1-naphthol was completely removed within 24 h by quinone adsorption on chitosan beads (0.20 cm3/cm3) at a PPO concentration of 100 U/cm3. The removal time was shortened by increasing the enzyme dose or the amount of added chitosan beads. 2-Naphthol was also completely removed at an initial concentration of 0.05 mM or less by prolonging the reaction time, since PPO-catalysed oxidation of 2-naphthol was much slower than that of 1-naphthol. In addition, this procedure was also applied to the removal of DHNs. These results revealed that the procedure constructed in this study was an effective technique to remove naphthols and DHNs from the aqueous medium.

Two-step grafting of 2-hydroxyethyl methacrylate (HEMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) onto a polyethylene plate for enhancement of Cr(VI) ion adsorption

ABSTRACT Polyethylene (PE) plates grafted with a neutral monomer, 2-hydroxyethyl methacrylate (HEMA), and a cationic monomer, 2-(dimethylamino)ethyl methacrylate (DMAEMA), (PE-g-PHEMA)-g-PDMAEMA plates were prepared by the two-step photografting. The Cr(VI) ion adsorption behavior of the (PE-g-PHEMA)-g-PDMAEMA plates was investigated as a function of the amounts of grafted HEMA, amount of grafted DMAEMA, initial pH value, and temperature. The adsorption capacity of the DMAEMA-grafted PE (PE-g-PDMAEMA) and (PE-g-PHEMA)-g-PDMAEMA plates had the maximum value at the initial pH value of 3.0, independent of the temperature. The adsorption capacity of (PE-g-PHEMA)-g-PDMAEMA plates increased with the amount of grafted HEMA (GHEMA) in the first-step grafting. The increase in the water absorptivity of the grafted layers and thereby the increase in the degree of protonation of dimethylamino groups on grafted PDMAEMA chains were found to lead to the increase in the adsorption capacity. This adsorption capacity was higher than or comparable to those of other polymeric adsorbents for Cr(VI) ions. The Cr(VI) ion adsorption behavior on both PE-g-DMAEMA and (PE-g-PHEMA)-g-PDMAEMA plates obeyed the mechanism of the pseudo-second-order kinetic model and was well expressed by Langmuir isotherm. The high values of the Langmuir constant suggest that the adsorption of Cr(VI) ions occurs through an electrostatic interaction between protonated dimethylamino groups on grafted PDMAEMA chains and ions. Cr(VI) ions were successfully desorbed from PE-g-PDMAEMA and (PE-g-PHEMA)-g-PDMAEMA plates in eluents such as NaCl, NaCl containing NaOH, NH4Cl, NH4Cl containing NaOH, and NaOH.