Atrazine transformation using synthetic enzymes prepared by molecular imprinting

Atrazine imprinted synthetic polymers were prepared using a combination of methacrylic acid and 2-sulfoethyl methacrylate that bound and converted atrazine and other 6-chlorotriazine herbicides to less toxic compounds. A chloride at the 6-position of the triazines was converted to a methoxy group by the polymer in a methanol-containing solvent, where the imprinting effects enhanced the catalytic activity. Competitive inhibition of the atrazine methanolysis was observed in the presence of a structurally related binder, ametryn, suggesting that the catalytic reaction proceeded in the binding sites generated by the molecular imprinting process.     

Phospholipid-linked quinones-mediated electron transfer on an electrode modified with lipid bilayers

Phospholipid-linked naphthoquinones separated by spacer methylene groups (C(n)), PE-C(n)-NQ (n=0, 5, 11), were synthesized to investigate the quinone-mediated electron transfers on a glassy carbon (GC) electrode covered with phospholipids membrane. The PE-C(n)-NQ could be incorporated in lipid bilayer composed of phosphatidylcholine and exhibited characteristic absorption spectral change corresponding to their redox state, quinone/hydroquinone. The cyclic voltammogram of PE-C(n)-NQ-containing lipid bilayer modified on a GC electrode indicated a set of waves corresponding to the consecutive two-electron and two-proton transfer reduction of the quinone moiety. The peak currents of PE-C(n)-NQ as a function of temperature showed a sharp break point in the current-temperature behavior, reflecting the gel-fluid phase transition. The shape of the cyclic voltammograms changed with the pH of the buffer solution. Below pH 6 the first step of the reduction of quinone was a monoprotonation of quinone, whereas above pH 10 the first step of the oxidation was a monodeprotonation of hydroquinone. This indicates that reaction sequences of quinone/hydroquinone were different with the change of the pH. These results showed that the PE-C(n)-NQ exhibited electron transfer associated with proton transfer in the lipid membranes, depending on the diffusivity of the redox species in the membrane and pH. Interestingly, less effect of the number of methylene of the spacer group on the peak currents was observed. Comparison of manganese porphyrin-mediated electron transfer that depends on the spacer methylene lengths [M. Nango, T. Hikita, T. Nakano, T. Yamada, M. Nagata, Y. Kurono, T. Ohtsuka, Langmuir 14 (1998) 407] is made.     

Sterilization of health care products by 5 MeV bremsstrahlung (X ray)

Radiation sensitivities of . pumilus and spores were examined to bremsstrahlung of 5 MeV EB and Cobalt -60 γ rays in order to confirm the effects of radiation and dose rate. Biological indicators (SPORTROL, NAmSA, USA) were irradiated with the X ray in the dose rate range of 4.7–47kGy/h. D-value of spores was 1.4–1.5 kGy, and that of was 1.1–1.3 kGy. The D-values of and have very small dose rate dependences to X ray, and the D-values are similar to those of γ ray. Dose distribution by X-ray and γ irradiation was measured for cartons containing 32 unit dialyzers. The D_max./D_min. of the X-ray irradiation (1.2) was smaller than that of γ ray (1.3).     

Pressure-Volume Behavior of PMMA-MMA Coexistence System as Polymerized at High Pressure

The pressure-volume (P-V) isotherms were measured for the poly(methy1 methacrylate) (PMMA)-methyl methacrylate (MMA) coexistence system polymerized by γ-ray irradiation at various pressures. The P-V isotherm of the coexistence system polymerized below 3000 kg/cm² was similar to that of the monomer. The specific volume of the coexistence system polymerized above 3000 kg/cm² hardly changes in the pressure range between 3000 kg/cm² and the polymerization pressure when measurements are made with successively decreasing or successively increasing pressures. The compressibility was of the order of 10^?6 (kg/cm²)^?1 in this pressure range. This indicated that the coexistence system polymerized above 3000 kg/cm² behaves like a solid in this pressure range. Above the polymerization pressure, the compressibility was of the order of 10^?5 (kg/cm²)^?1, indicating that the coexistence system behaves as liquid. We concluded that the solid-like behavior of the coexistence system polymerized above 3000 kg/cm² is caused by a strong interaction between as-polymerized polymer chains and monomer molecules due to propagation through monomer clusters having short-range order. The present results support that MMA is aligned in short-range order at suitable pressure and temperature as reported in the preceding paper.     

Polymerization of trimethylene carbonate in aqueous solutions: Reaction mechanism and characterization

Polymerization of a trimethylene carbonate (TMC) in an aqueous solution was investigated by gel permeation chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance. The polymerization reaction proceeded rapidly in the aqueous solution and high conversion was achieved in a relatively short time. 1,3‐Propanediol (PPD) formed by hydrolysis of TMC was used as the initiator. The TMC oligomer obtained by ring‐opening polymerization had a TMC unit backbone with terminal 3‐hydroxypropyl groups at both chain ends. The oligomer underwent transesterification reaction with elimination of PPD, resulting in a gradual increase in the molecular weight of the product. The molecular weight was affected by the concentration of TMC. The thermal properties of the polymers were investigated by differential scanning calorimetry. Polymers within the molecular weight (M_n) range from 6.0 × 10³ to 2.3 × 10⁴ g/mol crystallized, and endothermic peaks corresponding to the melting temperature were observed. The glass transition temperature increased with the molecular weight of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1485–1492, 2010     

Formation of Pickering emulsion by use of PCM and SiC and application to preparation of hybrid microcapsules with interfacial polycondensation reaction

It was tried to form Pickering emulsion by use of paraffin wax as a phase change material (PCM) and SiC as solid powder and to apply to the preparation of the hybrid microcapsules with the interfacial polycondensation reaction. Pickering emulsion could be formed by stirring PCM and SiC in the continuous water phase. The mean diameter of PCM droplets in the (O/W) emulsion decreased with the added amount of SiC. The SiC weight adhered on the surface of PCM droplets become the maximum in the continuous phase with pH 6.8. The hybrid microcapsules with the shell made of SiC and polyurea resin film could be prepared by using Pickering emulsion. There was a critical adhesion weight of SiC, above which the hybrid microcapsules could not be formed. Thermal conductivity of hybrid microcapsules could be improved as compared with the PCM microcapsules. Copyright © 2015 John Wiley & Sons, Ltd.     

Spray Pyrolysis Preparation of Apatite-Composite Particles for Biological Application

Apatite derived by sol-gel routes through an amorphous state or derived biomimetically is likely to provide chemically and biologically active surfaces. Thus apatite or apatite-composite particles were prepared by spray-pyrolysis of several solutions as they were applicable to medical treatment. Calcium lactate and ammonium dihydrogen phosphate aqueous solutions stabilized with ethylenediaminetetraacetic acid were sprayed ultrasonically and pyrolysed at 600°C to yield amorphous particles of apatite while apatite-ferric oxide composite powders were prepared from the solutions of calcium lactate and ferric nitrate. Solutions of calcium nitrate and titanium ethoxide in 0.5 N HNO₃ were also spray-pyrolysed at 600°C to prepare calcium titanate and titanium oxide particles trapped on a Ti substrate. Apatite could biomimetically be developed on the calcium titanate particles when they were soaked in an acellular simulated body fluid.     

Effects of Phosphorus Substituents on Reactions of α-Alkoxyphosphonium Salts with Nucleophiles

The effects of phosphorus substituents on the reactivity of α-alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α-alkoxyphosphonium salts, prepared from various acetals and tris(o-tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high-yielding nucleophilic substitution reactions of α-alkoxyphosphonium salts. The reactivity of these salts was determined by a balance between steric and electronic factors, respectively, represented by cone angles θ and CO stretching frequencies ν (steric and electronic parameters, respectively). In addition, a novel reaction of α-alkoxyphosphonium salts derived from Ph(3) P with Grignard reagents was observed to take place in the presence of O(2) to afford alcohols in good yields. A radical mechanism is proposed for this process that has gained support from isotope-labeling and radical-inhibition experiments.     

Synthesis of tubular titanate via a self-assembly and self-removal process

Novel morphology titanate tubes were successfully synthesized via a self-assembly and self-removal process. After the product was treated by calcinating and washing, crystalline TiO2 tubes were obtained. In this study, two new concepts are applied to design the synthetic route: (i) titanium glycolate rods obtained from an ethylene glycol-mediated process and titanate sheets synthesized using the hydrothermal process were used as the template and the precursor, respectively, and ii) the template was directly removed in the reaction without posttreatment. Furthermore, a possible mechanism was proposed for the formation of tubular structures.