Enzymatic Synthesis and Polymerization of Cyclic Trimethylene Carbonate Monomer with/without Methyl Substituent

The direct enzymatic synthesis of a cyclic trimethylene carbonate (1,3‐dioxane‐2‐one) monomer with/without a methyl substituent was carried out using dimethyl or diethyl carbonate and 1,3‐diol with the objective of producing aliphatic poly(trimethylene carbonate), a typical biodegradable synthetic plastic. The lipase‐catalyzed condensation of dimethyl or diethyl carbonate with aliphatic 1,3‐diols using immobilized Candida antarctica lipase (lipase CA) in an organic solvent at 70 °C afforded the corresponding methyl‐substituted and unsubstituted cyclic trimethylene carbonates. The cyclic trimethylene carbonates obtained by the reaction of dimethyl or diethyl carbonates with 1,3‐propanediol and 2‐methyl‐1,3‐propanediol were polymerized by lipase to produce the corresponding polycarbonates.

Total TMC yield as a function of the reaction time.     

Effect of compression on interaction between 1,4-dihydropyridine compounds and lactose monohydrate

Manidipine dihydrochloride or benidipine hydrochloride will change to hydrate form in part, when differential scanning calorimetric (DSC) measurement is carried out together with lactose monohydrate. This interaction was accelerated by compressing their mixture. It can be suggested that the interaction may cause by the disruption of crystal structure of lactose monohydrate due to compression to set free of water molecules. A new DSC peak at 170 degrees C, which was not observed in each component, appeared in DSC measurement of a mixture. This will be based on hydrate formed by the interaction, i.e., movement of water molecules. The profile of the plotting of the DSC peak area ratio before and after compression against the compression force changed by the molar ratio of lactose monohydrate in a mixture. In the case of low molar ratio of lactose monohydrate, profiles for manidipine dihydrochloride and benidipine hydrochloride differed from each other. This will be because manidipine dihydrochloride is stickier than benidipine hydrochloride. The profile for manidipine dihydrochloride became more gradual and showed lag compression force region when the amount of addition of the lubricant, magnesium stearate in a mixture increased. The endothermic peak area at 170 degrees C for manidipine dihydrochloride was larger than that for benidipine hydrochloride. It should be suggested that benidipine hydrochloride is easier to be transformed to its hydrate than manidipine dihydrochloride.     

Synthesis of thromboxane A2 analog DL-(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A2

A synthesis of the thromboxane A₂ analog, $\text{dl}$-(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A₂ is described.     

A catalytic immuno-reactor for the amperometric determination of human serum albumin

A catalytic immuno-reactor for the determination of human serum albumin (HSA) was constructed by using immobilized antibody and an amperometric detector. A sandwich assay with hemin-labeled antibody to catalyze the decomposition of hydrogen peroxide was used, the catalytic activity of the hemin-antibody conjugate being determined by measuring the decrease in hydrogen peroxide concentration. The reaction of hemin-labeled antibody with antigen was complete within 30 min and the current decrease was correlated with the HSA concentration. The relative standard deviation was about 9% at an HSA concentration of 1 mg ml^?1.     

Enhancement of conductance fluctuations in two-dimensional mesoscopic electron systems with valley structures

Conductance fluctuations are studied in twodimensional mesoscopic electron system with a two-hold valley degeneracy (n _v =2), which corresponds to the inversion layer of Si-MOSFET formed in (1,0,0) plane. It is shown that the intervalley scattering modifies conductance fluctuations depending on the ratio, Min { _c , _T }/ _v , where _v = ( – 2)/2 and _c , _T , and are, respectively, system traversal time, thermal diffusion time, intervalley scattering time and total life time of electrons. Conductance fluctuations are no longer universal and vary from G _univ 0.862·e ²/h to {ie223-5} at low temperatures even for isotropic systems. The conductance fluctuations increase with decreasing system size, increasing electron density and increasing intervalley scattering time. The effect of intervalley scattering is essentially the same as that of intersubband scattering as previously reported. At finite temperatures where _{T c} , the intervalley scattering modifies the fluctuations through the change in the energy correlation range to results in the reduction of the conductance fluctuations. In Si-MOSFET formed in (1, 1, 1) plane, wheren _v =6, more enhanced fluctuations are expected. Experimental studies are desired on theoretically predicted points.     

Long range scattering for non-linear Schrödinger and Hartree equations in space dimensionn≥2

We consider the scattering problem for the non-linear Schrödinger (NLS) equation with a power interaction with critical powerp=1+2/n in space dimensionsn=2 and 3 and for the Hartree equation with potential |x|^–1 in space dimensionn2. We prove the existence of modified wave operators in theL ² sense on a dense set of small and sufficiently regular asymptotic states.Laboratoire associé au Centre National de la Recherche Scientifique     

Mediated amperometric biosensor for hypoxanthine based on a hydroxymethylferrocene-modified carbon paste electrode

An amperometric enzyme electrode for the determination of hypoxanthine in fish meat is described. The hypoxanthine sensor was prepared from xanthine oxidase immobilized by covalent binding to cellulose triacetate and a carbon paste electrode containing hydroxymethylferrocene. The xanthine oxidase membrane was retained behind a dialysis membrane at a carbon paste electrode. The sensor showed a current response to hypoxanthine due to the bioelectrocatalytic oxidation of hypoxanthine, in which hydroxymethyiferrocene served as an electron-transfer mediator. The limit of detection is 6 × 10^?7 M, the relative standard deviation is 2.8% (n=28) and the response is linear up to 7 × 10^?4 M. The sensor responded rapidly to a low hypoxanthine concentration (7 × 10^?4 M), the steady-state current response being achieved in less than 1 min, and was stable for more than 30 days at 5 ° C. Results for tuna samples showed good agreement with the value determined by the conventional method.     

Camdas: An automated conformational analysis system using molecular dynamics

We present an automated conformational analysis program, CAMDAS (Conformational Analyzer with Molecular Dynamics And Sampling). CAMDAS performs molecular dynamics (MD) calculations for a target molecule and samples conformers from the trajectory of the MD. The program then evaluates the similarities between each of the sampled conformers in terms of the root- mean-square deviations of the atomic positions, clusters similar conformers, and finally prints out the clustered conformers. This MD-based conformational analysis is a broadly used method, and CAMDAS is intended to provide a convenient framework for the method. CAMDAS has the ability to find the representative conformers automatically from an arbitrarily given structure of the molecule. The accuracy of the program was examined using N- acetylalanine-N-methylamide, and the obtained result was consistent with that of the systematic search method. In the test calculation of cyclodecane, CAMDAS could identify most of the known conformers and their conformational enantiomers by examining only 5000 conformers. In addition, the potential-scaled method, which we have developed previously as an accelerating technique for MD, could find two additional conformers of cyclodecane that have not been reported. CAMDAS presents a convenient way to find the energetically possible conformers of a molecule, which is needed especially in the early stage of drug design.     

Critical investigation of methods for kinetic analysis of thermoanalytical data

Journal of Thermal Analysis and Calorimetry -     

Non-stoichiometry of YBa2Cu3O7-d Observed by Repeated Temperature Scanning

Repeated temperature scanning method was applied to observe non-stoichiometry of YBa₂Cu₃O₇-d, and interesting results were obtained. Two simultaneously occurring processes were separately observed in mass change; one is a fast process and the other is slow, so that their responses to the temperature change are quite different from each other. The fast process follows the cyclic temperature change, but the slow process is observed to be a gradual mass change. Kinetic behaviors of these two processes are also made clear by plotting the mass vs. the temperature. Furthermore, a hysteresis loop was observed in the plot of the mass vs. the temperature in a high temperature range presumably due to the third process, and it depends on the heating and cooling rates. This revised version was published online in July 2006 with corrections to the Cover Date.