Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

Proposed mechanism for the reaction catalyzed by a diterpene cyclase,aphidicolan-16beta-ol synthase: experimental results on biomimetic cyclization and examination of the cyclization pathway by ab initio calculations

To examine the mechanism of the cyclization reaction catalyzed by aphidicolan-16beta-ol synthase (ACS), which is a key enzyme in the biosynthesis of diterpene aphidicolin, a specific inhibitor of DNA polymerase alpha, skeletal rearrangement of 2a and biomimetic cyclization of 4b were employed. The structures of the reaction products, which reflect penultimate cation intermediates, allowed us to propose a detailed reaction pathway for the Lewis acid-catalyzed cyclizations and rearrangements. Isolation of these products in an aphidicolin-producing fungus led us to speculate that the mechanism of the ACS-catalyzed cyclization reaction is the same as that of a nonenzymatic reaction. Ab initio calculations of the acid-catalyzed reaction intermediates and the transition states indicate that the overall reaction catalyzed by ACS is an exothermic process though the reaction proceeds via an energetically disfavored secondary cation-like transition state. In conjunction with the solvent effect in the acid-catalyzed reactions, this indicates that the actual role of ACS is to provide a template which enforces conformations of the intermediate cations leading to the productive cyclization although it has been believed that the cation-pi interaction between cation intermediates and aromatic amino acid residues in the active site is important for the enzymatic catalysis. This study provided important information on the role of various cationic species, especially secondary cation-like structures, in both nonenzymatic and enzymatic reactions.     

High-speed 1.55 μm InGaAs/InGaAsP multi-quantum well λ/4-shifted DFB lasers

The high-speed modulation properties of 1.5 μm multiquantum-well λ/4-shifted DFB lasers are filly reviewed. In particular, the dependence of intrinsic dynamic properties, such as relaxation oscillation frequency, nonlinear damping phenomenon, and spectral chirping under 10 Gbit/s direct modulation, on the number of quantum wells is systematically investigated and compared with those of bulk lasers. The results indicate that the dependence of the above three factors on the number of wells is clearly explained by the linear gain saturation of the quantum-well lasers and that the optimum number of wells should be more than ten in order to increase the modulation bandwidth.     

Dioxygenases, key enzymes to determine the aglycon structures of fusicoccin and brassicicene, diterpene compounds produced by fungi

Fusicoccin A and cotylenin A are structurally related diterpene glucosides and show a phytohormone-like activity. However, only cotylenin A induces the differentiation of human myeloid leukemia cells. Since the cotylenin A producer lost its ability to proliferate during preservation, a study on the relationship between structure and activity was carried out and a modified fusicoccin A with hydroxyl group at the 3-position showed a similar biological activity with that of cotylenin A. We then searched for an enzyme source that catalyzes the introduction of a hydroxyl group into the 3-position and found that brassicicene C, which is structurally related to fusicoccin A with hydroxyl group at the 3-position, was produced by Alternaria brassicicola ATCC96836. We recently cloned a brassicicene C biosynthetic gene cluster including the genes encoding fusicocca-2,10(14)-diene synthase and two cytochrome P450s, which were responsible for the formation of fusicocca-2,10(14)-diene-8β,16-diol. In this study, we report that a α-ketoglutarate dependent dioxygenase, the gene coding for which was located in the cluster, catalyzed a hydroxylation at the 3-position of fusicocca-2,10(14)-diene-8β,16-diol. On the other hand, a α-ketoglutarate-dependent dioxygenase, which had been identified in a fusicoccin A biosynthetic gene cluster, catalyzed the 16-oxidation of fusicocca-2,10(14)-diene-8β,16-diol to yield an aldehyde (8β-hydroxyfusicocca-1,10(14)-dien-16-al), although both dioxygenases had 51% amino acid sequence identity. These findings suggested that the dioxygenases played critical roles for the formation of the fusicoccin A-type and cotylenin A-/brassicicene C-type aglycons. Moreover, we showed that short-chain dehydrogenase/reductase located in the fusicoccin A biosynthetic gene cluster catalyzed the reduction of the aldehyde to yield fusicocca-1,10(14)-diene-8β,16-diol.     

One-dimensional surface reconstruction as an atomic-scale template for the growth of periodically striped Ag films

The role of the In/Si(111)-(4 x 1)-In surface as an atomic-scale geometrical template for the growth of Ag thin films is clarified by scanning tunneling microscopy and low energy electron diffraction. Low-temperature grown Ag films are found to have stripe structures with a transverse periodicity equal to that of indium chains of the In/Si(111)-(4 x 1)-In. The stripes exhibit a structural transformation at the thickness of 6 monolayers (ML); this relaxation allows the stripes to persist up to a thickness as large as 30 ML (approximately = 7 nm) while maintaining their mean periodicity. We attribute this stability to a coincidental matching of the periodicity and the corrugation amplitude between the Ag film and the substrate, which is realized by periodic insertion of stacking faults into a Ag fcc crystal.     

In situ surface-enhanced infrared absorption spectroscopy for the analysis of the adsorption and desorption process of Au nanoparticles on the SiO2/Si surface

The adsorption and desorption of Au nanoparticles (AuNP) in colloidal D2O suspension on the (3-aminopropyl)triethoxysilane treated SiO2/Si surface was investigated by in situ attenuated total reflection surface enhanced infrared absorption (ATR-SEIRA) spectroscopy with a liquid flow cell. With increasing surface density of AuNP, the absorption of the vibrational modes of D2O and of the citrate molecules covering the AuNP increases due to SEIRA. Repulsive electrostatic Coulomb forces between the AuNP lead to the saturation of the AuNP surface density at submonolayer coverage. We show that the adsorption kinetics can be investigated by monitoring in situ the molecular vibrational modes of D2O and the citrate molecules. Furthermore, we clarify that the adsorption process can be described very well by a diffusion-limited first-order Langmuir kinetics model. When exposing a saturated AuNP submonolayer to 2-aminoethanethiol (AET)/D2O solution, the AuNP are removed from the surface and the IR absorption of the D2O vibrational modes become weaker again. Taking into account the time dependencies of the OD and the CH peaks, we propose a microscopic model where the AET molecules quickly adsorb on the AuNP by replacing most of the precovering citrate molecules exposed to the AET solution. As this takes place, the AuNP agglomerate-as we could detect with scanning electron microscopy-and are finally removed from the surface.     

Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates

Polysiloxanes are useful materials because of their functionality, such as high thermal stability, electrical resistance, and hydrophobicity. In this regard, we studied palladium-catalyzed formation of iodo- and bromopolysiloxanes from two types of hydrosiloxanes, α,ω-dihydropoly(dimethylsiloxane) (1) and cyclotetra(hydromethylsiloxane) (2), and their reactions. Treatment of 1 with mixtures of cyclic ethers or lactones and MeI or allylBr in the presence of a catalytic amount of PdCl₂ gave the corresponding α,ω-bis(haloalkoxy and haloalkanoyloxy)poly(dimethylsiloxane)s in good yields, via iodo- and bromopoly(dimethylsiloxane) intermediates. Transformation of the iodobutoxy-terminal units in the resulting poly(dimethylsiloxane) into aminoalkoxy groups was examined. The formation of α,ω-diiodo- and dibromopoly(dimethylsiloxane)s from 1 was confirmed by spectrometric analysis as well as by quenching experiments with ethanol. A reaction of α,ω-dibromopoly(dimethylsiloxane) with 2,5-dilithiothiophene gave a polydimethylsiloxane-thiophene alternating polymer. Similar palladium-catalyzed reactions of 2 with THF/MeI, THF/allylBr, and δ-valerolactone/allylBr afforded cyclo-(halobutoxy- and bromobutanoyloxymethylsiloxane)s in moderate yields. This would provide a new strategy for the introduction of various substituents to the terminal positions of linear polysiloxane and to the cyclosiloxane core.