Mutation detection in the drug-resistant hepatitis B virus polymerase gene using nanostructured reverse micelles.

The emergence of drug-resistant hepatitis B virus (HBV) has been reported in patients with prolonged administration of lamivudine, which is a potent drug for the prevention of HBV infection. Lamivudine-resistant HBV has several types of mutations at the YMDD motif of its DNA polymerase. We successfully demonstrated that monitoring the hybridization behavior in nanostructured reverse micelles enables us to detect single nucleotide polymorphisms (SNPs). With the aid of reverse micelles, a model 40-mer oligonucleotide containing a single-base substitution was clearly distinguished from the normal, complementary oligonucleotide. In addition, we extended this technique to a high-throughput analysis. The results obtained with a 96-well micro-plate reader indicated the possibility of SNPs detection toward multiple samples of patients.     

A Relationship Among Gentzen's Proof-Reduction,Kirby-Paris' Hydra Game and Buchholz's Hydra Game

We first note that Gentzen's proof-reduction for his consistency proof of PA can be directly interpreted as moves of Kirby-Paris' Hydra Game, which implies a direct independence proof of the game (Section 1 and Appendix). Buchholz's Hydra Game for labeled hydras is known to be much stronger than PA. However, we show that the one-dimensional version of Buchholz's Game can be exactly identified to Kirby-Paris' Game (which is two-dimensional but without labels), by a simple and natural interpretation (Section 2). Jervell proposed another type of a combinatorial game, by abstracting Gentzen's proof-reductions and showed that his game is independent of PA. We show (Section 3) that this Jervell's game is actually much stronger than PA, by showing that the critical ordinal of Jervell's game is φ_ω (0) (while that of PA or of Kirby-Paris' Game is φ₁ (0) = ?₀) in the Veblen hierarchy of ordinals.     

Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.     

Polymerizability of unsaturated monomers capable of forming stable radicals

Some unsaturated monomers bearing hindered phenol and arylamine groups capable of forming stable radicals were prepared. Radical polymerizations of vinyl monomers having such groups were investigated with the use of azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and tetraethylthiuram disulfide as initiator. Polymerizations of these monomers went normally only when azobisisobutyronitrile was used as initiator. The other initiators inhibited polymerizations remarkably or completely. The results suggest that radicals resulting from benzoyl peroxide and cumene hydroperoxide or tetraethylthiuram disulfide abstract hydrogen of the phenol or the amine to produce the stable radicals, thereby inhibiting the polymerization. Meanwhile, carbon radicals resulting from azobisisobutyronitrile add selectively to the vinyl double bonds of the monomers to initiate the polymerizations. The vinyl derivatives as well as allyl derivatives and cinnamic acid derivatives copolymerize easily with conventional monomers such as styrene, maleic anhydride, and butadiene, again, only when azobisisobutyronitrile was used as initiator. Antioxidative properties for styrene copolymers and butadiene-styrene copolymers incorporating the hindered phenol monomers were investigated.     

Rhodium-catalyzed addition of arylboron compounds to nitriles, ketones, and imines

The rhodium-catalyzed addition reactions of sodium tetraphenylborate and arylboronic acids to nitriles, ketones, and imines were examined. The reaction of nitriles could be carried out efficiently in the presence of a catalyst system of [RhCl(cod)]₂-dppp and H₂O to give the corresponding monoarylated products selectively. Although unactivated ketones and imines are known to be poor electrophiles for rhodium-catalyzed arylation, the phenylation of them with use of sodium tetraphenylborate proceeded smoothly in the presence of [RhCl(cod)]₂ and Rh(acac)(cod) as catalysts, respectively. The addition of NH₄Cl was found to be crucial to effectively conduct the reaction of ketones and imines.     

Fundamental investigation of thermal properties of rare-earth beta-diketonates

The thermal properties of the rare-earth chelates of Htfa (trifluoroacetylacetone) and Hhfa (hexafluoroacetylacetone) have been investigated. Thermogravimetric curves were obtained by heating samples in the injection chamber of a gas chromatograph, both in an atmosphere of helium, and of helium containing ligand vapour. None of the chelates was completely vaporized in a helium atmosphere at temperatures up to about 240 degrees , but the tfa chelate of Lu and all the hfa chelates were completely vaporized in the atmosphere of helium containing ligand vapour. The vapour pressures and heats of vaporization of these chelates were also measured.     

Carbamate mediated 1,3-asymmetric induction. A stereoselective synthesis of acyclic 1,3-diol systems

A highly regio- and stereo-selective functionalization of homoallylic carbamates with iodine is reported. The reaction has been applied to the preparation of key 1,3,5-triol intermediate $\text{2}$ employed in the synthesis of compactin ($\text{1}$).     

Photoinduced ionic polymerization. III. Cationic polymerization and copolymerization of cyclohexene oxide and α-methylstyrene in the presence of pyromellitic dianhydride

The photoinduced ionic polymerization of cyclohexene oxide was studied in the presence of pyromellitic dianhydride. The polymerization is initiated by the excited chargetransfer complex between cyclohexene oxide and the electron-acceptor and proceeds by a cationic mechanism. Photoinduced cationic polymerization of α-methylstyrene was also observed in the presence of pyromellitic dianhydride. The initiation mechanism of the polymerization was elucidated by means of electron spin resonance measurements. The concentration of pyromellitic dianhydride anion-radicals measured in this way was found to be proportional to the rate of polymerization. This result shows clearly that the photopolymerization is initiated by cation-radicals formed from photoexcited donoracceptor complexes. The attempted photocopolymerization of cyclohexene oxide and α-methylstyrene gave a mixture of homopolymers. The composition of the product depends on the wavelength of the light used.