Reductive electron injection into duplex DNA by aromatic amines

An assay based on photoinduced reaction and subsequent cleavage of duplex DNA containing a bromodeoxyuridine ((Br)U) residue and an abasic site was developed to screen aromatic amines for their ability to initiate charge transfer by reductive electron donation. Two candidates, N,N,N',N'-tetramethyl-1,5-diaminonaphthalene (TMDN) and 1,5-diaminonaphthalene (DAN), expressed the desired activity, and an oligodeoxynucleotide-TMDN conjugate was subsequently prepared to identify additional variables affecting the efficiency of electron injection and transfer into DNA. This system demonstrated only mild sensitivity to molecular oxygen but was strongly inhibited by high concentrations of 2-mercaptoethanol. The nucleobase counter to the attached TMDN strongly modulated charge transfer as evident by a 60-fold decrease in reduction of the distal (Br)U when the counterbase A was substituted for C. An inverse relationship between this reduction and quenching of TMDN fluorescence by the counterbase was also discovered and is consistent with a competition between radical recombination and electron migration away from the initial site of its injection into DNA.     

Aroma chemical emitted from Gerris paludum insularis

An aroma chemical emitted from Gerris paludum insularis was analyzed by means of GC and GC-MS. The main constituent was identified as iso amyl alcohol (3-methyl-1-butanol). The chemical showed a characteristic aroma of Gerris paludum insularis.     

The Elliptic Algebra and the Drinfeld Realization of the Elliptic Quantum Group

By using the elliptic analogue of the Drinfeld currents in the elliptic algebra , we construct a L-operator, which satisfies the RLL-relations characterizing the face type elliptic quantum group . For this purpose, we introduce a set of new currents in . As in the N=2 case, we find a structure of as a certain tensor product of and a Heisenberg algebra. In the level-one representation, we give a free field realization of the currents in . Using the coalgebra structure of and the above tensor structure, we derive a free field realization of the -analogue of -intertwining operators. The resultant operators coincide with those of the vertex operators in the -type face model.     

Intramolecular cyclization with nitrenium ions generated by treatment of N-acylaminophthalimides with hypervalent iodine compounds: formation of lactams and spiro-fused lactams

N-Phthalimido-N-acylnitrenium ions are generated from N-acylaminophthalimides, a new class of precursors, by treatment with hypervalent iodine compounds (PIFA and HTIB). In HFIP, the nitrenium ions undergo intramolecular electrophilic substitution reactions to afford N-aminonitrogen heterocycles in high yields. In TFEA, spirodienones bearing the 1-azaspiro[4.5]decane skeleton are obtained by treatment of N-phthalimido-3-(4-halogenophenyl)propanamides with HTIB as a result of ipso attack of the intermediate nitrenium ion. Similarly, using PIFA in TFEA, ipso cyclization of unactivated benzenoid compounds occurs to afford spirodiene derivatives. This involves loss of aromaticity despite the absence of other activating substituents on the phenyl group.     

Iodine atom transfer [3 + 2] cycloaddition reaction with electron-rich alkenes using N-tosyliodoaziridine derivatives as novel azahomoallyl radical precursors

Treatment of N-tosyliodoaziridine derivatives with Et(3)B efficiently produces various azahomoallyl radical (2-akenylamidyl radical) species which give oxygen-functionalized pyrrolidine derivatives through iodine atom transfer [3 + 2] cycloaddition with electron-rich alkenes such as enol ethers and ketene acetal. The present cycloaddition reaction proceeds regioselectively via C-N bond cleavage of an aziridinylalkyl radical intermediate and addition of the resulting azahomoallyl radicals to the terminal carbon of an alkene. The reaction of alkenes with the cyclohexenylamidyl radical generated from an optically active bicyclic iodoaziridine [(1S,2S,6S)-2-iodo-7-(p-toluenesulfonyl)-7-azabicyclo[4.1.0]heptane, 94% ee] also proceeds to give optically active octahydroindole derivatives (84-93% ee).     

A novel action of terpendole E on the motor activity of mitotic Kinesin Eg5

To reveal the mechanism of mitosis, the development of M phase-specific inhibitors is an important strategy. We have been screening microbial products to find specific M phase inhibitors that do not directly target tubulins, and rediscovered terpendole E (TerE) as a novel Eg5 inhibitor. TerE did not affect microtubule integrity in interphase, but induced formation of a monoastral spindle in M phase. TerE inhibited both motor and microtubule-stimulated ATPase activities of human Eg5, but did not affect conventional kinesin from either Drosophila or bovine brain. Although terpendoles have been reported as inhibitors of acyl-CoA:cholesterol O-acyltransferase (ACAT), the Eg5 inhibitory activity of TerE was independent of ACAT inhibition. Taken together, we demonstrate that TerE is a novel Eg5 inhibitor isolated from a fungal strain.     

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.     

Observation of the "self-healing" of an error field island in the large helical device

It was observed that the vacuum magnetic island produced by an external error magnetic field in the large helical device shrank in the presence of plasma. This was evidenced by the disappearance of flat regions in the electron temperature profile obtained by Thomson scattering. This island behavior depended on the magnetic configuration in which the plasmas were produced.     

Furan derivatives. Part 12 . Synthesis of 2,5-dioxacyclohepta[jkl]-as-indacenes

A variety of 2,5-dioxacyclohepta[jkl]-as-indacenes 5, 7–14 were synthesized as a new heterocycle by the treatment of diethyl (5,9-dioxobenzocyclohepten-1,4-diyloxy)diacetates 4a-e with potassium hydroxide or sodium hydride in dioxane. The mechanism of furan-ring formation from 4a-e was discussed.     

Formation and atomic structures of boron nitride nanohorns encaging boron nitride cluster

Boron nitride (BN) nanohorns were synthesized by arc-melting YB₆ powders. Method, and atomic structure models for BN nanohorns encaging Y@B₃₆N₃₆ were proposed from high-resolution electron microscopy. The molecular mechanics calculation indicated that BN clusters with metal atoms would be stabilized by being encaged in double-walled BN nanohorns.