Toda equation and special polynomials associated with the Garnier system

We prove that a certain sequence of τ-functions of the Garnier system satisfies Toda equation. We construct algebraic solutions of the system by the use of Toda equation; then show that the associated τ-functions are expressed in terms of the universal character which is a generalization of Schur polynomial attached to a pair of partitions.     

Fluorescence Energy Transfer Study of Interstrand DNA Cross-linking Caused by Rigid Bisintercalator

The intermolecular cross-linking of DNA with a rigid bisintercalator, 1,4-bis(( N -methylquinolinium-4-yl)vinyl)benzene (pMQVB) has been studied using fluorescence resonance energy transfer (FRET), fluorescence anisotropy measurements, and dynamic fluorescence microscopy. Short DNA duplexes, single-labeled with fluorescein (donor) and x-rhodamine (acceptor), were used as energy transfer partners. Due to the quenching effect of pMQVB on the emission of both fluorescein and x-rhodamine, the energy transfer was monitored using the corrected Stern-Volmer plots. The cross-linking ability of pMQVB depended on the ligand structure; the planar E , E isomer cross-linked DNA contrary to the non-planar E , Z isomer. Dynamic fluorescence microscopy observation also demonstrated the ability of pMQVB to cross-link large T4 DNA molecules.     

Photochemistry and photocuring properties of thiol‐substituted α‐aminoalkylphenone as radical photoinitiator

Thiol‐substituted α‐aminoalkylphenone was newly developed as a radical photoinitiator. Introduction of the thiol group drastically improved photosensitivity in an alkaline developable resist formulation composed of a prepolymer and a multifunctional acrylate monomer. The improvement in the photocuring speed was explained by a mechanism based on chain transfer reaction of the thiol group. Time‐resolved electron spin resonance (ESR) spectroscopy indicated that the thiol group attached to the chromophore does not influence the photochemical process to generate primary radicals. The photoinitiation of α‐aminoalkylphenone can be spectrally sensitized by 2,4‐diethylthioxanthone (DETX). However, thiol‐substituted α‐aminoalkylphenone showed smaller spectral sensitization than the corresponding compound without a thiol group. Time resolved laser flash photolysis indicated that the rate constant of the quenching of the triplet state of DETX by thiol‐substituted α‐aminoalkylphenone is twice as large as that by the corresponding one without a thiol group. This suggests that, besides energy transfer from DETX in the excited triplet state to the α‐aminoalkylphenone, the thiol group quenches the excited triplet state of DETX via charge transfer and/or hydrogen transfer, as supported by the ESR analysis using a spin trapping technique, and lowers the efficiency of the spectral sensitization effect. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1684–1695, 2005     

Reductive alkylation of indoles with alkynes and hydrosilanes under indium catalysis

Under Indium catalysis, diverse alkylindoles were successfully prepared with a flexible combination of indoles and alkynes in the presence of hydrosilanes. In addition to the hydrosilane, carbon nucleophiles are also available. This new method generates alkylindoles in yields over 70% with a broad scope of functional group compatibility.     

Reproducibility of Programmed-Temperature Retention Indices under Average Linear Velocity Carrier Gas Control of GC and GC�CMS

Programmed-temperature retention indices (PTRIs) are useful for the identification and quantification of chemicals by means of GC and GC/MS. To obtain reproducible PTRIs, we studied the influence of average linear velocity and column length under the constant average linear velocity control (CVC) using 55 pesticides and 33 fatty acid methyl esters. The PTRIs decreased with increasing average linear velocity, and the degree of decrease differs with the compounds. The PTRIs, however, were almost constant as long as the same average linear velocity was used even if the column length was changed. In addition, the correlation between the variation ratio in PTRI and the increase in average linear velocity was linear. Using the linear relationship between PTRIs and average linear velocities under CVC, highly reproducible PTRIs were obtained even if the capillary column length changes. Furthermore, the PTRIs determined by GC with FID, ECD, and FPD under atmospheric pressure were applied to GC/MS under vacuum or vice versa. From these results, it was confirmed that because CVC provides reproducible retention indices, CVC is advantageous for qualitative and quantitative analysis by GC and GC/MS.     

Convenient preparation of 4-arylmethyl- and 4-hetarylmethyl thiazoles by regioselective cycloaddition reactions of 3-sulfanyl- and selanylpropargyl alcohols

Complete details of thiazole syntheses by scandium-catalyzed cycloaddition reactions of 1-aryl- and 1,1-bisaryl-3-phenylsulfanylpropargyl alcohols with thioamides are described. Reactions of 1,1-bisarylpropargyl alcohols with thioamides and selenamide in MeNO₂/H₂O resulted in 4-bisarylmethyl-1,3-thiazoles 4aa-ic and 4H-4,4-bisaryl-1,3-thiazines 5ea-ga in high yields. Reactions in MeNO₂/D₂O resulted in 4-bisaryldeuteriomethyl-1,3-thiazoles 10ca-ia with high deuterium purity. Reactions of dialkyl and alkyl aryl propargyl alcohols are also described.     

Steady-state thermodynamics for heat conduction: microscopic derivation

Starting from microscopic mechanics, we derive thermodynamic relations for heat conducting nonequilibrium steady states. The extended Clausius relation enables one to experimentally determine nonequilibrium entropy to the second order in the heat current. The associated Shannon-like microscopic expression of the entropy is suggestive. When the heat current is fixed, the extended Gibbs relation provides a unified treatment of thermodynamic forces in the linear nonequilibrium regime.     

Universal Characters and an Extension of the KP Hierarchy

The universal character is a polynomial attached to a pair of partitions and is a generalization of the Schur polynomial. In this paper, we define vertex operators which play roles of raising operators for the universal character. By means of the vertex operators, we obtain a series of non-linear partial differential equations of infinite order, called the UC hierarchy; we regard it as an extension of the KP hierarchy. We investigate also solutions of the UC hierarchy; the totality of the space of solutions forms a direct product of two infinite-dimensional Grassmann manifolds, and its infinitesimal transformations are described in terms of the Lie algebra .     

Identification of spontaneous conversion products of unstable 2,4,6-trinitrotoluene metabolites, hydroxylamino-dinitrotoluenes, by combination of thin-layer chromatography and laser time-of-flight mass spectrometry

Two kinds of hydroxylamino-dinitrotoluenes, 2-hydroxylamino-4, 6-dinitrotoluene (2HADNT) and 4-hydroxylamino-2, 6-dinitrotoluene (4HADNT), are known to be major metabolites produced from 2,4,6-trinitrotoluene (TNT) by bacteria. The amounts of 2HADNT and 4HADNT in distilled water are found to spontaneously decrease with time, albeit abiotic conditions, and many white precipitates are educed in the processes of this phenomenon; however, how these compounds are converted is unclear. We evinced the mystery of this phenomenon by using thin-layer chromatography (TLC) and laser time-of-flight mass spectrometry (TOFMS). TLC analyses in the spontaneous conversion processes of 2HADNT, 4HADNT, and 2HADNT plus 4HADNT demonstrats that three novel spots emerge on the TLC plate, respectively. These products are individually extracted into acetonitrile by collecting each spot. The purity of these extracts, which have retention times of 14.0, 17.7, and 15.4 min, is approximately 98%, judging from the results of high-performance liquid chromatographic analyses. The spontaneous conversion products of 2HADNT, 4HADNT, and 2HADNT plus 4HADNT are identified as 4,4',6,6'-tetranitro-2,2'-azoxytoluene (2,2'AZT), 2,2',6,6'-tetranitro-4,4'-azoxytoluene (4,4'AZT), and 4,2',6, 6'-tetranitro-2,4'-azoxytoluene (2,4'AZT) by obtaining their mass spectra with laser TOFMS. It is confirmed that most of the spontaneous conversion products are 2,2'AZT, 4,4'AZT, or 2,4'AZT, judging from the results of mass balance in the spontaneous conversion processes of 2HADNT, 4HADNT, and 2HADNT plus 4HADNT.