Successive phase transitions of [(PyO)(H/D)][AuCl4] (PyO=C5H5NO)

³⁵Cl NQR as well as heat capacity measurements of [(PyO)H][AuCl₄] and its deuterated analog [(PyO)D][AuCl₄] revealed successive phase transitions at 70.5 and 62.5 K, and at 71 and 63 K, respectively. The NQR frequency varied continuously through the upper transition point while discontinuously through the lower transition point. In the intermediate-temperature phase a remarkable decrease in the signal intensity was observed. These NQR observations as well as the feature of the heat capacity anomaly in which a broad peak is succeeded by a sharp peak with decreasing temperature suggest a possibility of normal-incommensurate-commensurate phase sequence.     

Breakage of λ-DNA by inorganic tin and organotin compounds as environmental pollutants

In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H₂O₂) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl₂) and tetravalent inorganic tin (SnCl₄) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl₂) than in tetravalent inorganic tin (SnCl₄). Divalent inorganic tin (SnCl₂) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl₂ in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide.     

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.     

Hasse-Witt matrices of Fermat curves

Let m be an integer with m3. Let K and K be perfect fields of characteristic p and p such that (p,m)=1 and (p,m)=1, respectively. Moreover let A and A be algebraic function fields over K and K defined by x^m+y^m=a(0, ak) and x^m+y^m=a(a0 ak), respectively. Put g=(m–1)(m–2)/2. Denote by M(K,p,a) and M(K,p,a) the Hasse-Witt matrices of A and A with respect to the canonical bases of holomorphic differentials. Then we show that if p+p0(mod.m) then rank M(K,p,a)+rank M(K,p,a)=g and if pp1 (mod.m) then rank M(K,p,a)=rank M(K,p,a).     

Highly regio- and stereocontrolled SN2′ reactions of gem-difluorinated vinyloxiranes with monoalkylcopper reagents

Reaction of gem-difluorinated vinyloxiranes with RCu(X)Li allowed us to introduce the R group regioselectively at the fluorine-attached terminal carbon atom in an S_N2′ manner to afford (E)-allylic alcohols exclusively, while homoallylic alcohols with anti stereochemical relationship were found to be obtained selectively from higher-ordered cuprates derived from CuCl and RMgBr in a ratio of 1:3.     

Complexation of a hydrophobic thiazorylazophenol with Ni2+ at sodium dodecylsulfate micellar surface

Complexation of thiazorylazododecylphenol (TADP) with Ni2+ at the surface of sodium dodecylsulfate (SDS) micelles has been spectrophotometrically studied. Complicated spectral changes are analyzed by a factor and multivariate analysis, which implies the formation of [TDAP(OH-)Ni]0 as well as a simple 1:1 complex of Ni2+ with TDAP at the micellar interface. All of the equilibrium constants required to describe this system are substantially affected by electrolyte concentrations. Coexistent electrolytes vary the surface potential of the micelle, and in turn influence the equilibria taking place on the micellar surface. The electrostatic potential estimated based on the equilibrium shifts is more negative than that calculated according to Poisson-Boltzmann theory, which simply involves electrostatic effects. This disagreement is possibly caused by different aqueous environments around the micelle from bulk solution, which also facilitate the formation of unusual complex such as [TDAP(OH-)Ni]0.     

Synthesis of nitrogen-containing heterocycles 6. Formation and structures of imidazolinones and related compounds through cyclization of diaminomethylenehydrazones with dimethyl acetylenedicarboxylate

Diaminomethylenehydrazones 1 of aromatic and aliphatic carbonyl compounds react with dimethyl acetylenedicarboxylate (DMAD) at room temperature to give four types of heterocycles, (5-oxoimidazolin-4-ylidene) acetates 2, 3 and 6 , (2-imino-5-oxoimidazolidin-4-ylidene) acetate 4 and 6-oxo-1,6-dihydropyrimidine-4-carboxylates 5 according to the substitution patterns of 1 in moderate to high yields. Amino (N,N-dimethylamino)methylenehydrazones of ketones give exclusively (5-oxoimidazolin-4-yl-idene) acetates, both (Z)- and (E)-isomers 2 and 3 about the exocyclic alkenic linkage, with the (Z)-isomer 2 generally being predominant, while those of aldehydes give 5 . Diamino- and amino (N-methylamino)methylenehydrazones produce 5 and/or 6 and di (N-methylamino) methylenehydrazone gives (2-imino-5-oxoimidazolidin-4-ylidene) acetate 4 as the sole cyclized product.     

Photodimerization of benzene -photochromism of layered dithiacyclophane-

A novel cage compound was obtained by irradiation of a quadruple-layered dithiacyclophane and showed thermally reverse reaction.