Spontaneous copolymerization of 4-methylene-1,3-dioxolanes with maleic anhydride

The copolymerization of methylenedioxolanes, such as 4-methylene-1,3-dioxolane (I) and 2,2-dimethyl-4-methylene-1,3-dioxolane (II), with maleic anhydride (Manh) gives rise spontaneously to the alternating copolymers by the participation of charge-transfer (CT) complexes. The formation of CT complexes I-Manh and II-Manh was ascertained by UV and NMR spectroscopies. The equilibrium constants (K) could not be determined but were assumed to be small (K ? 1). For comparison with these systems an investigation of I-dimethyl maleate (DMM) and II-DMM systems was carried out to estimate K values 0.115 and 0.157 L/mol, respectively. To clarify the copolymerization mechanism I-Manh-acryronitrile was terpolymerized. Consequently it was concluded that the spontaneous copolymerization of I-Manh and II-Manh systems is effected by the CT complex monomer mechanism.     

Asymmetric epoxidation catalyzed by novel azacrown ether-type chiral quaternary ammonium salts under phase-transfer catalytic conditions

Asymmetric epoxidation of (E)-chalcone with alkaline hydrogen peroxide by novel chiral phase-transfer catalysts (chiral PTCs) with quaternary ammonium salts of azacrown ether proceeded in high yield and good enantioselectivity. Remarkably, this reaction depended on the length of the carbon chain on the nitrogen atom with the chiral PTCs and on the bulk of the base.     

Heat-set gel-like networks of lipophilic Co(II) triazole complexes in organic media and their thermochromic structural transitions

A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T(d)) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T(d) coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 degrees C. A pale pink solution is obtained at 0 degrees C, indicating the formation of octahedral (O(h)) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 degrees C, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 degrees C) and in the solution phase (temperature below 25 degrees C). These observations indicate that T(d) complexes are present as low-molecular weight species around at 25-27 degrees C. They are self-assembled to polymeric T(d) complexes by heating and form gel-like networks. Upon cooling the solution below 25 degrees C, T(d) complexes are converted to O(h) complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution --> blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires.     

High performance liquid chromatography with UV detection for the simultaneous determination of sympathomimetic amines using 4-(4,5-diphenyl-1H-imidazole-2-yl)benzoyl chloride as a label

A high performance liquid chromatographic method has been developed for the simultaneous determination of (+/-) fenfluramine (Fen) and phentermine (Phen) in addition to three other sympathomimetic amines-ephedrine (E), norephedrine (NE) and 2-phenylethylamine (2-PEA), using cyclohexylamine (CX) as an internal standard in plasma. The compounds were derivatized with 4-(4,5-diphenyl-1H-imidazole-2-yl)benzoyl chloride (DIB-Cl) to give the DIB-derivatives. The derivatives were then separated using an isocratic HPLC system with UV detection. The limits of detection for Fen, Phen, E, NE and 2-PEA in plasma ranged from 0.32 to 22.9 pmol on column at a signal-to-noise ratio of 3. The recoveries following alkaline extraction from plasma samples of known concentrations were found to be more than 94% for the studied compounds. This method might be useful for the screening of the studied sympathomimetic amines in human plasma samples in forensic as well as toxicological studies. Furthermore, the developed method was modified for the simultaneous determination of Fen and Phen in human and rat plasma using fluoxetine as an internal standard. The methods are reproducible and precise. Finally, the two drugs were administered intraperitoneally to rats in combination, and their plasma levels over the investigated time course were successfully determined.     

Synthesis of a soluble ureido-naphthyridine oligomer that self-associates via eight contiguous hydrogen bonds

[structure; see text] An iterative synthetic route to organic-soluble ureido-naphthyridine oligomers has been developed. Use of this protocol allowed synthesis of a short ureido-naphthyridine oligomer, which presents a self-complementary DDAADDAA hydrogen bonding array (D = hydrogen bond donor, A = hydrogen bond acceptor). Strong self-association via eight hydrogen bonds was observed in organic solution.     

Stereoselective pyrroline-ring formation through the cyclization of conjugated azomethine ylides at the periphery of pyrido[1,2-a]pyrimidine system

The thermal reaction of N-benzyl-N-[3-(N-substituted imino)methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-2-yl]amino acid esters, generated from aldehyde esters and primary amines, provides 2,3-dihydropyrido[1,2-a]pyrrolo[2,3-d]pyrimidin-4(1H)-one derivatives effectively and stereoselectively. Therein, the stereoselective generation of conjugated azomethine ylides from the imine esters and their cyclization is essential for the pyrroline-ring formation.     

Molecular bilayer-based superstructures of a fullerene-carrying ammonium amphiphile: structure and electrochemistry

The synthesis of a water-soluble C60-carrying single-chain ammonium amphiphile, 10- (N-methyl-2-fulleropyrrolidyl)decyltrimethylammonium bromide (1) as well as the characterization of aqueous solutions and cast films of 1 are described. X-ray diffraction study suggests that cast films of 1 form a multilayer structure based on biomembrane-like molecular bilayers. Electron microscopy has revealed that 1 produces both fibrous and disk-like aggregates with 10-12 nm of thickness through self-organization of 1 in aqueous solution. Differential scanning calorimetry, dynamic light scattering, FTIR, and UV-visible absorption studies were also carried out to characterize aqueous solutions and cast films of 1. Electrochemistry for an aqueous solution and for cast films of just 1 and 1 incorporated in lipid films on electrodes was conducted. It was found that films of just 1 and of 1/lipid cast on electrodes showed electron transfer reactions leading to the generation of the fullerene dianion or trianion. In contrast, electrochemistry of aqueous solution of 1 at a bare electrode gives a cathodic current near -0.5 to -0.6 V against SCE; however, an anodic current for the solution did not appear.     

Intramolecular charge-transfer fluorescence from 9,9′-bianthryl absorbed on porous glass

9,9′-bianthryl (BA) absorbed on porous glass exhibits both intramolecular charge-transfer (CT) and anthracene-like fluorescence. The CT fluorescence exhibits no temperature dependence, suggesting that orientational relaxation on the time scale of fluorescence decay is absent. Complex fluorescence decay characteristics from BA and 9,10-diphenyl anthracene (DA) absorbed on the glass are interpreted in terms of absorption on a variety of sites.     

Disposition of triazolam in the rat by brain microdialysis and semi-micro column high-performance liquid chromatography with UV absorbance detection

A semi-micro column high-performance liquid chromatography with ultraviolet detection for the determination of triazolam is described. The method was applied to determine plasma and brain microdialysate concentrations of triazolam after single intravenous bolus of 2.5 mg/kg to rat. The separation was achieved on a 250 x 1.5 mm i.d. C(18) column and the column effluent was monitored at 222 nm. The detection limits at a signal-to-noise ratio of 3 obtained using spiked plasma and artificial cerebrospinal fluid were 2.1 and 0.7 ng/mL, respectively. The intra- and inter-day reproducibility of the present method were satisfactory with the highest relative standard deviation of 9.1 (n > or = 5). The present method was successfully applied to study the disposition of triazolam in rat (n = 5) by analyzing plasma and brain microdialysate samples.     

Measurement of reaction rate distributions in a plastic phantom irradiated by 40- and 65-MEV quasi-monoenergetic neutrons

Reaction rate distributions in a plastic phantom were measured with solid state nuclear track detectors and a fission counter for 40- and 65-MeV quasi-monoenergetic neutrons generated by the 7Li(p,n) reactions with 43- and 68-MeV protons at AVF cyclotron of Japan Atomic Energy Research Institute. Measured distributions were compared with calculated ones.