Linear dichroism and fluorescence polarization of diphenyl polyenes in stretched polyethylene films

A study of the linear diehroism and fluorescence polarization of diphenylpolyenes (C₆H₅—(CH=CH)_n—C₆H₅) with n = 1,2,3,4,6,8 in stretched polyethylene films shows that the polyenes orient in the anisotropic matrix with their transition dipole (emission and absorption, π → π^*) aligned with the direction of stretch. The maximum dichroic ratio is observed for 1,6-diphenyl-1,3,5-hexatriene (DPH), with n = 3, whereas the values are substantially lower for n < 3 or n > 3. The high orientation of DPH and poor alignment of the higher polyenes may be accounted for in terms of the growing flexibility of the polyene chains with increasing chain length. The results justify the use of DPH as a convenient fluorescence probe for biological and synthetic membranes.     

A dual-electrode approach for highly selective detection of glucose based on diffusion layer theory: experiments and simulation

A dual-electrode configuration for the highly selective detection of glucose in the diffusion layer of the substrate electrode is presented. In this approach, a glassy carbon electrode (GCE, substrate) modified with a conductive layer of glucose oxidase/Nafion/graphite (GNG) was used to create an interference-free region in its diffusion layer by electrochemical depletion of interfering electroactive species. A Pt microelectrode (tip, 5 microm in radius) was located in the diffusion layer of the GNG-modified GCE (GNG-G) with the help of scanning electrochemical microscopy. Consequently, the tip of the electrode could sense glucose selectively by detecting the amount of hydrogen peroxide (H2O2) formed from the oxidization of glucose on the glucose oxidase layer. The influences of parameters, including tip-substrate distance, substrate potential, and electrolyzing time, on the interference-removing efficiency of this dual-electrode approach have been investigated systematically. When the electrolyzing time was 30 s, the tip-substrate distance was 1.8 a (9.0 microm) (where a is the radius of the tip electrode), the potentials of the tip and substrate electrodes were 0.7 V and 0.4 V, respectively, and a mixture of ascorbic acid (0.3 mM), uric acid (0.3 mM), and 4-acetaminophen (0.3 mM) had no influence on the glucose detection. In addition, the current-time responses of the tip electrode at different tip-substrate distances in a solution containing interfering species were numerically simulated. The results from the simulation are in good agreement with the experimental data. This research provides a concept of detection in the diffusion layer of a substrate electrode, as an interference-free region, for developing novel microelectrochemical devices.     

Constraint Variational Calculations on Excited States

The difficulties of the SCF and MCSCF calculations on excited states have been reviewed. Three constraint variational methods are then developed which can perform the SCF and MCSCF calculations on excited states in the scheme of the generalized Brillouin theorem method. The proper constraints and the ways to incorporate the constraints into the variational calculations on excited states have been studied and the comparison with other approaches have been accessed.     

Conjugated enynes as a new type of substrates for olefin metathesis

[reaction: see text] It has been demonstrated for the first time that conjugated enynes can be employed as a facile substrate in olefin metathesis with the use of a bispyridine-substituted ruthenium benzylidene catalyst. Cross-metathesis of the enynes with alkenes turns out to proceed with preferential formation of (Z)-isomers over (E)-isomers up to >25:1 in moderate to good yields. The intramolecular version of conjugated enynes affords novel butadienyl cycloalkenes, which are a highly useful synthetic building blocks, in acceptable yields.     

Complexation of plutonium(IV) with sulfate at variable temperatures

The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method. A NaBrO₃ solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO₄ ⁻ complexes, dominant in the aqueous phase, were calculated from the effect of [HSO₄ ⁻] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures using the Van’t Hoff equation.     

Reactivity ratios for copolymerization of vinyl chloride with 2-methylpentyl vinyl brassylate by computerized linearization

A computerized version of the Fineman-Ross linearization procedure was used to determine reactivity ratios for copolymerization of vinyl chloride (monomer 1) and 2-methylpentyl vinyl brassylate (monomer 2). From differential refractometry data for the products of low-conversion copolymerization, the procedure gave r₁ = 1.06 and r₂ = 0.234. The ratios computed from chlorine contents of the same products were r₁ = 1.10 and r₂ = 0.239. The polarity factor (e₂) and general monomer reactivity (Q₂) calculated for monomer 2 from these ratios were, respectively, ?0.95 to ?0.98 and 0.032–0.033. The interquartile range for the copolymerization of a mixture of 60% monomer 1 and 40% monomer 2 was 1.4%. These values suggest that from suitable proportions of reactants, sufficiently homogeneous distribution of monomers can be achieved in copolymers of vinyl chloride and 2-methylpentyl vinyl brassylate to offer the possibility of effective internal plasticization.     

Tetracyclic triterpenoids from Melia azedarach, L.—III

From petroleum ether extracts of the bark of M. azedarach four novel tetracyclic triterpenoids have been isolated and characterized to be C₃₀ compounds of the euphane (20R) series. Previously known triterpenoids from Meliaceae have all been 20S compounds. Kulinone 1 is the first known euphane or tirucallane (20S) derivative oxygenated in the D ring; kulactone 2, kulolactone 3 and methyl kulonate 4 are additionally oxygenated in the side chain. Compounds 2 and 3 have a 2-oxa-trans-bicyclo[3,3,0]-octanone structure.