Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method

Porous films of p‐type CuInS₂, prepared by sulfurization of electrodeposited metals, are surface‐modified with thin layers of CdS and TiO₂. This specific porous electrode evolved H₂ from photoelectrochemical water reduction under simulated sunlight. Modification with thin n‐type CdS and TiO₂ layers significantly increased the cathodic photocurrent and onset potential through the formation of a p–n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H₂ production under the present reaction conditions.     

New analytical method for the study of the metabolism of gentiopicroside in rats after oral administration by LC–TOF‐MS following picolinoyl derivatization

The metabolism of gentiopicroside (GPS) in vivo was studied for the first time by LC–MS following picolinoyl derivatization. Incubation of erythrocentaurin, one of the main in vitro metabolites of GPS by intestinal bacteria, with liver microsome indicated that GPS might be metabolized to a final metabolite 3,4‐dihydro‐5‐(hydroxymethyl)isochroman‐1‐one (HMIO) in vivo. After hydrolysis with sulfatase, HMIO was successfully detected in rat plasma after oral administration of GPS by LC–MS following picolinoyl derivatization. 4‐Methoxyphenyl methanol was used as an internal standard to quantify HMIO in rat plasma. A metabolic pathway of GPS in rats is proposed. The monoterpene compound GPS was found to be metabolized to dihydroisocoumarin, which may be responsible for the pharmacological effect of GPS.     

Complexation of poly(vinyl alcohol)–congo red aqueous solutions. 3. Dynamic light scattering study

Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g⁽²⁾(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, D_f (fast) and D_s (slow) were evaluated. D_f was converted to the apparent correlation length, ξ_app, via the mode-mode coupling hypothesis. The estimated ξ_app was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, D_s oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. D_s seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc.     

Study of the thermal degradability of poly(α-methylstyrene) with modified end groups

To induce degradabilities in polymers in response to environmental conditions, endm odification reactions of poly(α-methylstyrene) (PMS) derivatives were carried out. 2-Phenylallyl halide derivatives such as 2-phenylallyl bromide, 2-(p-tolyl)allyl bromide, and α-trifluoromethylstyrene were found to be suitable end-modification agents. For example, the ω-2-phenylallyl-PMS derivative was prepared with almost quantitative functionality by the reaction of the living PMS derivative with 2-phenylallyl bromide. In a similar way, ω-3,3-difluoro-2-phenylallyl- and ω-2-(4-toly)allyl-PMS derivatives were synthesized. Based on thermogravimetric analysis, the onset of the degradation temperature of the endmodified PMS derivatives decreased in the following order: ω-hydrogen- > ω-3,3-difluoro-2-phenylallyl- > ω-2-phenylallyl- > ω-2-(p-tolyl)allyl-PMS. Actually, the onset temperature of ω-2-(p-tolyl)allyl-PMS derivatives was 50°C lower than that of ω-H-PMS derivatives. These results indicate that the active species is produced effectively at the endunsaturated bond, which initiates depolymerization of the polymer at rather low temperatures. Therefore, it is concluded that a 2-phenylallyl substituent at the end of the PMS chain induces effective degradation through a radical mechanism.     

Analysis of charge transfer distance between Ru(bpy)32+ complexes incorporated into a nafion film as studied by spectrocyclic voltammogram

An ITO electrode was coated by a Nafion film incorporating Ru(bpy)₃²⁺ complex as redox centers either by mixture casting method, adsorption method, or swelling method and the electrochemical reactivity of the modified electrode was determined by the in-situ spectrocyclic voltammogram (SCV) in a sodium perchlorate aqueous solution at pH 1.2. A modified Poisson statistics equation was used to estimate the charge transfer distance (Ro) between the Ru(bpy)₃²⁺ complexes. The estimated charge transfer distances for the electrodes prepared by swelling method (Ro = 1.63 nm for the electrode modified in M/W 1:10, and 1.69 nm in M/W 1:2) and adsorption method (Ro = 1.61 nm) were longer than that for mixture casting method (Ro = 1.5 nm). Based on the different procedure of Ru(bpy)₃²⁺ complex incorporation in the Nafion film, the reasons that affect the apparent charge transfer distance were discussed.     

A hydrogel with rubber elasticity transition

Reaction between dimethyldivinylsilane and 3,6-diazaoctane in the presence of 3-lithio-3,6-diazaoctane yields a new telechelic oligomer, poly(silamine), which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain. Poly(silamine) shows unique phase transition properties in response to the degree of protonation of amino groups in the polymer. Poly(silamine) also shows a strong interaction with several anions. Due to the interaction between poly(silamine) and anions along with the protonation of amino groups in the poly(silamine), the rubber elasticity of poly(silamine) is drastically changed. A discrete volume change can be observed when the environmental pH of the poly(silamine) gels is varied. This can be explained not only by a change in ionic osmotic pressure but also by a change in the rubber elasticity of the networks in the gel.     

Synthesis and reactions of optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl-(o-methoxyphenyl)phosphine-borane

Cyclohexyl(o-methoxyphenyl)menthyloxyphosphineborane and t-butyl(o-methoxyphenyl)menthyloxyphosphine-borane were prepared from dichlorocyclohexylphosphine and t-butyldichlorophosphine by successive treatments with (−)-menthol, o-methoxyphenylmagnesium bromide, and borane-THF complex. The separated pure diastereomers of each of the compounds underwent reaction with lithium naphthalenide to afford optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl(o-methoxyphenyl)phosphine-borane, respectively. These secondary phosphine-boranes reacted readily with various electrophiles in the presence of bases with virtually net retention of configuration. A new chiral phosphine ligand, (S,S)-1,2-bis[cyclohexyl(o-methoxyphenyl)phosphino]ethane was synthesized via the optically pure phosphine-boranes.     

Fragmentation of the metastable molecular ion of methyl lactate: The formation of oxygen-protonated methanol [CH3OH2]+ involving double hydrogen atom transfers

The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1^+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H₃, CO, CH₃?O, and ?OOCH₃, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH₃OH ₂ ⁺ ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 ^+· are present in the resultant protonated methanols.