Analysis to obtain precise density fluctuation of supercritical fluids by small-angle X-ray scattering

A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO₂, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of T_r = T/T_c = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most.     

Dithiol-mediated immobilization of CdS nanoparticles from reverse micellar system onto Zn-doped silica particles and their high photocatalytic activity

Cds nanoparticles, prepared in a reverse micellar system, were immobilized directly onto alkanedithiol-modified Zn-doped silica particles, which were themselves prepared via hydrolysis of tetraethylorthosilicate in the presence of Zn(NO(3))(2) followed by contact with dithiol molecules. The resulting CdS-Zn-SiO(2) composite was then used as a photocatalyst for the generation of H(2) from 2-propanol aqueous solution. Under UV irradiation (lambda>300 nm), a high photocatalytic activity was observed for the CdS-Zn-SiO(2) composite material. This is effected by electron transfer from the photoexcited ZnS (dithiol-bonded Zn on SiO(2)) to CdS nanoparticles. The photocatalytic activity is increased with a decrease in the number of methylene groups in the dithiol molecules, according to the rank order 1,10-decanedithiol <1,6-hexanedithiol <1,2-ethanedithiol.     

Reaction of 2-dialkylamino-5-phenyl-1,3-oxathiolium cation with sulphur ylides

The reaction of 2-dialkylamino-5-phenyl-1,3-oxathiolium cation 1 with sulphur ylides 2 was investigated. The behavior of 1 was solvent-dependent. In CH₂Cl₂, carbamate ester 3 was obtained: in CH₃CN, the intermediate sulphonium salt 5, which on hydrolysis gave 3, was isolated. On the other hand, reaction in MeOH gave the diphenacyl derivative 6. The reaction mechanism is discussed.     

Cinnamate ester containing liquid crystalline side chain polymers

The synthesis of methacrylate esters of 4-cyanophenyl-(4-(ω-hydroxyalkyloxy)) cinnamates, with spacer lengths of 2 and 6 methylene units and the synthesis of the corresponding acrylate ester with a spacer of 2 methylene units are described. The methacrylate monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with the analogous benzoate monomer of spacer length 6. The acrylate ester could not be polymerized successfully under the same reaction conditions. Polymers were characterized by NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermo-optic observations. Of the monomers prepared, only the cinnamate with a hexamethylene spacer shows a mesophase, seen on supercooling of the melt. All of the polymers prepared were liquid crystalline, with smectic behavior predominating in the polymethacrylates with the longer spacer group. A narrow nematic region is seen just below the clearing temperature with a range of 3–9°C, nematic character is increased in the copolymer series with the degree of incorporation of the cinnamate monomer with the spacer group of length 2.     

Synthetic studies on carbapenem antibiotics from penicillins. IV. Stereoselective kinetic protonation of a chiral azetidinone enolate

A stereoselective kinetic protonation of the azetidinone enolate $\text{B}$ was studied and an efficient synthesis of$\text{2}$(cis) was achieved via aldol reaction of $\text{5}$ with acetone followed by the kinetic protonation with Ph₃SnH as proton source.     

Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Preparation of ZnO nanoparticles in a reverse micellar system and their photoluminescence properties

ZnO nanoparticles with spherical morphology and narrow size distribution were obtained by calcination of Zn(OH)2 nanoparticles, which were prepared in a polyethylene glycol mono-4-nonylphenyl ether (NP-5)/cyclohexane reverse micellar system and incorporated into polyurea (PUA) via an in situ polymerization of hexamethylene diisocyanate (HDI). The resulting ZnO nanoparticles demonstrated a near-UV emission and a green emission, the intensity ratio of which depended on calcination conditions. For the nanoparticles studied, the calcination atmosphere influenced remarkably the photoluminescence properties such as intensity ratio of the near-UV emission to green emission, rather than the size, morphology, and crystallinity of the ZnO nanoparticles. The green emission decreased by calcination in O2 flow but increased by calcination in N2 flow, as compared with the case calcined in air flow. This finding suggests that the green emission is enhanced with the increase of the number of oxygen vacancies of the ZnO nanoparticles and thus the photoluminescence properties of the nanoparticles were successfully controlled by the calcination condition, without changing the size and morphology.