Visible-light-sensitive photocatalytic reaction on chromium-containing mesoporous silica: selective partial oxidation of propane with molecular oxygen

The photocatalytic reactivities of chromium-containing mesoporous silica molecular sieves (Cr-HMS) under visible light irradiation have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O groups. In the presence of propane with molecular oxygen, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein, with high selectivity, while a complete oxidation proceeded under UV light irradiation mainly to produce CO₂. The charge-transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactions.     

Developing a hybrid emulsion polymerization system to synthesize Fe3O4/polystyrene latexes with narrow size distribution and high magnetite content

A hybrid emulsion polymerization was formulated for synthesizing Fe₃O₄/polystyrene composite latex. This system, containing binary droplets that are magnetic (Mag)‐droplets with a diameter of 100–200 nm and styrene (St)‐droplets with a diameter of 3–4 μm, was obtained by mixing Mag‐miniemulsion and St‐macroemulsion. With extremely low surfactants concentration (?critical micelle concentration, CMC), the nucleated loci are selectively controlled in the Mag‐droplets, as the result of smaller droplet size and larger surface ratio. Both water‐soluble potassium persulfate (KPS) and oil‐soluble 2,2′‐azobis(2‐isobutyronitrile) was adopted to initiate the polymerization. In the presence of KPS, magnetic polystyrene latices with particles size of 60–200 nm, narrow size distribution, and high magnetite content (86 wt % measured by TGA) were attained successfully. The synthesized magnetic Fe₃O_4/polystyrene latices assembled into well‐ordered hexagonal structure in the surface of a carbon supported copper grid. The influence of various parameters on various aspects of the as‐synthesized Fe₃O₄/polystyrene was investigated in detail: type of initiator on composite morphology, feed ratio of Mag‐miniemulsion and St‐macroemulsion on magnetite content, and hydrophobic agent or amount of surfactant on size and size distribution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5285–5295, 2007     

Intake of different chemical species of dietary arsenic by the japanese,and their blood and urinary arsenic levels

We calculated the intake of each chemical species of dietary arsenic by typical Japanese, and determined urinary and blood levels of each chemical species of arsenic. The mean total arsenic intake by 35 volunteers was 195±235 (15.8-1039) μg As day^?1, composed of 76% trimethylated arsenic (TMA), 17.3% inorganic arsenic (As_i), 5.8% dimethylated arsenic (DMA), and 0.8% monomethylated arsenic (MA): the intake of TMA was the largest of all the measured species. Intake of As_i characteristically and invariably occurred in each meal. Of the intake of As_i, 45-75% was methylated in vivo to form MA and DMA, and excreted in these forms into urine. The mean measured urinary total arsenic level in 56 healthy volunteers was 129±92.0 μg As dm^?3, composed of 64.6% TMA, 26.7% DMA, 6.7% As_i and 2.2% MA. The mean blood total arsenic level in the 56 volunteers was 0.73±0.57 μg dl^?1, composed of 73% TMA, 14% DMA and 9.6% As_i. The urinary TMA levels proved to be significantly correlated with the whole-blood TMA levels (r = 0.376; P<0.01).     

Hydrogel‐like elastic membrane consisting of semi‐interpenetrating polymer networks based on a phosphorylcholine polymer and a segmented polyurethane

To obtain a hydrogel‐like elastic membrane, we prepared semi‐interpenetrating polymer networks (IPNs) by the radical polymerization of methacrylates such as 2‐methacryloyloxyethyl phosphorylcholine (MPC), 2‐hydroxyethylmethacrylate, and triethyleneglycol dimethacrylate diffused into segmented polyurethane (SPU) membranes swollen with a monomer mixture. The values of Young's modulus for the hydrated semi‐IPN membranes were less than that for an SPU membrane because of higher hydration, but they were much higher than that for a hydrated MPC polymer gel (non‐SPU). According to a thermal analysis, the MPC polymer influenced the segment association of SPU. The diffusion coefficient of 8‐anilino‐1‐naphthalenesulfonic acid sodium salt from the semi‐IPN membrane could be controlled with different MPC unit concentrations in the membrane, and it was about 7 × 10² times higher than that of the SPU membrane. Fibroblast cell adhesion on the semi‐IPN membrane was effectively reduced by the MPC units. We concluded that semi‐IPNs composed of the MPC polymer and SPU may be novel polymer materials possessing attractive mechanical, diffusive‐release, and nonbiofouling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 68–75, 2003     

Stereoselective synthesis of (25R)-25,26-dihydroxy-23-oxovitamin D3 and its enzymatic conversion to (25R)-1α,25,26-trihydroxy-23-oxovitamin D3, a putative metabolite of vitamin D3

(25$\text{R}$)-25,26-Dihydroxy-23-oxovitamin D₃ was synthesized efficiently and stereoselectively, and it was converted enzymatically to (25$\text{R}$)-1α,25,26-trihydroxy-23-oxovitamin D₃, a putative metabolite of 1α,25-dihydroxyvitamin D₃. The spectral and chemical properties of (25$\text{R}$)-25,26-dihydroxy-23-oxovitamin D₃ and its 1α,hydroxylated derivative disagree with those reported for the isolated metabolite.     

Diastereomeric Difference of the Self-Inclusion Complex of N(N′-Formyl-Phenylalanyl)-Deoxyamino-β-Cyclodextrin Caused by the Interaction between the Arm and the Rim of the Cavity

A complete assignment of proton resonances for N(N-formyl d-phenylalanyl)-deoxyamino--cyclodextrin (1d) was performed by means of 1D and 2D NMR,¹H–^1H-COSY, ¹H–^13C-COSY, TOCSYand NOESY spectroscopy. Based on 2D-NMR ROESY and circular dichroism spectroscopy, the conformation of 1d was determined; the phenyl group stays inside the distorted cyclodextrin (CyD) cavity forming a self-inclusion complex, which is almost the same as N(N-formyl l-phenylalanyl)-deoxyamino--CyD (1l). The remarkable diastereomeric difference was observed in the chemical shifts of H(5) and H(6) protons at the narrow rim of the CyD cavity and induced circular dichroism spectra. These results suggest the existence of hydrogen bonds between the hydroxyl group on CyD and the amide groups on the arms, which provides the difference in the molecular recognition properties.     

Polymerization of β-cyanopropionaldehyde. IV. Polymerization by the adducts of β-cyanopropionaldehyde with triethylaluminum

Adducts (X, Y, and Z) between triethylaluminum and β-cyanopropionaldehyde (CPA) have been prepared and characterized. It was found that an equimolar amount of triethylaluminum undergoes Grignard type addition reaction with aldehyde group of CPA to give aluminum alkoxide and that another equimolar quantity of triethylaluminum undergoes coordination with the nitrile group of CPA (adduct X, in which the molar ratio of CPA to aluminum is 1:2). The coordinated triethylaluminum in adduct X may be changed to aluminum alkoxide by the addition of further equimolar amount of CPA (adduct Y, molar ratio = 1:1); on the other hand, heating at 130°C affords mixtures of aluminum aldimine and aluminum ketenimine structures (adduct Z, molar ratio = 1:2). From the cryoscopic measurement, adduct Z may be regarded as a coordinated polymer joined through bridged structures I and II. In the polymerization of CPA at ?78°C, the stereoregularity of the resulting poly-(cyanoethyl)oxymethylene was found to increase in the order: X < triethylaluminum < Y < Z. The polymerizations with triethylaluminum, X, and Y are considered to be initiated by NCCH₂CH₂CH(C₂H₅)? O? Al(C₂H₅)₂. The degree of association of the species may influence the stereoregularity of the polymer.     

Stereoselectivity in the collision-activated reactions of gas phase salt complexes

The collision-activated dissociations (CAD) of gas phase salt complexes composed of chiral ions were studied in a quadrupole ion trap mass spectrometer. Because both partners in the salt are chiral, diastereomeric complexes can be formed (e.g., RR, RS). Two general types of complexes were investigated. In the first, the complex was composed of deprotonated binaphthol and a chiral bis-tetraalkylammonium dication. CAD of these complexes leads to the transfer of a proton or an alkyl cation to the binaphtholate leading to a singly-charged tetraalkylammonium cation. During CAD, diastereomeric complexes give significantly different product distributions indicating reasonable stereoselectivity in the process. In the second system, the complexes involved a peptide dianion and a chiral tetraalkylammonium cation. These systems may be viewed as very simple models for the interactions of peptides/proteins with small chiral molecules. Again, stereoselectivity was evident during CAD, but the extent was dependent on the nature of the peptide and not observable in some cases. To better understand the structural features needed to achieve stereoselectivity in gas phase salt complexes, representative transition states were modeled computationally. The results suggest that it is critical for the asymmetry of the nucleophile (i.e., anion) to be well represented in the vicinity of its reactive center.