Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Effect of increasing pressure on the structure and temperature-induced changes in magnetic properties of heterospin complexes

Russian Chemical Bulletin - The study is concerned with structural rearrangements in the crystals of heterospin complexes Cu(hfac)2 with nitroxide radicals LR (hfac is hexafluoroacetylacetonate, LR...     

Development of a Simulation Model for Solid Objects Suspended in a Fluctuating Fluid

We introduce a new scheme for the future application of Real-coded Lattice Gas (RLG) to the numerical simulation of suspended solid objects in a fluctuating fluid environment. The reproduction of Brownian motion for a single solid object is verified through the Gaussian distribution of its displacements. The effectiveness of the solid–solid interaction model is also confirmed in an N-body simulation.     

Rhodium-catalyzed addition of arylstannanes to carbon-heteroatom double bond

The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)₂]BF₄) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species.     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 2₁-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004     

Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

Effect of α‐cyclodextrin on the crystallization of poly (3‐hydroxybutyrate)

The effect of α‐cyclodextrin (α‐CD) on the crystallization behavior of poly(3‐hydroxybutyrate) (PHB) was investigated with polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. We found that the addition of α‐CD can greatly accelerate the crystallization of PHB and that α‐CD has a potential not only to enhance the nucleation but also to accelerate the crystallization of PHB. Compared to a conventional nucleation agent, such as talc, α‐CD is a natural product and has many advantages because it is environmentally friendly and safe to humans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3461–3469, 2004     

Measurement of circular dichroism spectra of liquid/liquid interface by centrifugal liquid membrane method.

The direct measurement of the circular dichroism (CD) spectra of liquid/liquid interface has been achieved for the first time by the centrifugal liquid membrane (CLM) method combined with a conventional CD spectropolarimetry. In the sample chamber of the CD spectropolarimeter, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at ca. 7000 rpm to generate a two-phase liquid membrane with a high specific interfacial area. The CD spectra of the J-aggregate of protonated 5,10,15,20-tetraphenylporphyrin formed at the toluene/sulfuric acid interface in the rotating cell have been measured. The results demonstrated the novelty and advantages of this method.