Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.     

Free-energy analysis of the electron-density fluctuation in the quantum-mechanical/molecular-mechanical simulation combined with the theory of energy representation

The relationship is investigated for QM/MM (quantum-mechanical/molecular-mechanical) systems between the fluctuations of the electronic state of the QM subsystem and of the solvation effect due to the QM-MM interaction. The free-energy change due to the electron-density fluctuation around its average is highlighted, and is evaluated through an approximate functional formulated in terms of distribution functions of the many-body coupling (pairwise non-additive) part of the QM-MM interaction energy. A set of QM/MM simulations are conducted in MM water solvent for QM water solute in ambient and supercritical conditions and for QM glycine solute in the neutral and zwitterionic forms. The variation of the electronic distortion energy of the QM solute in the course of QM/MM simulation is then shown to be compensated by the corresponding variation of the free energy of solvation. The solvation free energy conditioned by the electronic distortion energy is further analyzed with its components. It is found that the many-body contribution is essentially equal between the free energy and the average sum of solute-solvent interaction energy.     

Initial testing of a high-repetition-rate electron-beam-pumped KrF laser amplifier

The initial test results of the high-repetition-rate (rep-rate) electron-beam (e-beam) pumped KrF laser amplifier under development in our laboratory are reported. This amplifier is aimed at producing a laser energy of 20 J per pulse at a rep rate of 1 Hz. Thus far, 700 consecutive e-beampulses (250 kV, 270 J/pulse) were generated at a rep rate of 1 Hz. The laser gas was repetitively pumped by the e-beams injected through the water-cooled diaphragm foils. Received: 5 February 2001 / Published online: 21 March 2001     

Estimation of the latent track size of CR-39 using atomic force microscope

As a frame work of the study for the latent track size measurement using atomic force microscope, we have measured the minute etch pits and the extremely small amount of bulk etch of CR-39 at the beginning of chemical etching, and obtained its growth curves in nanometer dimensions. The pieces of CR-39 were exposed to 6 MeV/nC and Fe ions with normal incidence angle and were etched in 70°C 7 N NaOH solution for 0.5,1,2,3,5 min. The diameters of latent track were estimated to be 17 nm for Fe ions and 8 nm for C ions, respectively. These values are comparable to the experimental data on the average ‘track core diameters’ that have been obtained by various experimental techniques.     

A report on the 31st Symposium on Heteroatom Chemistry of the Chemical Society of Japan

The 31st domestic Chemical Society of Japan Symposium on Heteroatom Chemistry was held in Wakayama during the period of December 8–10, 2004, under the management of Waro Nakanishi and Satoko Hayashi of Wakayama University. About 250 chemists from various academic institutes and industries enjoyed five plenary lectures, 40 oral presentations, and 72 poster presentations. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:535–547, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20134     

Synthesis and polymerization of new styryl and methacryloyl monomers containing acidic saccharide moieties

New styryl‐type water‐insoluble and methacryloyl‐type water‐soluble monomers, N‐(p‐vinylbenzyl)‐1,2‐O‐isopropylidene‐6‐D ‐glucofuranuronamide and N‐(2‐methacryloylamino)ethyl‐1,2‐O‐isopropylidene‐6‐D ‐glucofuranuronamide, were synthesized from the most common acidic saccharide, D ‐glucuronic acid. Their radical homopolymerizations and copolymerizations with styrene and acrylamide were tried under various conditions. The isopropylidene groups in the resulting polymers were removed in a mixture of trifluoroacetic acid and water (2/1 v/v) to give the corresponding polymers with many pendant D ‐glucopyranuronyl groups with reactive reducing groups. The pendant reducing ends may be useful as potential binding sites under a hydrophilic atmosphere. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3893–3901, 2001     

Theoretical prediction of vertical transition energies of diaminosilylenes and aminosubstituted disilenes

Vertical electronic transition energies of diaminosilylenes and their dimers (disilenes and nitrogen‐bridged) were investigated by ab initio and density functional calculations. A good linear correlation was found between the observed UV transition energies of various silylenes and disilenes and those of model compounds calculated using the CIS and TD–DFT methods. On the basis of these computations the experimental UV absorption maximum observed for the dimer of (i‐Pr₂N)₂Si: (λ_max 439 nm at 77 K), could be assigned to an Si? Si bonded dimer with an unusually long Si? Si distance of 2.472 Å, and the isomeric amino‐bridged cyclic dimer could be discarded. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1536–1541, 2001     

Melt rheology and structure of silicone resins

Rheological investigation and X-ray analysis of silicone resins have been performed to get a fundamental understanding of the relationship between melt rheology and structure. Rheological properties of the melts of silicone resins were characterized by dynamic shear measurements. Samples were a series of silicone resins having different side groups, such as methyl, phenyl, methylphenyl, and propylphenyl. A time-temperature superposition based on the WLF rule was successfully applicable. The free volume fraction at the glass transition temperature and the free volume expansion coefficient were estimated from the C₁ and C₂ values of the WLF-equation. The loss modulus G′′ was found to be proportional to the angular frequency in a double-logarithmic plot over a wide frequency range. However, the storage modulus G′ exhibited a bending in a intermediate frequency region for all silicone resins. The shape of the G′ curve is unexpected from the results of gel permeation chromatography (GPC) and differential scanning calorimeter (DSC), which demonstrate that the silicone resins are amorphous polymers of relatively low molecular weight. To get more insight into the rheological properties of the silicone resins which indicate a heterogeneous structure, X-ray analysis was carried out. The X-ray measurement displayed two peaks, one broad peak around 4.5?Å of d-spacing which corresponds to a random amorphous structure, and the other higher intensity peak from 8.5?Å to 12?Å. This peak strongly depends on the size of organic side groups. From the rheological characterization and the X-ray analysis, it can be concluded that the silicone resins consist of two components; one of them shows a random amorphous and the other a regular structure even in the molten stage.