Growth of bubble-free Ti-doped Al2O3 single crystal by the czochralski method

The behaviour of bubble entrapment in Ti-doped Al₂O₃ single crystals grown by the Czochralski method was studied from the view point of crystal growth conditions such as the crystal rotation rate and kinds of growth atmosphere. The entrapment of bubbles was not correlated with the shape of solid-liquid interface dependent on crystal rotation rate. We found that the use fo He atmosphere, instead of the conventional atmosphere such as Ar, suppresses the formation of bubbles.     

Grafting of hyperbranched poly(amidoamine) onto carbon black surfaces using dendrimer synthesis methodology

To modify carbon black surface, the surface grafting of hyperbranched poly(amidoamine) onto the surface by using dendrimer synthesis methodology was investigated. Carbon black having amino groups (initiator sites) was prepared by the reduction of surface nitro groups introduced by nitration of aromatic rings. It was found that hyperbranched poly(amidoamine) was propagated from carbon black surface by repeating two processes: (1) Michael addition of methyl acrylate (MA) to surface amino groups and (2) amidation of the resulting esters with ethylenediamine: the percentage of poly(amidoamine) grafting reached to 96.2% after 10th‐generation. The grafting of hyperbranched poly(amidoamine) onto polystyrene‐bead as a model compound of carbon black was also achieved by the above procedures. However, the theoretical propagation of poly(amidoamine) dendrimer was not achieved, because of steric hindrance of grafted polymer. Hyperbranched poly(amidoamine)‐grafted carbon black gave a stable dispersion in a good solvent for poly(amidoamine). Copyright © 2001 John Wiley & Sons, Ltd.     

Crown ether strategy toward chemical activation of biological protein functions

The chemical activation of biological proteins is outlined, in which small molecules are used to alter the chemical and physical properties of biological proteins through direct or indirect interactions. Crown ethers have the potential to modulate the protein functions by supramolecular complexations, because they bind alkylammonium and other ionic residues of the proteins as well as ionic components in their systems. Two interesting examples are described in which crown ether derivatives improved the protein functions: (1) enhancement of reactivity and enantioselectivity in lipase‐catalyzed asymmetric reactions; and (2) generation of catalytic activity in the oxidation with cytochrome c. This chemical activation based on crown ether chemistry can be viewed as a complementary method to biological mutation in modifying the biological protein functions.     

An Outer Approximation Algorithm Guaranteeing Feasibility of Solutions and Approximate Accuracy of Optimality

We treat a concave programming problem with a compact convex feasible set. Assuming the differentiability of the convex functions which define the feasible set, we propose two solution methods. Those methods utilize the convexity of the feasible set and the property of the normal cone to the feasible set at each point over the boundary. Based on the proposed two methods, we propose a solution algorithm. This algorithm takes advantages over classical methods: (1) the obtained approximate solution is always feasible, (2) the error of such approximate value can be evaluated properly for the optimal value of such problem, (3) the algorithm does not have any redundant iterations.     

Growth of LiNbO3 epitaxial films by oxygen radical-assisted laser molecular beam epitaxy

LiNbO₃ films were epitaxially grown on c-sapphire substrates using oxygen radical-assisted laser molecular beam epitaxy (MBE). X-ray diffraction-based structural analysis showed that the films were epitaxial. Triple-axis rocking curve measurements of the LiNbO₃ (0 0 0 6) reflection revealed that the film was highly c-oriented with an extremely narrow mosaic; the full width at half maximum of the LiNbO₃ (0 0 0 6) rocking curve was 0.0036°, comparable to the value of high-quality bulk crystals. The surface of the film was very smooth, with a surface roughness r.m.s. value, measured by atomic force microscope, of 0.4 nm for a film of thickness 15 nm. The chemical composition of the film measured by X-ray photoelectron spectroscopy (XPS) was stoichiometric within the accuracy of XPS measurement.     

Low temperature thermodynamical properties of the organic chain conductor (TMTSF)AsF

We report on specific heat measurements of the quasi-one-dimensional organic salt (TMTSF)₂AsF₆ in its spin density wave state between 75 mK and 7 K. Similarly to (TMTSF)₂PF₆, we find discontinuities in the lattice contribution at 1.9 K an d 3.5 K ascribed to sub-spin density wave phases. Time-dependent effects due to dynamics of low-energy excitations in metastable states occur only below 0.2 K which yields an activation energy for the equilibrium energy relaxation process of 0.34 K, 4-5 times smaller than found for (TMTSF)₂PF₆. Finally the reduction of the low-energy excitations contribution to the specific heat in comparison to PF₆ reveals an intermediate cubic-like regime between 0.25 and 0.5 K that we tentatively describe as the phason contribution of the incommensurate spin density wave modulation. Received: 17 March 1998 / Revised: 27 July 1998 / Accepted: 22 September 1998     

A Complete Frequency-Field Chart for the Antiferromagnetic Resonance in MnF2

Antiferromagnetic resonance (AFMR) measurements on a well characterized single crystal sample of MnF₂ have been performed using various kinds of millimeter and submillimeter sources up to 570 GHz and a superconducting magnet up to 20 T. All the AFMR modes predicted from the theory have been observed. We report a complete frequency-field chart for these AFMR modes.     

Free‐radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio

Free‐radical copolymerizations of vinyl acetate (VAc = M₁) and other vinyl esters (= M₂) including vinyl pivalate (VPi), vinyl 2,2‐bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) with fluoroalcohols and tetrahydrofuran (THF) as the solvents were investigated. The fluoroalcohols affected not only the stereochemistry but also the polymerization rate. The polymerization rate was higher in the fluoroalcohols than in THF. The accelerating effect of the fluoroalcohols on the polymerization was probably due to the interaction of the solvents with the ester side groups of the monomers and growing radical species. The difference in the monomer reactivity ratios (r₁, r₂) in THF and 2,2,2‐trifluoroethanol was relatively small for all reaction conditions and for the monomers tested in this work, whereas r₁ increased in the VAc‐VF6Pi copolymerization and r₂ decreased in the VAc‐VPi copolymerization when perfluoro‐tert‐butyl alcohol was used as the solvent. These results were ascribed to steric and monomer‐activating effects due to the hydrogen bonding between the monomers and solvents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 220–228, 2000     

Stereocontrol in the free‐radical polymerization of methacrylates with fluoroalcohols

The free‐radical polymerization of methyl methacrylate (MMA), ethyl methacrylate (EMA), isopropyl methacrylate (IPMA), and tert‐butyl methacrylate (t‐BuMA) was carried out under various conditions to achieve stereoregulation. In the MMA polymerization, syndiotactic specificity was enhanced by the use of fluoroalcohols, including (CF₃)₃COH as a solvent or an additive. The polymerization of MMA in (CF₃)₃COH at −98 °C achieved the highest syndiotacticity (rr = 93%) for the radical polymerization of methacrylates. Similar effects of fluoroalcohols enhancing syndiotactic specificity were also observed in the polymerization of EMA, whereas the effect was negligible in the IPMA polymerization. In contrast to the polymerizations of MMA and EMA, syndiotactic specificity was decreased by the use of (CF₃)₃COH in the t‐BuMA polymerization. The stereoeffects of fluoroalcohols seemed to be due to the hydrogen‐bonding interaction of the alcohols with monomers and growing species. The interaction was confirmed by NMR measurements. In addition, in the bulk polymerization of MMA at −78 °C, syndiotactic specificity and polymer yield increased even in the presence of a small amount {[(CF₃)₃COH]/[MMA]_o < 1} of (CF₃)₃COH. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4693–4703, 2000     

Characterization of dissolved organic matter released from Microcystis aeruginosa.

The contribution of dissolved organic matter (DOM) released from phytoplankton (Microcystis aeruginosa) during cultivation and biodegradation was examined to clarify the causes of the organic pollution of Lake Biwa. Two peaks, peak 2 (retention time (RT) = 32 min) and peak 3 (RT = 35 min), were detected in the algal DOM released from Microcystis aeruginosa during cultivation and biodegradation by gel chromatography with a fluorescence detector (Ex = 340 nm, Em = 435 nm). As these peaks correspond with the peaks detected in the surface water of Lake Biwa, one can conclude that the algal DOM released from Microcystis aeruginosa during cultivation and biodegradation makes a considerable contribution to the refractory organic matter in Lake Biwa. Three fluorescence maxima were observed in the cultivation of Microcystis aeruginosa: a fulvic-like fluorescence peak (peak A) with Ex/Em values of 320/430 nm, a protein-like fluorescence peak (peak C) with Ex/Em values of 280/360 nm, and another peak with Ex/Em values of 240/370 nm. The fluorescence material of peak C has a larger MW than that of peak A. The algal-derived DOM from Microcystis aeruginosa has similar fluorescence to fulvic acid of soil origin but exhibits mainly hydrophilic characteristics. In the biodegradation of Microcystis aeruginosa, a fulvic-like fluorescence peak (peak B) with Ex/Em values of 250/440 nm and a peak with Ex/Em values of 320/380 nm were observed.