Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Vacuum‐driven fluid manipulation by a piezoelectric diaphragm micropump for microfluidic droplet generation with a rapid system response time

Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (V_p‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐V_p‐p increments over the range of 200?250 V_p‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications.     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

Silicon-Based Integrated Optic Pressure Sensor Using Intermodal Interference between TM-Like and TE-Like Modes

In this paper, a silicon-based integrated optic pressure sensor using an intermodal interference between the fundamental TM-like and TE-like modes is described. The sensor consists of a micromachined rectangular diaphragm and a straight polystyrene optical waveguide passing over the diaphragm. Its sensitivity is theoretically known to be strongly dependent on the position of the waveguide over the diaphragm. To experimentally investigate such dependence, we fabricated a sensor with a 1.2 mm ×10 mm ×20 μm diaphragm, over which waveguides were placed at 50 μm intervals. The measured phase sensitivity was 98 mrad/kPa for the waveguide nearest to the diaphragm edge. The measurement was also carried out for the other waveguides. As theoretically expected, the largest sensitivity was obtained for the waveguide nearest to the edge.     

Temperature dependence of the exafs spectrum in YBa2Cu3O7−δ compounds

The temperature dependence of the extended X-ray absorption fine structure (EXAFS) is studied in the high T_c superconductors, YBa₂Cu₃O_7−δ. The measurements were done at the Cu K-edge for samples of two orthorhombic phases (T_c≈90 K and ≈58 K, respectively) and a nonsuperconducting tetragonal phase. Interatomic distances and mean square relative displacements σ² for Cu-O bonds are determined by the least squares refinement. The results indicate that values of σ² increase near T_c for both the orthorhombic samples. It is concluded that this anomalous behavior related to T_c is caused by an anomalous vibration of oxygen atoms in the Ba-O layer. Changes in the Cu-O distances from 300 to 20 K are not found.     

Preparation of benzoylchitosans and their chiroptical properties in dilute solutions

Two benzoyl substituted chitosan derivatives, 3,6‐O‐dibenzoylchitosan (DBC) and 2‐N‐3,6‐O‐tribenzoylchitosan (TBC), were prepared, and their optical activities in organic solvent were investigated by circular dichroism (CD). For TBC, two splitting bands (a negative one at 288 nm and a positive one at 274 nm) corresponding to the ¹L_b transition of the benzoyl group were observed in chloroform and dichloromethane, while only a negative CD band was recorded in N, N‐dimethylformamide (DMF). These results indicated that the transition moments of benzoyl groups were orderly arranged along the helical polymer chain when TBC was dissolved in a solvent with low polarity, but the same ordered structure did not appear in a polar solvent of DMF. For DBC, only negative CD signals corresponding to the ¹L_b transition of the benzoyl group were observed, regardless of the solvent property, which indicated that the chromophores were not arranged in an ordered fashion with appropriate geometry to interact with one another to induce bi‐signate CD signals. Adding methanol or DMF to the solution of TBC/chloroform resulted in a progressive decrease of the intensity of the positive split band at 274 nm. The intensity of the positive band was weakened upon heating a solution of TBC/chloroform from 20 to 60 °C. The results suggested that the ordered arrangement of the chromophores in the TBC system was dependent on solvent and sensitive to temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4107–4115, 2004     

The epitaxial growth of gaas using alkylarsine: Part 2. molecular orbital calculation

Semi-empirical molecular orbital calculations were carried out for the compounds (C₂H₅)₃As, (C₂H₅)₃Ga and RAsH₂ (R = C₂H₅, i-C₃H₇, i-C₄H₉, and t-C₄H₉) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C₂H₅)₃As with (C₂H₅)₃Ga, we found that the β-elimination of (C₂H₅)₃As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C₂H₅AsH₂ than that in (C₂H₅)₃As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH₂, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested.     

Convenient synthesis of alkoxyhalosilanes from hydrosilanes

Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl₂ or NiCl₂ afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported.