Synthesis of boron cluster lipids: closo-dodecaborate as an alternative hydrophilic function of boronated liposomes for neutron capture therapy

We succeeded in the synthesis of the double-tailed boron cluster lipids 4a-c and 5a-c, which have a B12H11S moiety as a hydrophilic function, by S-alkylation of B12H11SH (BSH) with bromoacetyl and chloroacetocarbamate derivatives of diacylglycerols for a liposomal boron delivery system on neutron capture therapy. Calcein encapsulation experiments revealed that the liposomes, prepared from the boron cluster lipid 4b, DMPC, PEG-DSPE, and cholesterol, are stable at 37 degrees C in FBS solution for 24 h. [reaction: see text].     

"O-acyl isopeptide method" for peptide synthesis: synthesis of forty kinds of "O-acyl isodipeptide unit" Boc-Ser/Thr(Fmoc-Xaa)-OH

The O-acyl isopeptide method has recently received attention as an efficient synthetic method for peptides. Herein, forty kinds of "O-acyl isodipeptide unit" Boc-Ser/Thr(Fmoc-Xaa)-OH (1-40) were effectively synthesized in two-steps without epimerization. The O-acyl isodipeptide units are important building blocks to enable the routine use of the O-acyl isopeptide method.     

Effects of Hydrogen for Different Stereospecific Active Sites on Ultra Low TiCl3 Loading Supported Catalyst

The relationship between the stereospecificity of active sites and hydrogen effects on propylene polymerization was investigated for MgCl₂‐supported TiCl₃ catalysts at ultra‐low Ti contents. Hydrogen had no effect on the catalyst activities for isospecific sites and for aspecific sites. The efficiency of hydrogen as a chain‐transfer agent was found to depend on the stereospecificity of the active sites. Hydrogen was effective for isospecific sites but was not effective for aspecific sites. From the viewpoint of hydrogen dissociation, isospecific sites should have hydrogen dissociation sites in their surroundings. Therefore, isospecific sites may be in the island to be affected by hydrogen and isolated sites may be aspecific or have low isospecificity.

     

Dynamics of 15N natural abundance in wood-decomposing fungi and their ecophysiological implications

Nine species of basidiomycota and one species of ascomycota were grown in an ammonium sulphate media and on beech wood; and the general (15)N dynamic patterns of the hyphae were examined. The fungal body initially became depleted in (15)N in both the types of incubation. However, the underlying mechanisms were quite different, that is, significant fungal (15)N drop on the beech wood is associated with the fungal N reallocation and the uptake of atmospheric ammonia and/or NO(x), in addition to isotope fractionation during assimilation. Although the (15)N values of the wood-decomposing basidiocarps were generally close to the (15)N values of the wood, it does not always indicate that the wood derived N was the sole N source for the fungi throughout the growth periods as shown in our wood-decomposing experiment.     

Be and P NMR analyses on Be complexation with cyclo-tri-μ-imidotriphosphate anions in aqueous solution

Microscopic information on the complexation of Be²⁺ with cyclo-tri-μ-imidotriphosphate anions in aqueous solution has been gained by both ⁹Be and ³¹P NMR techniques at −2.3 °C. Separate NMR signals corresponding to free and complexed species have been observed in both spectra. Based on an empirical additivity rule, i.e., proportionality observed between the ⁹Be NMR chemical shift values and the number of coordinating atoms of ligand molecules, the ⁹Be NMR spectra have been deconvoluted. By precise equilibrium analyses, the formation of [BeX(H₂O)₃]⁺ and [BeX₂(H₂O)₂]⁰ (X = non-bridging oxygen donor as a coordination atom in the phosphate groups) has been verified, and the formation of complexes coordinating with the nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. Instead, the formation of one-to-one (ML) complexes, one-to-two (ML₂), together with two-to-one (M₂L) complexes (L = cP₃O₆(NH)₃) has been disclosed, the stability constants of which have been evaluated as log K_ML = 3.87 ± 0.03 (mol dm⁻³)⁻¹, log K_ML2 = 2.43 ± 0.03 (mol dm⁻³)⁻² and log K_M2L = 1.30 ± 0.02 (mol dm⁻³)⁻², respectively. ³¹P NMR spectra measured concurrently have verified the formation of the complexes estimated by the ⁹Be NMR measurement. Intrinsic ³¹P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be²⁺, together with the ³¹P-³¹P spin-spin coupling constants have been determined.     

Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters

Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.     

Growth of ZnTe layers on (111) GaAs substrates by metalorganic vapor phase epitaxy

ZnTe layers were grown on (111) GaAs substrates by metalorganic vapor phase epitaxy using dimethylzinc and diethyltelluride as the source materials. X-ray diffraction analysis revealed that epitaxial ZnTe layers can be obtained on (111) GaAs substrates. X-ray rocking curves, Raman spectroscopy, and photoluminescence measurements showed that the crystal quality of ZnTe layers depends on the substrate temperature during the growth. A high-crystalline quality (111) ZnTe heteroepitaxial layer with strong near-band-edge emission at 550 nm was obtained at a substrate temperature of 440 °C.     

New description of structural disorder in silica glass

Structural changes in cristobalite and silica glass and melt are investigated at high temperatures by molecular dynamics simulations. The calculated interaction energies are analyzed employing a new method called ‘atomistic energy distribution analysis’. Each pair-interaction energy is divided into equal halves which are allocated to each atom. Therefore, each atom has the summed-up value (‘atomistic potential energy’) of half the pair-interaction energies. First, an analysis of atomistic energy distribution functions show a correspondence with structural changes such as α–β phase transition, cristobalite melting and glass transition of SiO₂, in harmony with the results obtained in our preceding study. Moreover, this study demonstrates the different roles of oxygen and silicon in terms of structural changes. Finally, newly defined order parameters offer the possibility of distinguishing structures resulting from different thermal histories through introduction of higher moments.     

Heteroepitaxial growth of InN layers on (1 1 1) silicon substrates

Indium nitride (InN) layers were grown on (1 1 1) silicon substrates by reactive magnetron sputtering using an indium target. Atomic force microscope, X-ray diffraction, and Raman spectroscopy analysis revealed that highly c-axis preferred wurtzite InN layers with very smooth surface can be obtained on (1 1 1) silicon substrates at a substrate temperature as low as 100 °C. The results indicate that the reactive sputtering is a promising growth technique for obtaining InN layers on silicon substrates at low substrate temperature with low cost and good compatibility with microelectronic silicon-based devices.     

Influence of plasma power and substrate temperature on structure of nanocrystalline germanium carbon thin films by VHF plasma CVD

The influence of plasma power and substrate temperature on the structure of nanocrystalline germanium carbon thin films was investigated. Films were deposited by the very high frequency plasma chemical vapor deposition technique using hydrogen diluted monomethylgermane (MMG). Plasma power strongly affected the decomposition of hydrogen and MMG. Crystalline volume fraction and bonding states of the atoms in the films depends on plasma power and substrate temperature. FT-IR measurements also revealed that Ge–H_n and CH_n bonds are sensitive to these factors.