Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species

A treatment of cobalt oxide supported gold nanoparticles (Au/Co₃O₄) under syngas atmosphere effectively generated a cobalt carbonyl-like active species in the reaction vessel. The preparation of Au/Co₃O₄ was quite simple and the in situ generated cobalt species could be used as a stable and easy handling alternative for dicobalt octacarbonyl without bothersome purification prior to use. The reactions, which are sensitive to the purity of the dicobalt octacarbonyl, such as the alkoxycarbonylation of epoxides and the Pauson-Khand reaction, smoothly progressed with Au/Co₃O₄.     

Synthesis of hollow CaCO3 nanospheres templated by micelles of poly(styrene-b-acrylic acid-b-ethylene glycol) in aqueous solutions

An asymmetric triblock copolymer, poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG), was synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Micelles of PS-b-PAA-b-PEG with PS core, PAA shell, and PEG corona were then prepared in aqueous solutions, followed by extensive characterization based on dynamic light scattering, zeta-potential, and transmission electron microscopy (TEM) measurements. The well-characterized micelles were used to fabricate hollow nanospheres of CaCO(3) as a template. It was elucidated from TEM measurements that the hollow nanospheres have a uniform size with cavity diameters of ca. 20 nm. The X-ray diffraction analysis revealed a high purity and crystallinity of the hollow nanospheres. The hollow CaCO(3) nanospheres thus obtained have been used for the controlled release of an anti-inflammatory drug, naproxen. The significance of this study is that we have overcome a previous difficulty in the synthesis of hollow CaCO(3) nanospheres. After mixing of Ca(2+) and CO(3)(2-) ions, the growth of CaCO(3) is generally quite rapid to induce large crystal, which prevented us from obtaining hollow CaCO(3) nanospheres with controlled structure. However, we could solve this issue by using micelles of PS-b-PAA-b-PEG as a template. The PS core acts as a template that can be removed to form a cavity of hollow CaCO(3) nanospheres, the PAA shell is beneficial for arresting Ca(2+) ions to produce CaCO(3), and the PEG corona stabilizes the CaCO(3)/micelle nanocomposite to prevent secondary aggregate formation.     

Formation of a silicato complex of zinc in aqueous solution and its accelerating effect on the formation of silica scales in cooling water systems

This study elucidates the effect of zinc (Zn), which is an anticorrosive water additive, on the formation of silica scales from cooling water. In these experiments, the silica scales were analyzed by EPMA, and the results indicate that Zn is sorbed into the silica scales during formation. Measurements of the solubility of Zn(OH)(2) at various concentrations of silicic acid demonstrate that Zn is present as a silicato complex of Zn (SCZ) in cooling water. From adsorption experiments of the SCZ on silica and alumina, which are major components of the silica scales, it can be concluded that the SCZ accelerates the formation of silica scales from cooling water.     

Kinetics of phase separation and coarsening in dilute surfactant pentaethylene glycol monododecyl ether solutions

We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C(12)E(5)) solutions focusing on the growth law of separated domains. The solutions confined between two glass plates were found to exhibit the phase inversion, characteristic of the viscoelastic phase separation; the majority phase (water-rich phase) nucleated as droplets and the minority phase (micelle-rich phase) formed a network temporarily, then they collapsed into an usual sea-island pattern where minority phase formed islands. We found from the real-space microscopic imaging that the dynamic scaling hypothesis did not hold throughout the coarsening process. The power law growth of the domains with the exponent close to 1/3 was observed even though the coarsening was induced mainly by hydrodynamic flow, which was explained by Darcy's law of laminar flow.     

Easy access to fully functionalized chiral tetrahydro-β-carboline alkaloids

A four-step synthetic route to fully substituted chiral tetrahydro-β-carbolines (THBCs) is described. Starting from the (R,S,S)-Friedel-Crafts/Henry adduct obtained from three-component coupling of an indole, nitroalkene, and aldehyde catalyzed by imidazoline-aminophenol-CuOTf, the (1S,3S,4R)-THBCs were readily synthesized in a three-step operation including reduction of the nitro-functionality and Pictet-Spengler cyclization.     

A theoretical and experimental study on translational and internal energies of H2O and OH from the 157 nm irradiation of amorphous solid water at 90 K

The photodesorption of H(2)O in its vibrational ground state, and of OH radicals in their ground and first excited vibrational states, following 157 nm photoexcitation of amorphous solid water has been studied using molecular dynamics simulations and detected experimentally by resonance-enhanced multiphoton ionization techniques. There is good agreement between the simulated and measured energy distributions. In addition, signals of H(+) and OH(+) were detected in the experiments. These are inferred to originate from vibrationally excited H(2)O molecules that are ejected from the surface by two distinct mechanisms: a direct desorption mechanism and desorption induced by secondary recombination of photoproducts at the ice surface. This is the first reported experimental evidence of photodesorption of vibrationally excited H(2)O molecules from water ice.     

Comparative study of complete and incomplete Freund's adjuvants for immunization of a drug immunogen using enzyme immunoassay methods

Highly sensitive and accurate enzyme immunoassays (EIAs), a sandwich EIA for mouse immunoglobulin G (IgG) and an enzyme linked immunosorbent assay for mouse antibody specific to viomycin (VM), were developed. Accuracy and specificity of the assay results were confirmed before their application. The changes of total IgG and antibody specific to VM in mice, immunized with a VM-immunogen with or without two types of Freund's adjuvants under various conditions, were assessed by means of the newly developed EIA methods. Both methods were very useful tools to follow the immunization processes of mice, and complete and incomplete Freund's adjuvant were found to have similar adjuvant activities for production of antibody specific to VM, judging from the amounts of anti-VM antibody formed. It seems to be important that too many booster injections should be avoided in the immunization of mice with a hapten immunogen.     

Asymmetric Colliding-Pulse Mode-Locking in InGaAsP Semiconductor Lasers

Asymmetric colliding-pulse mode-locking was successfully demonstrated in an InGaAsP laser. This laser had a single saturable absorber section located partway along the cavity length, and showed mode-locking operation at harmonics of the cavity roundtrip frequency. The method verified that optical pulse repetition up to subterahertz rates can be generated with nearly 1-mm-long mode-locked InGaAsP lasers.     

An active resonator system for CW-ESR measurement operating at 700 MHz

An active resonator system operating at 700 MHz, which can attain a high Q for CW-ESR measurements of a high loss sample, was developed. This system consisted of a loop-gap resonator (LGR), a receiver coil, an excitation coil, and a phase tunable amplifier. A part of the RF power at the LGR was picked up by the receiver coil, amplified, and irradiated to the LGR again by the excitation coil, which made up a feedback circuit. Because the feedback circuit provided the energy that canceled the loss in the resonator, the Q of the active resonator system increased. When a sample tube (inner diameter, 20 mm; axial length, 31 mm) containing a nitroxide radical and physiological saline solution was placed in the resonator, the Q could be varied from 55 to 4000. It was possible to obtain a Q of the active resonator system with sample that was higher than that of the value of the LGR without a sample in a no-feedback condition. The ESR signal intensity increased up to 7 times with the increase in Q. The sensitivity increased up to 50%, which was a much smaller advance than that of the Q, because the noise level also increased with the increase in signal intensity.