Synthesis and Characterization of Cellulose Carbamates Having α-Amino Acid Moieties

Summary The reaction of cellulose with N-carbonyl α-amino acid ester 1 leading to cellulose carbamate 2 was carried out in N,N-dimethylacetamide at 100 °C. For N-carbonyl L-leucine ethyl ester (1a), the degree of the carbamate substituent (DS) in 2a was 2.5 for [1a]/[glucose units in cellulose] = 3.0 and reached ca. 3.0 for [1a]/[glucose units in cellulose] = 4.0. Cellulose carbamate 2a was highly soluble in not only aprotic polar solvents but also other organic solvents such as ethyl ether and methyl alcohol. The chiral discrimination ability of 2a was higher than those of the cellulose carbamates having L-phenylalanine and L-aspartic acid moieties.     

Size Controlled Synthesis of Gold Nanoparticles by Porphyrin with Four Sulfur Atoms

Tetradentate thioacetyl porphyrin ligand (1) was synthesized to protect gold nanoparticles. 1-protected gold nanoparticles were characterized by UV-vis spectroscopy and XPS. Analysis by XPS showed that all of four thioacetyl groups of 1 were dissociated and bound to the surface of gold nanoparticles in thiolate form. The size of 1-protected gold nanoparticles (GN:1) was controlled by thioacetyl group/HAuCl₄ molar ratio and approached to 2 nm. Compared with a protecting ligand without porphyrin plane (2) or dodecanethiol, 1 can control the size of gold nanoparticles efficiently probably due to the tetradentate ligation effect.     

Development of anchored oligothiophenes on substrates for the application to the tunable transparent conductive films

Bis(triethoxysilyl)-substituted oligothiophene with a moderate π-conjugation length was newly synthesized and polymerized to give a polysilsesquioxane network having oligothiophene units dispersed homogeneously without phase separation. The polymer was fixed on glass or ITO substrate by spin-coating and annealing. The resulting film exhibited a high mechanical strength due to the covalent bonding with the substrates, and was electrochemically stable even after 300 redox cycles in electrolyte solution. Chemical oxidation of the polymer films yielded electrically conductive and almost transparent films.     

Preparation and Characterization of Highly Fluorescent, Glutathione-coated Near Infrared Quantum Dots for in Vivo Fluorescence Imaging

Fluorescent probes that emit in the near-infrared (NIR, 700–1,300 nm) region are suitable as optical contrast agents for in vivo fluorescence imaging because of low scattering and absorption of the NIR light in tissues. Recently, NIR quantum dots (QDs) have become a new class of fluorescent materials that can be used for in vivo imaging. Compared with traditional organic fluorescent dyes, QDs have several unique advantages such as size- and composition-tunable emission, high brightness, narrow emission bands, large Stokes shifts, and high resistance to photobleaching. In this paper, we report a facile method for the preparation of highly fluorescent, water-soluble glutathione (GSH)-coated NIR QDs for in vivo imaging. GSH-coated NIR QDs (GSH-QDs) were prepared by surface modification of hydrophobic CdSeTe/CdS (core/shell) QDs. The hydrophobic surface of the CdSeTe/CdS QDs was exchanged with GSH in tetrahydrofuran-water. The resulting GSH-QDs were monodisperse particles and stable in PBS (phosphate buffered saline, pH = 7.4). The GSH-QDs (800 nm emission) were highly fluorescent in aqueous solutions (quantum yield = 22% in PBS buffer), and their hydrodynamic diameter was less than 10 nm, which is comparable to the size of proteins. The cellular uptake and viability for the GSH-QDs were examined using HeLa and HEK 293 cells. When the cells were incubated with aqueous solutions of the GSH-QDs (10 nM), the QDs were taken into the cells and distributed in the perinuclear region of both cells. After 12 hrs incubation of 4 nM of GSH-QDs, the viabilities of HeLa and HEK 293 cells were ca. 80 and 50%, respectively. As a biomedical utility of the GSH-QDs, in vivo NIR-fluorescence imaging of a lymph node in a mouse is presented.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

The effects of air pollution and climatic factors on atmospheric corrosion of marble under field exposure

The atmospheric corrosion of marble was evaluated in terms of SO₂ concentration as air pollution and climatic factors such as rainfall, relative humidity, temperature and so on under the field exposure. Marble of calcite type (CaCO₃) was exposed to outdoor atmospheric environment with and without a rain shelter at four test sites in the southern part of Vietnam for 3-month, 1- and 2-year periods from July 2001 to September 2003. The thickness loss of marble was investigated gravimetrically. X-ray diffraction and X-ray fluorescent methods were applied to study corrosion products on marble. The corrosion product of marble was only gypsum (CaSO₄ · 2H₂O) and was washed out by rain under the unsheltered exposure condition. It was found that the most substantial factors influencing the corrosion of marble were rainfall, SO₂ concentration in the air and relative humidity. Based on the results obtained, we estimated the dose-response functions for the atmospheric corrosion of marble in the southern part of Vietnam.     

A corrosion prediction method for weathering steels

Japanese Specification for Highway Bridges [Japan Road Association: Specification for Highway Bridges—I & II, 2002.3] has been revised in 2002, which clearly states that degradation of bridge members, including those of weathering steels, to occur in prolonged period of time must be taken into account at the design stage to realize long term structural durability. To cope with the revised paradigm, SABI chemistry committee in Japan Society of Corrosion Engineers has proposed durable state concept [SABI Chemistry Committee of Japan Society of Corrosion Engineers, in: Proc. 132nd Symposium for Corrosion and Protection, 2001.6.25, p. 3], which is defined as a condition in which corrosion rate of steel is slow enough not to form thick rust [H. Kihira, K. Shiotani, H. Miyuki, T. Nakayama, M. Takemura, Y. Watanabe, Doboku Gakkai Ronbun-shu (J. Japan Soc. Civil Engineers) No. 745/I-65, 2003.10, pp.77-87]. Since corrosiveness of atmosphere differs by location, a corrosion prediction method for both conventional and advanced weathering steels [H. Kihira, A. Usami, K. Tanabe, M. Ito, G. Shigesato, Y. Tomita, T. Kusunoki, T. Tsuzuki, S. Ito, T. Murata, in: Electrochemical Society Proceedings, vol. 99-26, 2000, pp. 127-136] is needed to ensure structural durability for future. Thus, versatile computational scheme for it has been derived through mathematical modeling based upon the durable state concept.     

Recovery retardation in equal channel angular pressed Al–Zr alloy during friction stir welding

The effect of Zr on reduction of hardness and microstructure in an FS weld of equal channel angular-pressed Al alloy was investigated. Zr addition to Al suppressed dynamic recovery in the thermomechanically affected zone and enabled retention of the high hardness of the ECA-pressed material throughout the weld.     

Tensile properties of ultrahigh strength PAN-based, ultrahigh modulus pitch-based and high ductility pitch-based carbon fibers

The tensile properties and fracture behavior of ultrahigh tensile strength PAN-based (T1000GB), ultrahigh modulus pitch-based (K13D) and high ductility pitch-based (XN-05) carbon fibers have been investigated. The statistical distributions of the tensile strength were characterized. The Weibull modulus for the T1000GB, K13D and XN-05 fibers were calculated to be 5.9, 4.2 and 7.9, respectively. The results clearly show that for PAN- and pitch-based carbon fibers, the Weibull modulus decreases with an increase in the tensile modulus and the mean tensile strength.