Cathodic performance of LiMn1−xMxPO4 (M = Ti, Mg and Zr) annealed in an inert atmosphere

To improve the cathodic performance of olivine-type LiMnPO₄, we investigated the optimal annealing conditions for a composite of carbon with cation doping. Nanocrystalline and the cation-doped LiMn_1−xM_xPO₄ (M = Ti, Mg, Zr and x = 0, 0.01, 0.05 and 0.10) was synthesized in aqueous solution using a planetary ball mill. The synthesis was performed at the fairly low temperature of 350 °C to limit particle size. The obtained samples except for the Zr doped one consisted of uniform and nano-sized particles. The performance of LiMnPO₄ was much improved by an annealing treatment between 500 and 550 °C with carbon in an inert atmosphere. A small amount of metal-rich phosphide (Mn₂P) was detected in the sample annealed at 900 °C. In addition, 1 at.% Mg doping for Fe enhanced the rate capability in our doped samples. The discharge capacity of LiMn_0.99Mg_0.01PO₄/C was 146 mAh/g at 0.1 mA/cm² and 125 mAh/g even at 2.0 mA/cm².     

Synthesis and characterization of 1,3,2-diazaboroine derivatives for organic thin-film transistor applications

2,2′-(1,4-Phenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [PND] and 2,2′-(4,4′-biphenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [BND] were synthesized and characterized by using differential scanning calorimetry (DSC) measurements, single crystal X-ray structure analysis, UV–vis absorption and electrochemical measurements, thin-film X-ray diffraction (XRD) and AFM studies. Organic field-effect transistors (OFETs) were fabricated by vacuum deposition with a bottom contact geometry using Au electrodes. Annealing treatment optimizes the organic active layer and increases the charge carrier mobility. Field-effect mobilities of 7.2 × 10^?3 for PND and 4.1 × 10^?4 cm² V^?1 s^?1 for BND were found.     

Solvated structure of C60 nanowhiskers

This work characterizes the structure of C₆₀ nanowhiskers prepared by the liquid-liquid interfacial precipitation method in the C₆₀-saturated m-xylene and isopropyl alcohol system. Transmission electron microscopy and X-ray diffraction measurement show that the C₆₀ nanowhiskers had a hexagonal structure with cell dimensions a = 2.407 nm and c = 1.018 nm which is different from pristine C₆₀. The structure of the C₆₀ nanowhiskers in solution is different from that of the solvated structure reported for the C₆₀ nanotubes but similar to that reported for the C₆₀ bulk crystal solvated with m-xylene. X-ray diffraction analysis also showed a shift to fcc structure after solvent evaporation. The C₆₀ nanowhiskers prepared using toluene as solvent also showed a similar solvated structure, and a more rapid structural change into fcc upon drying was again observed.     

Covalently cross-linked multilayer thin films composed of diazoresin and brilliant yellow for an optical pH sensor

The multilayered thin films composed diazoresin (DR) and brilliant yellow (BY) were fabricated by a layer-by-layer (LbL) deposition technique, and the ionic bonds between diazonium ion in DR and sulfonate residues in BY were converted to covalent bonds by UV light irradiation. The cross-linking between BY and DR prevented BY from desorption even in a pH 13 solution. The cross-linked (DR/BY)₁₀DR film exhibited pH-dependent absorption spectra in pH 9-13, and the response was repeatable and quick. The pH response time of the films was within a few seconds upon change from pH 9.0 to 13.0, and ca. 40 s upon change from pH 13.0 to 9.0.     

Synthesis of glucose-substituted poly(<Emphasis Type="Italic">p</Emphasis>-phenylene)s with twisted main-chain in one direction due to induced axial chirality

Summary The peracetylated and free glucose-substituted poly(p-phenylene)s were synthesized by the coupling polymerization of a dibromobenzene monomer using Ni complex and the subsequent deacetylation by hydrazine monohydrate. The polymerization was carried out using bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)₂) as a coupling agent with 2,2’-bipyridyl (bpy) and 1,5-cyclooctadiene (COD) in a mixed solvent of DMF and toluene. The structure of the product was confirmed by ¹H and ¹³C NMR measurements to be the poly(p-phenylene) having peracetylated glucose residues. The M_n values were estimated by GPC analysis with DMF as eluent to be 7300–9800. The fluorescence analysis of the polymer was carried out in comparison with that of the dimeric model compound. The CD spectrum of the polymer indicated that the main-chain was twisted and immobilized in one direction due to the chirality and bulkily of the peracetylated glucose residues. The deacetylation using hydrazine monohydrate completely took place to give the free glucose-substituted poly(p-phenylene).     

Observation of the solid-state formation of a TTF–CA complex by terahertz spectroscopy

The solid-state synthesis of a tetrathiafulvalene–chloranil (TTF–CA) complex was demonstrated, and progress in the formation of the complex was monitored using a GaP Raman terahertz (THz) spectrometer. Clear transitions in the THz absorption spectra indicated that the mixture of TTF and CA became the black phase TTF–CA complex. The results of X-ray diffraction, Raman scattering, and FTIR spectra are presented as supporting evidence.     

Purification and properties of a low-molecular-weight phytase from Cladosporium sp. FP-1

A fungus producing high levels of phytase was isolated from air and identified as Cladosporium sp. The phytase production was stimulated by phytate in the medium used. The maximum production of phytase (108 U/ml) occurred in a medium containing 1.0 g of phytate per 100 ml. The phytase was purified to electrophoretic homogeneity by ion-exchange chromatography and gel filtration. Based on SDS-PAGE analysis, the molecular weight of the purified phytase was calculated to be approximately 32.6 kDa, and the narrow protein band indicated that this phytase is not glycosylated. The phytase has an optimum pH of 3.5, and an optimum temperature of 40 degrees C. The phytase activity was stimulated by 2-mercaptoethanol and dithiothreitol, and inhibited by Ba2+, Pb2+, iodoacetate, p-chloromercuribenzoate and phenylmethylsulfonyl fluoride. The phytase displayed high affinity for phytate and the Km was 15.2+/-3.1 microM. NMR analyses (1D and 2D) indicated that the end hydrolysis product of phytate was myo-inositol 1,2,5-triphosphate.     

Mutational analysis of structure--activity relationships in human tumor necrosis factor-alpha

To determine the region of human tumor necrosis factor-alpha(TNF-), essential for cytotoxic activity against mouse L-M cells,single amino-acid-substituted TNF- mutant proteins (muteins)were produced in Escherichia coli by protein engineering techniques.An expression plasmid for TNF- was mutagenized by passage throughan E.coli mutD5 mutator strain and by oligonucleotide-directedmutagenesis. Approximately 100 single amino-acid-substitutedTNF- muteins were produced and assayed for cytotoxic activity.The cytotoxic activities of purified TNF- muteins, e.g. TNF-31T,-32Y, -82D, -85H, -115L, -141Y, -144K and -146E, were < 1%of that of parent TNF-. These results indicate that the integrityof at least four distinct regions of the TNF- molecule is requiredfor full biological activity. These regions are designated asfollows: region I, from position 30 to 32; region II, from position82 to 89; region III, from position 115 to 117; region FV, fromposition 141 to 146. In addition, TNF-141Y could not completelycompete with parent TNF- for binding to the receptor. This demonstratesthat region IV, and at least aspartk acid at position 141, mustbe involved in the TNF receptor binding site.     

Influence of temperature on the fatigue strength of compressed-hydrogen tanks for vehicles

The influence of environmental temperatures on the fatigue strength of compressed-hydrogen tanks for vehicles was investigated. The fatigue strength of Type-3 tanks was found to decrease in a low-temperature environment and increase in a high-temperature environment. The Type-3 tank has been subjected to autofrettage to improve fatigue strength. The investigation clarified that the effect of autofrettage changes according to the environmental temperature due to the difference between the coefficients of thermal expansion of carbon fiber reinforced plastic and aluminum alloy. This causes fatigue strength to change with changes in temperature. The Type-4 tank has a very long fatigue life and did not break after 45,000 cycles in a room-temperature or low-temperature environment. In a high-temperature environment, however, the tank broke in fewer than 45,000 cycles. The fatigue of carbon fiber reinforced plastic was promoted in the high-temperature environment, resulting in breakage of the tank. These results indicate that the fatigue strength of the tanks is influenced by the environmental temperature.