Lubrication of Si3N4 and Al2O3 in water with and without addition of silane coupling agents in the range of 0.05–0.10 mol/l

To improve water lubrication of ceramics at a lower sliding velocity, the effect of the addition of silane coupling agents was investigated. Si₃N₄ and Al₂O₃ were slid against themselves in water with and without the addition of silane coupling agents in amounts ranging from 0.05 to 0.10 mol/l. Silane coupling agents containing one or more amino groups were effective in reducing the friction of Si₃N₄ and Al₂O₃ in water. Si₃N₄ also showed significant wear reduction but not Al₂O₃. However, the addition of a silane coupling agent containing an epoxy group increased both friction and wear of Si₃N₄. Improved lubricative characteristics of Si₃N₄ in water and in silane coupling agent solutions were obtained when Si₃N₄ contained smaller amounts of sintering additives. The adsorption behaviour of a silane coupling agent on ceramics was examined using both Fourier transform infrared spectroscopy and thin layer chromatography to clarify the interaction between the silane coupling agent and the ceramics. The role of polysiloxane film formation on ceramics is discussed to demonstrate the lubrication properties of ceramics.     

Hypergravity of 10<Emphasis Type="Italic">g</Emphasis> Changes Plant Growth,Anatomy, Chloroplast Size,and Photosynthesis in the Moss <Emphasis Type="Italic">Physcomitrella patens</Emphasis>

The photosynthetic and anatomical responses of bryophytes to changes in gravity will provide crucial information for estimating how these plant traits evolved to adapt to changes in gravity in land plant history. We performed long-term hypergravity experiments at 10g for 4 and 8 weeks using the moss Physcomitrella patens with two centrifuges equipped with lighting systems that enable long-term plant growth under hypergravity with irradiance. The aims of this study are (1) to quantify changes in the anatomy and morphology of P. patens, and (2) to analyze the post-effects of hypergravity on photosynthesis by P. patens in relation to these changes. We measured photosynthesis by P. patens for a population of gametophores (e.g., canopy) in Petri dishes and plant culture boxes. Gametophore numbers increased by 9% for a canopy of P. patens, with 24–27% increases in chloroplast sizes (diameter and thickness) in leaf cells. In a canopy of P. patens, the area-based photosynthesis rate (A _canopy) was increased by 57% at 10g. The increase observed in A _canopy was associated with greater plant numbers and chloroplast sizes, both of which involved enhanced CO₂ diffusion from the atmosphere to chloroplasts in the canopies of P. patens. These results suggest that changes in gravity are important environmental stimuli to induce changes in plant growth and photosynthesis by P. patens, in which an alteration in chloroplast size is one of the key traits. We are now planning an ISS experiment to investigate the responses of P. patens to microgravity.     

Evidence for the formation of interpenetrated spherulites in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) blends investigated by atomic force microscopy

The spherulitic morphology in poly(butylene succinate-co-butylene carbonate)/poly(l-lactic acid) (PEC/PLLA) blends was investigated by atomic force microscopy (AFM) to obtain direct evidence for the formation of interpenetrated spherulites (IPS), where the spherulites of PEC penetrate into PLLA spherulites. The observation actually revealed that PEC crystals penetrated into interfibrillar regions of edge-on lamellae in a PLLA spherulite. The penetration process was also investigated by AFM with a temperature controller. An edge-on PLLA lamella or a fibril that ran nearly perpendicular to the growth direction of a PEC spherulite obstructed the growth of PEC spherulite. The PEC crystals filled the blocked space after growing around the PLLA lamella. These results showed that the spherulites of PEC and PLLA grow on the same layer instead of forming a layered structure of two spherulites. All the results supported the formation of IPS.     

Synthesis of Optically Active Dendrimers Having Chiral Bisphosphine as a Core

Summary First and second generation chiral dendrimers P-1G1, P-2G1, P-1G2 and P-2G2 containing chiral bisphosphine as a core were synthesized via a reaction of chiral bisphosphine compound (S,S)-1 with benzyl ether dendrons. This is the first example of chiral dendrimers containing chiral phosphorus atoms. To investigate the effect of chiral phosphorus atoms on their conformations, optically inactive dendrimer P′-2G1 was synthesized as well using optically inactive initiator 1′ which was the mixture of rac-1 ((S,S)-1 and (R,R)-1) and meso-1. Their structures were characterized by ¹H, ¹³C, ³¹P NMR, and HRMS. According to CD measurement, optically active dendrimers exhibited the Cotton effect induced by the chirality of phosphorus atoms, while optically inactive dendrimer P′-2G1 showed no Cotton effect.     

Role of network nematicity in swelling and phase equilibria of polymer networks in nematic solvents

Swelling and phase equilibria of polymer networks in a low molecular mass liquid crystal (LC) have been investigated as a function of network nematicity. LC networks with varying nematicity were prepared by copolymerization of mixtures of mesogenic monomers and non-mesomorphic (styrene) monomers with various compositions. Molar fraction of mesogenic monomer (x) in copolymer network strongly influences the swelling behavior as well as the nematic-isotropic (N-I) transitions in both dry and swollen states. The swollen networks of sufficiently high x with strong nematicity exhibit a sharp N-I transition and simultaneously undergo a discontinuous change in gel volume, i.e. volume phase transition. Meanwhile, the swollen networks of x≤0.8 with less nematicity show a broad N-I transition, and the resulting volume change proceeds continuously over a finite temperature range. When x decreases further down to less than 0.5, the nematicity of the dry networks vanishes. The nematic ordering in the swollen copolymer networks of x<0.5 occurs at the same temperature as the N-I transition temperature of the pure nematic solvent (T_NI^S), which yields the inflection in the swelling-temperature curve. A mean field theory considering network nematicity as a variable describes the effects of x on volume phase transition such as a shift of T_NI^G and a change in the magnitude of volume transition, apart from the emergence of continuous volume transition due to the broad N-I transition. The purely isotropic network of x=0 appreciably swells in the nematic solvent. The solvent inside the gel forms the nematic phase at the temperatures below which conflicts with the classical theoretical prediction that nematic ordering of LC solvent in fully swollen isotropic network never occurs.     

The structure of the core polyol of the ether lipids fromSulfolobus acidocaldarius

The major ether-type lipid structures ofSulfolobus acidocaldarius (ATCC33909) were composed of caldarchaeol and calditoglycerocaldarchaeol. However, the characterization by nuclear magnetic resonance spectroscopy and mass spectrometry showed that the structure of calditol in calditoglycerocaldarchaeol is not nonitol, 2-(1′,2′,3′-trihydroxypropyl)1,2,3,4,5,6-hexahydroxyhexane, but 2-hydroxymethyl-1-(2,3-dihydroxypropoxy),2,3,4,5-cyclopentanetetraol with an ether linkage in the molecule. Such an intermolecular ether linkage was resistant, to BCl₃ treatment, but nonresistant to 57% HI degradation treatment conducted at 100°C for 60 h, producting 2-hydroxymethyl-1,2,3,4,5-cyclopentanepentaol from calditol as reaction product. Further, it was confirmed that the structure of calditol is essentially a derivative of glycerol, and hydrocarbon chains were conjugated to the glycerol-like site in the structure. The calditol with an ether linkage in the molecule suggested an important role regarding the properties of heat-resistance and acid-resistance observed inSulfolobales. Presented at the international workshop on “Molecular Biology and Biotechnology of Extremophiles and Archaebacteria,” Wako, Japan, August 1993.     

Pd-catalyzed hydrosilylation polymerization of a dihydrosilane with diyne/triyne mixed systems affording crosslinked silylene-divinylene polymers and their properties

Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy₃ (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td₅ values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm.     

关于城市的变异

面对仓促巨变的亚洲城市的严峻现实，设计者，包括建筑师、规划师和艺术家们，试图将个体的主张有效的介入城市生活，应对复杂的城市问题。作为2002上海双年展的策展人，作者介绍了由她推荐的十个艺术家和建筑师的作品。     

Fabrication of hierarchically porous spherical particles by assembling mesoporous silica nanoparticles via spray drying

A new type of hierarchically porous materials is fabricated by assembling mesoporous nanoparticles via spray drying. Well-dispersed mesostructured silica nanoparticles (MSN), whose particle size distribution was narrow in the range of 20 nm and 50 nm, were prepared by a thermal deposition method. By spray drying a MSN suspension, MSN were assembled into spherical secondary particles. After calcination, the spherical particles have two types of mesopores, mesopores of 3 nm in size inside of calcined MSN and larger inter-nanoparticle mesopores of about 15-20 nm. This hierarchical pore system should provide nanospaces for efficient mass transport of guest species with different sizes.