Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004     

Terahertz time-domain spectra of aromatic carboxylic acids incorporated in nano-sized pores of mesoporous silicate.

Terahertz time-domain spectroscopy (THz-TDS) is used to study the intra- and intermolecular vibrational modes of aromatic carboxylic acids, for example, o-phthalic acid, benzoic acid, and salicylic acid, which form either intra- or intermolecular hydrogen bond(s) in different ways. Incorporating the target molecules in nano-sized spaces in mesoporous silicate (SBA-16) is found to be effective for the separate detection of intramolecular hydrogen bonding modes and intermolecular modes. The results are supported by an analysis of the differences in the peak shifts, which depend on temperature, caused by the different nature of the THz absorption. Raman spectra revealed that incorporating the molecules in the nano-sized pores of SBA-16 slightly changes the molecular structures. In the future, THz-TDS using nanoporous materials will be used to analyze the intra- and intermolecular vibrational modes of molecules with larger hydrogen bonding networks such as proteins or DNA.     

Nonlinear Cauchy problems with small analytic data

We study the lifespan of solutions to fully nonlinear Cauchy problems with small real- or complex-analytic data. Our proofs are based on the method of majorants and the fixed point theorem for a contraction mapping.

     

Spherical dye-doped silica particles

Organic dyes such as water soluble porphyrins were incorporated into monodispersed SiO₂ particles using the sol-gel technique (the Stober synthesis) and their monomeric and dimeric properties were investigated by aiming at the microcavity effect. Doping efficiencies of dyes into SiO₂ particles depended on dye's hydrophilic properties. The doping efficiency of a porphyrin, TTMAPP, decreased with increasing the nominal content in the starting solution and the doping content showed the maximum value of 1.6×10^–5 mol/g SiO₂. With increasing the TTMAPP content, spectra of doped particles were changed from dimeric to monomeric nature; the absorption peak due to dimers disappeared and halfwidth of absorption at Soret band decreased. This unusual change was caused by the decrease of particle sizes by dye doping. The TTMAPP-doped sample having monomeric spectrum showed the fluorescence life time of 8.5 nsec and photochemical hole burning at about 5 K.     

Crystal structure of the clathrate of 5,12-dihydro-5,12-o-benzenonaphthacene-1,4-dione with benzene (2:1).

In the crystal of the title compound, the quinone fragment of the host (1) participates in weak D-A interactions with a neighboring naphthalene moiety of 1 and with the guest molecule via fairly short intermolecular face-to-face contacts. An intermolecular electrostatic interaction between a quinone-oxygen atom and a neighboring quinone ring is suggested by short O...C contacts. There exist several C-H...O hydrogen bonds, one of which seems to contribute to the formation of a centrosymmetric dimer of 1.     

Quantitative assessment of solid oxide electrochemical doping

Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al₂O₃ (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al₂O₃ and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi₂Sr₂CaCu₂O_y (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm⁻²). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm⁻²). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount.     

Thermal properties and fracture toughness of a liquid‐crystalline epoxy resin cured with an aromatic diamine crosslinker having a mesogenic group

A mesogenic‐type curing agent was synthesized to introduce a mesogenic group not only into epoxy resin backbones but also into the crosslink units. In the mesogenic curing agent system, the domain size became larger, and the network arrangement in each domain existed to a greater extent than that in a system cured with the ordinary diamine curing system according to the evidence from polarized optical micrographs and polarized Fourier transform infrared mapping measurements. Moreover, the fracture toughness of the system was considerably improved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2486–2494, 2006     

Thermoanalytical characterization of carbon/carbon hybrid material, Apple Woodceramics

Woodceramics, a carbon/carbon composite of plant-originated carbon reinforced by glassy carbon from phenolic resin, was prepared from apple pomace at carbonizing temperatures of 1073 K (AWC800) and 1473 K (AWC1200), and characterized by thermoanalytical methods and X-ray diffraction (XRD). Simultaneous differential scanning calorimetry (DSC) and thermogravimetric (TG) showed complicated overlapping reactions similar to those of coal. The initial temperature of pyrolysis was obtained by fitting logistic functions to observed TG data. The results suggested that AWC1200 contained more volatile matter than AWC800. In an inert atmosphere, complicated devolatilization takes place. In an oxidizing atmosphere, thermal change occurs roughly in four steps: desorption of physically adsorbed matter; pyrolysis into aliphatic and aromatic fragments; ignition; combustion of char. The oxidation resistance of AWC1200 was superior to AWC800.     

Remarkably large positive and negative allosteric effects on ion recognition by the formation of a novel helical pseudocryptand

In supramolecular chemistry, a great deal of attention has focused on regulating guest binding via an external stimulus. To utilize the same effector for both highly guest-selective positive and negative allosteric effects, however, stricter and more precise regulation of the host structure is required. A novel allosteric host 1 binds Fe(II) to afford the pseudocryptand, 1.Fe(II), which bears a cavity that is surrounded by three polyether chains in a helical fashion. The binding selectivity of 1 (Na+ > K+ > Rb+ > Cs+) is the opposite of 1.Fe(II) (Cs+ > Rb+ > K+ > Na+). Single-ion transport through a liquid membrane shows ion selectivity similar to the equilibrium constants. To the best of our knowledge, this is the first example of an allosteric recognition system, in which the same effector, that is, Fe(II), exhibits both large positive and negative allosteric effects on equilibrium and dynamic recognition events. The X-ray analysis and 1H NMR examination indicate that the combination of the macrobicyclic effect and the intramolecular interchain interactions (CH-pi interaction and steric hindrance) finely controls the positive and negative allosteric effects, which depend on the size of the guest. The helical framework opens a new general method for constructing more sophisticated, controllable receptors for helical biomolecules, for example, DNA and proteins, and helical molecular devices such as a molecular coil or spring responding to a stimulus.     

Preparation and thermal analysis of synthetic malachite CuCO3·Cu(OH)2

The synthesis of malachite CuCO₃·Cu(OH)₂ or Cu₂CO₃(OH)₂ was studied through titrations of copper(II) salt solutions with a solution of sodium carbonate at different temperatures. The precipitates were characterized by TG, IR and chemical analysis. The composition varies depending on thepH of the solution and the temperature. Purer malachite was synthesized by simple mixing of a solution of copper(II) nitrate or sulfate with a solution of sodium carbonate at 50°C.The kinetics of the thermal decomposition of synthetic malachite was described by eitherR ₃ orA _m(m=1.2–1.4) law, according to TG analysis, both isothermal and nonisothermal. The Arrhenius parameters determined using three different integral methods showed the kinetic compensation effect, which is correlated to the working temperature interval analyzed.The authors thank Mr. H. Takemoto for analyzing kinetics of the thermal decomposition of synthetic malachite.