Preparation and ionic conductivity of transparent glass−ceramics containing a large quantity of lithium−mica

In order to crystallize a large quantity of the lithium?mica in glass?ceramics, 5.1 mass% MgF₂ was added to the starting materials of the parent glasses having chemical compositions of Li_(1+x)Mg₃AlSi_3(1+x)O_10+6.5xF₂ (x = 0.5 and 1.0). Transparent glass?ceramics, in which a large quantity of lithium?mica with particle size of <50 nm was separated, could be prepared from the MgF₂-added parent glass with x = 0.5. While the parent glass, which had a binodal phase separation structure, did not exhibit electrical conductivity, the transparent glass–ceramic was given conductivity by the formation of an interlocking structure of mica. As the separated mica formed a tighter interlocking structure, the conductivity increased and reached a value of 2.0 × 10^?3 S/cm at 600 °C. The MgF₂-added parent glass with x = 1.0 was not transparent because of coarse spinodal phase separation. The conductivity was 4.3 × 10^?4 S/cm at 600 °C but was significantly decreased by the separation of mica.     

Thermal rearrangements of allyl 2,2-dichlorovinyl and 1,2,2-trichlorovinyl sulfides

Unique rearrangements of allyl 2,2-dichlorovinyl and 1,2,2-trichlorovinyl sulfides have been found. On heating the former gave 1,2-dichloro-l,4-pentadienes and the latter 2,3-dichloro-5-chloromethyl-4,5-dihydrothiophenes and 3,5,6-trichloro-3,4-dihydro-2H-thiopyranes .     

Primary dependence of 7-aryl-2,5-di-t-butyl-1,3,5-cycloheptatriene valence tautomerism on the π-acceptor strength of the 7-aryl substituent

¹³C NMR studies showed that the population of the norcaradiene form of the title systems containing p-CH₃O, H, and p-CF₃ on the 7-aryl group increases in this order. The result is consistent with the prediction from the π-acceptor strength of the aryl group estimated by INDO calculations.     

Polymerization of allyl esters of unsaturated acids. VII. Copolymerization of methyl allyl maleate and fumarate with styrene

Radical copolymerizations of methyl allyl maleate (MAM) and methyl allyl fumarate (MAF) with styrene (St) are carried out in bulk using AIBN as an initiator at 60°C, and their copolymerization behaviors are compared in detail. The different rate features are observed with each other; thus in the MAF-St copolymerization the rate was quite enhanced and, also, the maximum rate was found at the molar ratio of 1:1 in the monomer feed, whereas no maximum phenomenon of the rate was apparent for the MAM—St copolymerization. The copolymerizability of MAF with St was quite high, whereas that of MAM was very poor. The cyclization of MAM or MAF was hindered by the highly reactive St monomer. These results are discussed in terms of the formation of the charge—transfer complex between MAF and St and, furthermore, the cyclocopolymerization kinetics involving the 17 elementary reactions as the propagation reactions.     

A simplified optical method for measuring residual stress by rapid cooling in thermosetting resin strip

This paper presents a simplified optical method for measuring the residual stresses by rapid cooling in thermosetting resin strips. First, the fundamental equations for calculating the residual stress from the residual birefringence were obtained by the linear photoviscoelastic theory. The specimens were then subjected to rapid cooling. After rapid cooling, the residual stress was measured by two methods, the simplified optical method mentioned above and the well-known layer-removal method. The effectiveness of the simplified optical method was discussed by comparing results of the two methods.     

In situ observation of formation of misfit dislocations in pseudomorphic monolayer overgrowth of metals and non-metals

Epitaxial overgrowth in cases of deposit and substrate combinations of PbSe/PbS, Au/Pd and Pd/Au were observed in situ in an electron microscope. It was found that the growth proceeds with the very characteristic features of monolayer overgrowth as implied by the theory of Frank and Van der Merwe; no indication of nucleation was observed and the formation of misfit dislocations was noticed over the whole area of films at certain critical thicknesses of the overgrowths. Points were noted which distinguish the monolayer overgrowth from the case where misfit dislocations are introduced in nucleated islands, to which Matthews has counted the growth processes in these combinations. The importance of climb motion as well as slip motion was stressed as the mechanism of introduction of misfit dislocations. Some results of electron diffraction and electron microscopy of films prepared in separate evaporation units were also quoted. These were to examine the relation between misfit dislocation density and mean lattice parameter and the effect of degree of vacuum on the growth mode and to indicate that the same growth mode takes place for some other combinations of IV–VI compounds, SnTe/PbSe, PbTe/PbS and PbTe/PbSe.     

Kinetics and activation parameter analysis for the prebiotic oligocytidylate formation on Na(+)-montmorillonite at 0-100 degrees C

The kinetic analysis of the temperature dependence of the formation of oligocytidylate (oligo(C)) from the 5'-monophosphorimidazolide moiety of cytidine (ImpC) in the presence of Na (+)-montmorillonite (Na (+)-Mont) catalyst has been carried out at 0-100 degrees C. The rate constants for the formation of oligo(C), hydrolysis of ImpC with and without Na (+)-Mont and degradation of oligo(C) were determined. The apparent activation parameters were 30.8 +/- 3.9 kJ mol (-1) ( Ea), 28.3 +/- 4.0 kJ mol (-1) (Delta H++), and -231 +/- 13 J mol (-1) K (-1) (Delta S++) for the formation of the 2-mer; 45.6 +/- 2.9 kJ mol (-1) ( Ea), 43.0 +/- 3.0 kJ mol (-1) (Delta H++), -164 +/- 10 J mol (-1) K (-1) (Delta S++) for the 3-mer; and 45.2 +/- 0.6 kJ mol (-1) ( Ea), 42.7 +/- 0.7 kJ mol (-1) (Delta H++), -159 +/- 2 J mol (-1) K (-1) (Delta S++) for the 4-mer in the presence of Na (+)-Mont. An increasing trend for the rate constants for the formation of oligo(C) in the order 2-mer < 3-mer <4-mer was observed at high temperatures, which is consistent with that observed at low temperatures. These analyses implied for the first time that the associate formation between an activated nucleotide monomer and an elongating oligonucleotide prior to the phosphodiester bond formation during the elongation of an oligonucleotide on a clay surface would be based on the interaction between the two reactants at the phosphoester and/or ribose moieties rather than at the nucleotide bases. The hydrolysis rate of ImpC at 25-100 degrees C was 5.3-10.6 times greater in the presence of Na (+)-Mont than in its absence. Although the degradation of oligo(C) in the presence of Na (+)-Mont was slower than the formation of the 3-mer and longer oligo(C) on Na (+)-Mont, its yield decreased with temperature. This is mainly because the ratios of the rate constant of the 2-mer formation to those of ImpC hydrolysis and the 3-mer and 4-mer formation decrease with an increase in temperature, which is attributed to the enthalpy and entropy changes for the formation of the 2-mer. This trend resembles the case of the template-directed formation of oligo(G) on a poly(C) template but is different from the Pb (2+)-ion-catalyzed oligo(C) formation. According to the kinetics and activation parameter analyses regarding the clay reaction and other prebiotic polymerase models, the possible pathways for the oligonucleotide formation are discussed and compared.     

Non-Completeness of Zograf–Takhtajan's Kähler Metric for Teichmüller Space of Punctured Riemann Surfaces

Zograf and Takhtajan introduced a new K?hler metric on the Teichmüller space T _g , _n (n>0), in calculating the first Chern form of the Quillen metric for families of -operators. The metric is described in terms of the Eisenstein–Maass series. We prove that it is incomplete. And we also give an alternative proof of non-completeness of the Weil–Petersson metric. For that, we use the pinching family, constructed by Wolpert, whose tangent vectors are always represented by using the relative Poincaré series associated with the pinched geodesic. Received: 18 September 1995 / Accepted: 7 March 1999     

Utilization of microgravity to improve the crystal quality of biologically important proteins: chaperonin-60, GrpE, B-subunit of V-type ATPase, and MIF

Protein crystallization experiments under microgravity were performed by using commercial vapor diffusion apparatus (CVDA) hardware on the STS-84 shuttle mission. Chaperonin-60, GrpE, the B subunit of V-type ATPase, and the selenomethionine substituted proteins of macrophage migration inhibitory factor (MIF) were selected as target proteins. The results indicate that microgravity positively affected their crystal growth, supporting the practical utilization of microgravity for the protein structure determination.