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81.
The stability of several poly(N-propargylamides) was investigated in solution and in solid state on the basis of molecular weight change with time, and further their thermal stability was investigated by TGA. When the stability of poly(N-propargylamides) with varying pendent groups was compared, polymers with pendent groups of moderate size showed the highest stability in solution. Too short and too bulky pendent groups were not favorable for the stability of polymers. When poly(N-propargylheptanamide) (poly(6)) was stored in THF as solution at −20 °C in the absence of oxygen in dark, its degradation rate was the lowest. The degradation rate of poly(6) depended on the solvents used, which may be related to different solubility of oxygen in these solvents. Polymers with high cis contents degraded faster than polymers with low cis contents did. Addition of TEMPO and DPPH into the poly(6)/THF solution more or less depressed the degradation of poly(6). The degradation of polymer main chain in solution was always accompanied by the decrease of cis content, i.e. geometric isomerization from cis- to trans-structure. When the polymers were stored in the solid state at −20 °C, the polymers having alkyl pendent groups with moderate length were more stable than those with bulky pendent groups. Geometric isomerization occurred along with degradation in the solid state as well. 相似文献
82.
Miscibility has been investigated in blends of poly(butylene succinate) (PBSU) and poly(vinyl phenol) (PVPh) by differential scanning calorimetry in this work. PBSU is miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer–polymer interaction parameter, obtained from the melting depression of PBSU using the Nishi–Wang equation, is composition dependent, and its value is always negative. This indicates that PBSU/PVPh blends are thermodynamically miscible in the melt. Preliminary morphology study of PBSU/PVPh blends was also studied by optical microscopy (OM). OM experiments show the spherulites of PBSU become larger with the PVPh content, indicative of a decrease in the nucleation density, and the coarseness of PBSU spherulites increases too with increasing the PVPh content in the blends. 相似文献
83.
Summary
Poly(N-hydroxyethyl-L-glutamine) (PHEG) hydrogels were prepared by aminolysis of
poly( -benzyl L-glutamate) with 2-aminoethanol and hydrophobic or hydrophilic
crosslinkers, and the effect of the hydrophobicity of the crosslinkers was evaluated.
The swelling properties, tensile properties and enzymatic degradation behavior were
studied in phosphate buffered saline (PBS). The swelling ratio and degradation rate of
these hydrogels were highly dependent on the hydrophobicity of the crosslinkers,
while tensile properties were dependent on the swelling ratio, but not on the
hydrophobicity of the crosskinkers. 相似文献
84.
Yasumasa?Minemoto Shuji?AdachiEmail author Yuji?Shimada Toshihiro?Nagao Toshio?Iwata Yoshie?Yamauchi-Sato Takaya?Yamamoto Tadashi?Kometani Ryuichi?Matsuno 《Journal of the American Oil Chemists' Society》2003,80(7):675-678
The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand,
the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors
for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius
equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA
or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested
that the autoxidation mechanisms for the CLA and PUFA were essentially the same. 相似文献
85.
Toshio Ogasawara Takashi Ishikawa Takashi Matsuzaki 《Journal of the American Ceramic Society》2003,86(5):830-837
The thermal response and oxidation of Tyranno™ Lox-M fiber-reinforced Si-Ti-C-O matrix composites in high-enthalpy dissociated air was investigated in an arc jet facility (an arc wind tunnel). The maximum surface temperature reached 1310–1670°C. Catalytic recombination of oxygen and nitrogen on the composite surface under dissociated air was not significant. Surface recession was insignificant below 1600°C surface temperatures and above 5 kPa of oxygen partial pressure at the stagnation point. Passive-to-active oxidation transition of the composite agreed with Balat's theory for monolithic silicon carbide. A glass sealant prevented active oxidation of the composite for short-time exposures. 相似文献
86.
Hidetaka Yoshikawa Katsuya Fukuyama Yoichiro Nakahara Takehisa Konishi Nobuyuki Ichikuni Yasuko Yoshikawa Noboru Akuzawa Yoichi Takahashi Keiko Nishikawa 《Carbon》2003,41(15):2931-2938
The structure of bromine residue compounds was investigated by X-ray absorption fine structure (XAFS) in order to interpret where and how bromine is present in carbons with different degrees of graphitization. The residue compounds can be classified into three groups, as obtained from X-ray absorption near edge structure (XANES) spectra and the values of the intramolecular distance rBr–Br determined by extended X-ray absorption fine structure (EXAFS). In Group I, prepared from the host carbons heat treated at temperatures higher than 1900 °C, bromine exists in the interlayer space of graphite in the form of Br2 molecules with interaction of the π electrons of graphite. In Group III, from carbon heat treated at 1000 °C, most of the bromine probably reacts with carbon atoms having a dangling bond or functional groups. For Group II, where the host carbons are heat treated at intermediate temperatures, it is likely that bromine exists in undeveloped defects with a unique electronic state. 相似文献
87.
The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt. 相似文献
88.
Nomura SM Tsumoto K Hamada T Akiyoshi K Nakatani Y Yoshikawa K 《Chembiochem : a European journal of chemical biology》2003,4(11):1172-1175
Functional protein synthesis was observed in cell-sized lipid vesicles following encapsulation of a gene-expression system. Expression of rsGFP (red-shifted green fluorescent protein) within individual vesicles was observed by fluorescence microscopy. Interestingly, at the early stage of the reaction, the expression efficiency inside the vesicle was remarkably higher than that in the solution outside. The synthesized rsGFP in individual vesicles is safe from attack by proteinase K added to the external aqueous solution. Studies on cell-sized vesicles expressing protein should contribute to a fundamental understanding of certain aspects of living systems and will be useful for practical applications, such as the construction of microreactors. 相似文献
89.
The methods to estimate the surface tension of polymer solids using contact angles have been reviewed in the first part. They are classified into the following three groups depending on the theories or the equations applied: (1) the methods using the Young's equation alone, (2) the methods using the combined equation of Young and Good-Girifalco, and (3) the methods using the equations of work of adhesion. Some notes and comments are given for each method and results are compared with each other. The two-liquids method for rather high energy surface is also introduced. Next, some new possibilities to evaluate the surface tension of polymer solids are presented by our new contact angle theory in consideration of the friction between a liquid drop and a solid surface. The advancing and receding angles of contact (θ a and θ r ) are explained by the frictional tension γF and accordingly two kinds of the critical surface tension γC (γCa and γCr ) are given. This work has shown that one of the recommendable ways to evaluate γS is either the maximum γLV cos θa or the maximum γC using the advancing contact angle θa alone, and another way is the arithmetic or the harmonic mean of the γCa and γCr . A depiction to determine the γC such as ln(1 + cos θ0 ) vs. γLV with cos θ0 = (cos θ0 + cos θr )/2 has also been proposed. 相似文献
90.
Toshio Honda 《Sequential Analysis》2013,32(3-4):239-251
Suppose that {Xn} is a strongly mixing process with unknow marginal density f(x) and that we estimate f(x) by a kernel estimator [fcirc]n(x|hn)and want to achive the MISE no larger than some preassigned postive number w. However,the appropriate sample size n*depends on a functional of the unknow density function. Therefore some sequential procedure is required and we adopt a fully sequential procedure. In this paper we investigate the asymptotic properties of the procedure and show that the producure is asymptotically efficient in a certain sense as w→0. The results are almost the same in the i.i.d. setting. our result extend a class of models to which the methodology can be applied. For example economic variable,experiments on a single subject in which obervation are not indepent, and so on. 相似文献