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1.
Shigeyuki Toki Igors Sics Benjamin S. Hsiao Syozo Murakami Masatoshi Tosaka Sirilux Poompradub Shinzo Kohjiya Yuko Ikeda 《Journal of Polymer Science.Polymer Physics》2004,42(6):956-964
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 相似文献
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Arakawa Y Ohnishi M Yoshimura N Yoshifuji S 《Chemical & pharmaceutical bulletin》2003,51(8):1015-1020
Synthesis of (1R,2S,5S,6R,8S)-3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid (2) from trans-4-hydroxy-L-proline (5) was attempted. A Diels-Alder reaction of 3,4-dehydroproline derivative 9 and cyclopentadiene afforded a single stereoisomer 11. The Diels-Alder adduct was smoothly converted to the hydrochloride of 2 (24) via RuO(4) oxidation. Although some racemization of the material or product was observed during the synthetic processes, the amino acid 24 proved to be optically pure. 相似文献
4.
The determination of nanometer thick layers of poly(methyl methacrylate) coated on to the surface of poly(ethylene terephthalate) film has been investigated by high resolution pyrolysis gas chromatography without sample pretreatment or modification of the instrumentation used. A good linear relationship was observed between the quantity of the characteristic pyrolysate and the thickness of the poly(methyl methacrylate) layer; the detection limit was sufficient to enable the quantitation of poly(methyl methacrylate)-to-poly(ethylene terephthalate) film thickness ratios of 1:20000 in composite materials. 相似文献
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The elution behaviors of the biogenic amines, histamine (HA) and its metabolite methyl histamine (MHA), were evaluated by means of on-column derivatization (OCD)-capillary electrochromatography (CEC) which employed a monolithic octadecylsilica (ODS) capillary column (20 cm of effective length x 50 microm of inner diameter). Five kinds of alkylthiols, e.g., 2- hydroxyethylthiol (or 2-mercaptoethanol (2-ME)), ethanethiol (ET), 1-propanethiol (1-PT), 2-methyl-1-propanethiol (2-MPT) and 1-butanethiol (1-BT) were separately presented at 5 mM each in the OCD-CEC separation run buffer consisting of 60% acetonitrile in 5 mM o-phthalaldehyde (OPA)-10 mM borate buffer (pH 10). When 2-ME was present in the run buffer solution, both derivatives corresponding to HA and MHA migrated separately, but closely together through the capillary column. Replacement of 2-ME with 1-BT in the run buffer solution caused a delay in their elution profiles on the electrochromatogram and the separation between those two peaks became remarkably improved. The elution times of HA and MHA followed the increase in alkyl chain length or hydrophobicity of thiol, 1-BT > 2-MPT > 1-PT > ET > 2-ME. Performance of on-line preconcentrations of HA and MHA was also evaluated by varying the electrokinetic injection voltage from 1 kV to 8 kV. The peak area counts corresponding to HA recorded about 50 times higher when 2 kV was applied for 240 s to a 0.1 mM HA solution than when 8 kV was applied for 5 s. This method was next applied to a sample of human urine spiked with HA and MHA at levels of 0.1 microM each. Although HA and MHA peaks were not identifiable among the peaks corresponding to the materials in the urine matrix when OPA/2-ME was employed in a run buffer for the OCD-CEC, the separation and identification of their peaks became possible by replacing 2-ME with 1-BT in the run buffer solution. 相似文献
7.
We report on the effect on performance of varying the length of the capillary during throughout in-capillary derivatization (TICD) capillary electrophoresis (CE). Performance was evaluated by on-line coupling with a sample and CE runbuffer loading device that was newly introduced for this study. The device was assembled with a low cost using two 5 mm inner diameter (ID) disposable polyethylene syringes. First, a sequence was manually formed consisting of a 200 microL run buffer solution plug, a 100 microL sample plug and another 200 microL run buffer solution plug. Each plug was separated from its neighbor by a 100 microL air plug. When each plug reached the injection point where both a platinum-wire anode and the end of the separation capillary tube were located, 340 V/cm separation voltage (electrophoresis voltage) and 34 V/cm injection voltage were applied to the capillary for 3 s. Then the analytes were derivatized during migration in 50 microm ID capillaries filled with 2 mM o-phthalaldehyde (OPA)/N-acetylcysteine (NAC) in a 20 mM phosphate-borate buffer (pH 10), followed by separating and detecting of OPA derivatives by absorbance of 340 nm. Derivatization, separation, and detection were performed systematically using capillaries which varied in length from 5 to 80 cm. In the case of TICD-CE of a mixture containing 1 mM aspartic acid (Asp) and 20 mM m-nitorophenol (MNP) as a test solution, it was determined that peak area and peak width ratios of Asp to MNP did not depend on capillary length. Enantiomeric separations of DL-alanine (Ala) and Asp were examined using a run buffer consisting of a 45 microM beta-cyclodextrin (CD)-2 mM OPA/NAC-20 mM phosphate-borate buffer (pH 10). Even though the resolution of these enantiomeric pairs decreased with decreasing capillary length, as expected, the peaks corresponding to both enantiomeric amino acids were identified even when a 5 cm capillary was used. An 8-component amino acid mixture was also tested with 5 cm and 10 cm capillaries. 相似文献
8.
The treatment of octafluorocyclopentene with organolithium reagents gave the corresponding symmetrical disubstituted perfluorocyclopentenes in good to high yields. The reaction with Grignard reagents led to the monosubstituted perfluorocyclopentenes, which were subjected to the further nucleophilic substitution reaction using another Grignard or aryllithium reagents, unsymmetrical disubstituted perfluorocyclopentenes being obtained in high yields. 相似文献
9.
Yagi S Ezoe M Yonekura I Takagishi T Nakazumi H 《Journal of the American Chemical Society》2003,125(14):4068-4069
A novel porphyrinic receptor 1 in which two zinc porphyrins are bridged by two diarylurea linkers was developed for recognition of a viologen derivative (hexyl viologen, HV). The electronic absorption spectra as well as the 1H NMR experiments revealed that the HV molecule was bound to the cleft in 1 mainly through carbonyl dipole-charge interactions to afford a 1:1 complex. From the steady-state fluorescence spectroscopic study, the photoinduced electron transfer (PET) from 1 to HV was extremely facilitated by the receptor-substrate complexation. The receptor 1 also formed a 1:1 complex with 1,4-diazabicyclo[2.2.2]octane (DABCO) through two Zn-N coordination interactions, and, using DABCO as an inhibitor, we suppressed the PET reaction via the substrate exchange. 相似文献
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