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31.
Fukuji Higashi Toshio Mashimo 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1697-1701
The reaction promoted by thionyl chloride and pyridine could selectively activate carboxyl groups of hydroxybenzoic acids to give polyesters of high inherent viscosities up to 3.8. Favorable conditions were studied in terms of the temperatures for the initial reaction with the acids and subsequent aging at room temperature. Copolymers of several combinations of hydroxybenzoic acids with high molecular weights were obtained in quantitative yield by carrying out the polycondensation at 80°C for 3 h. The reaction could also produce high molecular polyesters in a simpler process without the initial activation of dicarboxylic acids by adding a mixture of these monomers to the condensing agent, and a tough film- and fiberforming polymer was obtained from 4,4′-dihydroxyphenylsulfone of low nucleophilicity whose polymer of high molecular weight is difficult to obtain. The process was also successfully applied to the direct copolycondensations of hydroxybenzoic acids, aromatic dicarboxylic acids, and bisphenols to produce polyesters of ηinh up to 5.6. 相似文献
32.
Fukuji Higashi Michihide Ozawa Akihiko Mochizuki 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):637-643
The reaction promoted by diphenyl chlorophosphate (DPCP) in pyridine was successfully applied to the preparation of soluble aromatic copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, bisphenols, and a wide range of mol % aromatic diamines. Dropwise addition of a mixture of bisphenols and diamines (more favorably of bisphenols and then diamines) to the mixture of dicarboxylic acids activated by DPCP led the reactions homogeneously even with high mol % of diamines to produce copolymers of good solubility. This improved copolymer solubility was roughly estimated by sequence distribution of polyamide and polyester units in the copolymers, which was studied in a model reaction and in the copolycondensations by simultaneous and stepwise addition of bisphenols and diamines. 相似文献
33.
34.
Yusuke Yoshimura Ryuichiro Hibi Akiho Nakata Moeka Togashi Shoujiro Ogawa Takayuki Ishige Mamoru Satoh Fumio Nomura Tatsuya Higashi 《Biomedical chromatography : BMC》2019,33(7)
A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D3 [25(OH)D3] and 24,25‐dihydroxyvitamin D3 [24,25(OH)2D3] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D3‐3‐ and ‐25‐glucuronides, or 24,25(OH)2D3‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D3 and 24,25(OH)2D3, respectively. The 3‐glucuronide was not present for 24,25(OH)2D3, unlike 25(OH)D3, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)2D3. 相似文献
35.
Taishi Nakanishi Dr. Jun Kikuchi Dr. Atsushi Kaga Prof. Dr. Shunsuke Chiba Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8230-8234
A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides. 相似文献
36.
Katsumi Katoh Seiichiro Nagayama Eiko Higashi Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1239-1244
In the hydrosilylation of 1,6-divinyl(perfluorohexane) (FDV) with trichlorosilane (TCS) in the presence of catalytic chloroplatinic acid (Pt-Cat) under an air atmosphere (0.99 MPa), a runaway reaction accompanied by a severe pressure release occurred when Fe2O3 was present as an impurity in the system. In this study, we investigated the mechanism of action of Fe2O3 on this hydrosilylation by monitoring the thermal behavior of TCS/FDV/Pt-Cat/Fe2O3 mixtures with various compositions, using an accelerating rate calorimeter (ARC). In the case of TSC/FDV/Pt-Cat, a typical hydrosilylation composition in the industrial process, heat release, possibly due to hydrosilylation, began at 90 °C. On the other hand, for TCS/FDV/Pt-Cat/Fe2O, the heat release due to hydrosilylation was hardly observed, but abrupt heat and pressure releases occurred at higher temperatures (>170 °C). Like TCS/FDV/Pt-Cat/Fe2O3, TCS/FDV, which contain neither Pt-Cat nor Fe2O3, released heat and pressure at high temperatures (>210 °C), while the heat and pressure release rates were comparatively low. From these results, the runaway reaction may occur when hydrosilylation is prevented, and Fe2O3 behaves as a negative catalyst for hydrosilylation. In the FT-IR spectrum of TCS/FDV/Pt-Cat/Fe2O3 after heating, an absorption peak at approximately 1,710 cm?1, which may be attributed to a carbonyl group, was observed. Thus, it is considered that the runaway reaction observed during the hydrosilylation results from the action of Fe2O3 as a negative catalyst for hydrosilylation as well as as an oxidation catalyst for the by-product generated from the reaction between TCS and FDV. 相似文献
37.
Katsumi Katoh Nobuyuki Saeki Eiko Higashi Yuki Hirose Masahiko Sugimoto Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1275-1279
As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts. 相似文献
38.
Formation of One‐Dimensional Helical Columns and Excimerlike Excited States by Racemic Quinoxaline‐Fused [7]Carbohelicenes in the Crystal 下载免费PDF全文
Dr. Hayato Sakai Sho Shinto Prof. Yasuyuki Araki Prof. Takehiko Wada Prof. Tomo Sakanoue Prof. Taishi Takenobu Prof. Taku Hasobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10099-10109
A series of quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light‐emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited‐state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady‐state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single‐crystal analysis. Introduction of appropriate substituents (i.e., 4‐methoxyphenyl) in the HeQu unit enabled the construction of one‐dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π‐stacking between two neighboring [7]carbohelicenes and intercolumn CH ??? N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time‐resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units. 相似文献
39.
Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques 下载免费PDF全文
Dr. Shinobu Takao Dr. Oki Sekizawa Dr. Shin‐ichi Nagamatsu Dr. Takuma Kaneko Dr. Takashi Yamamoto Dr. Gabor Samjeské Dr. Kotaro Higashi Dr. Kensaku Nagasawa Dr. Takuya Tsuji Dr. Motohiro Suzuki Dr. Naomi Kawamura Dr. Masaichiro Mizumaki Prof. Dr. Tomoya Uruga Prof. Dr. Yasuhiro Iwasawa 《Angewandte Chemie (International ed. in English)》2014,53(51):14110-14114
There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation. 相似文献
40.
Yu Suzuki Takanori Higashi Takahiro Yamamoto Hideyasu Okamura Takehiro K. Sato Tetsuo Asakura 《Molecules (Basel, Switzerland)》2022,27(2)
Spider dragline silk is a biopolymer with excellent mechanical properties. The development of recombinant spider silk protein (RSP)-based materials with these properties is desirable. Formic acid (FA) is a spinning solvent for regenerated Bombyx mori silk fiber with excellent mechanical properties. To use FA as a spinning solvent for RSP with the sequence of major ampullate spider silk protein from Araneus diadematus, we determined the conformation of RSP in FA using solution NMR to determine the role of FA as a spinning solvent. We assigned 1H, 13C, and 15N chemical shifts to 32-residue repetitive sequences, including polyAla and Gly-rich regions of RSP. Chemical shift evaluation revealed that RSP is in mainly random coil conformation with partially type II β-turn structure in the Gly-Pro-Gly-X motifs of the Gly-rich region in FA, which was confirmed by the 15N NOE data. In addition, formylation at the Ser OH groups occurred in FA. Furthermore, we evaluated the conformation of the as-cast film of RSP dissolved in FA using solid-state NMR and found that β-sheet structure was predominantly formed. 相似文献