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21.
Toshiyuki Moriuchi Toshikazu Hirao 《Journal of inclusion phenomena and macrocyclic chemistry》2012,74(1-4):23-40
This review describes an outline of dipeptide-induced chirality organization by using molecular scaffolds. A variety of ferrocene-dipeptide conjugates as bioorganometallics are designed to induce chirality-organized structures of peptides. The ferrocene serves as a reliable organometallic scaffold with a central reverse-turn unit for the construction of protein secondary structures via intramolecular hydrogen bondings, wherein the attached dipeptide strands are constrained within the appropriate dimensions. Another interesting feature of ferrocene-dipeptide conjugates is their strong tendency to self-assemble through contribution of available hydrogen bonding sites for helical architectures in solid states. Symmetrical introduction of two dipeptide chains into a urea molecular scaffold is performed to induce the formation of the chiral hydrogen-bonded duplex, wherein each hydrogen-bonded duplex is connected by continuous intermolecular hydrogen bonds to form a double helix-like arrangement. 相似文献
22.
Kazuo Koyama Takashi Hirao Akira Toriba Kazuichi Hayakawa 《Biomedical chromatography : BMC》2013,27(5):583-588
The quality of starch‐containing foods may be significantly impaired by contamination with very small amounts of α‐amylase, which can enzymatically hydrolyze the starch and cause viscosity loss. Thus, for quality control, it is necessary to have an analytical method that can measure low amylase activity. We developed a sensitive analytical method for measuring the activity of α‐amylase (from Bacillus subtilis) in starch‐containing foods. The method consists of six steps: (1) crude extraction of α‐amylase by centrifugation and filtration; (2) α‐amylase purification by desalting and anion‐exchange chromatography; (3) reaction of the purified amylase with boron‐dipyrromethene (BODIPY)‐labeled substrate, which releases a fluorescent fragment upon digestion of the substrate, thus avoiding interference from starch derivatives in the sample; (4) stopping the reaction with acetonitrile; (5) reversed‐phase solid‐phase extraction of the fluorescent substrate to remove contaminating dye and impurities; and (6) separation and measurement of BODIPY fluorescence by HPLC. The proposed method could quantify α‐amylase activities as low as 10 mU/mL, which is enough to reduce the viscosity of starch‐containing foods. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
23.
Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair 下载免费PDF全文
Xinyi Ye Adhitya Mangala Putra Moeljadi Kek Foo Chin Prof. Dr. Hajime Hirao Dr. Lili Zong Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2016,55(25):7101-7105
The first enantioselective tungstate‐catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug‐like phenyl and heterocyclic sulfides under mild conditions with H2O2, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)‐Lansoprazole, a commercial proton‐pump inhibitor. The active ion‐pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies. 相似文献
24.
S. Nakahama M. Kobayashi T. Ishizone A. Hirao M. Kobayashi 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1845-1855
Abstract N,N-Dimethyl-, diethyl-, and dipropylacrylamides were polymerized with 1,1-bis(4′-trimethylsilylphenyl)-3-methylpentyllithium (I) in the presence and absence of diethylzinc in THF. Although the polymers produced with I in the absence of diethylzinc have rather broad molecular weight distributions, the addition of diethylzinc to the polymerization systems causes narrow molecular weight distributions of the polymers. The addition of diethylzinc also affect the stereospecificities of the polymers obtained. The poly(N,N-diethylacrylamide) produced with I/diethylzinc (molar ratio of 1/3-15) is highly syndiotactic, while the one obtained with I is isotactic. The configuration of the poly(N,N-dimethylacrylamide) is changed from isotactic to syndio and heterotactic rich by the addition of diethylzinc to the polymerization mixture. Little effect of diethylzinc is observed on the stereospecificity of the polymerization of N,N-dipropylacrylamide. The stoichiometric additive effect of Et2Zn toward the initiator in the polymerization of DEAA suggests that the coordination of Et2Zn aggregates with the propagating carbanionic species narrows the molecular weight distribution and controls the tacticity of the polymer. 相似文献
25.
The acceleration effect of poly(ethylene oxide) on nucleophilic reactions was investigated. The enhancement of the reaction rate was interpreted by the cooperative solvation of alkali metal ions with ethereal oxygens of PEO resulting in active nucleophilic anions. In relation to the complex formation of alkali metal ions with PEO, the oligo(ethylene oxide) derivatives were prepared as the synthetic ionophores, which were able to transport alkali metal ions selectively through a liquid membrane against the alkali metal ion concentration. 相似文献
26.
Syntheses of cyclic oligomer and polymer were attempted with magnesiacyclohexane as the initiator in HMPA. The oligomer of α-methylstyrene, initiated by magnesiacyclohexane, was treated with dimethyldichlorosilane in order to obtain a stable cyclic oligomer. The products were investigated by GPC, IR, NMR, and elemental analysis. It was found that magnesia-cyclohexane could not be activated enough by HMPA, and that the magnesium-carbon bond was not stable in HMPA, and that the chain transfer reaction might occur repeatedly during the polymerization. Consequently, the yield of cyclic oligomer was so low that cyclic compounds could not be discriminated from the linear oligomer. 相似文献
27.
28.
Dr. Toru Amaya Riyo Suzuki Prof. Dr. Toshikazu Hirao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):653-656
N,N′‐Diphenyl‐p‐benzoquinonediimine, a redox‐active unit of polyaniline, efficiently induced the oxidative homocoupling of various aryl‐ and vinylmagnesium reagents in suppressing the side reactions, such as 1,2‐ or 1,4‐addition reaction. 相似文献
29.
30.
Kazuyoshi Kanamori Norio Ishizuka Kazuki Nakanishi Kazuyuki Hirao Hiroshi Jinnai 《Journal of Sol-Gel Science and Technology》2003,26(1-3):157-160
The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels. 相似文献