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251.
Akihiro Yokoyama Yuko Inagaki Tomomi Ono Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2011,49(6):1387-1395
Random copolymers of poly(p‐benzamide)s having a methyl‐substituted tri(ethylene glycol) unit as a chiral side chain and a nonsubstituted tri(ethylene glycol) or branching alkyl unit as an achiral side chain were synthesized by copolymerization of N‐substituted 4‐aminobenzoic acid ester monomers with a base in the presence of an initiator. Copolymerizations of the chiral (S)‐monomer with N‐tri(ethylene glycol) achiral monomer and with the racemic monomer were carried out by the addition of a mixture of two monomers and an initiator to a solution of a base all at once, affording the corresponding random copolymers. On the other hand, random copolymerization of the chiral monomer with monomer having an achiral branching alkyl side chain required dropwise addition of the achiral monomer to a mixture of the chiral monomer, the initiator, and the base. These copolymers formed helical structures, but analysis of the CD spectra indicated the absence of cooperativity between the monomer units along the copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
252.
Ohkoshi E Nagashima T Sato H Fujii Y Nozawa K Nagai M 《Journal of chromatography. A》2009,1216(11):2192-2194
A simple, rapid and reproducible method was developed to isolate high-purity baicalin from Scutellariae Radix, the dried roots of Scutellaria baicalensis Georgi. The method involves partition/recrystallization steps without repeated column chromatography or special instruments. Isolated baicalin was characterized by comparisons of TLC, HPLC, IR, MS, and NMR data with an authentic sample. Moreover, beta-glucuronidase hydrolysis of baicalin sequentially yielded glucuronic acid and baicalein as confirmed by co-TLC with authentic samples. The purity of baicalin was more than 97% with yield ca. 8.7% (w/w). The method presented here appears suitable for commercial application. 相似文献
253.
Takahashi H Shida T Hitomi Y Iwai Y Miyama N Nishiyama K Sawada D Ikegami S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(22):5868-5877
An efficient divergent synthesis of L-sugars and L-iminosugars from D-sugars is described. The important intermediate, delta-hydroxyalkoxamate, prepared from D-glucono-/galactono-1,5-lactone, was cyclized under Mitsunobu conditions to give the O-cyclized oxime compound and the N-cyclized lactam compound as mixtures. A more detailed investigation revealed that the appropriate protecting groups and solvents controlled the specificity for the O-/N-cyclization of the delta-hydroxyalkoxamate. Suitable protection at the 6-position of delta-hydroxyalkoxamate, derived from D-glucono-1,5-lactone, afforded the corresponding O-alkylation product alone. Thus we succeeded in applying this to the total synthesis of L-iduronic acid. In contrast, with both TBDMS as the protecting group and RCN as the solvent the efficient conversion of D-glucono/galactono-1,5-lactone into the corresponding L-iminosugars (L-idonolactam and L-altronolactam) was achieved. 相似文献
254.
G-Protein Coupled Receptors (GPCRs) are one of the most important targets for pharmaceutical drug design. Over the past 30 years, mounting evidence has suggested the existence of homo and hetero dimers or higher-order complexes (oligomers) that are involved in signal transduction and some diseases. The number of reports describing GPCR oligomerization has increased, and in 2003, the organization of mouse rhodopsin into two-dimensional arrays of dimers was determined by an atomic force microscopic analysis. The analysis of the mouse rhodopsin complex has enabled us to discuss the oligomerization based on structural data. Although many unsolved problems still remains, the idea that GPCRs directly interact to form oligomers has been gradually accepted. One of the recent findings in the GPCR investigations is the clarification of the mechanisms of GPCR oligomerization at a molecular level. Most of these studies have suggested the importance of transmembrane alpha-helices for GPCR oligomerization. In this review, we will first summarize the importance of GPCR oligomerization and the functions of GPCRs. Then, we will explain the involvement of transmembrane alpha-helices in the oligomerization and a drug design strategy that targets these regions for GPCR oligomerization. Considering the current drug design methods, which are based on the modification of the protein-protein interactions of soluble regions of proteins, a "peptide mimic approach" that targets the transmembrane alpha-helices constituting the interfaces would be promising in drug discovery for GPCR oligomerization. For that purpose, we must know the positions of the interfaces. However, problems specific to membrane proteins have made it difficult to identify the positions of the interfaces experimentally. Therefore, information about the interfaces predicted by bioinformatics approaches is valuable. At the end of this review, several bioinformatics approaches toward interface prediction for oligomerization are introduced. The benefits and the pitfalls of these approaches are also discussed. 相似文献
255.
Yosuke Katsumura Guozhong Wu Mingzhang Lin Yusa Muroya Tomomi Morioka Yohei Terada Xifeng Li 《Research on Chemical Intermediates》2001,27(7-8):755-763
Transient radicals (hydrated electron, (SCN)2 .- and CO3 .-) formed in supercritical water have been observed by the pulse radiolysis technique. The change of spectra of these radicals with temperature has been measured. It was found that the spectra and absorption coefficients of the radicals, e- aq and (SCN)2 .-, are strongly dependent on the temperature of the water. Since it was found that the absorption spectrum and molar absorption coefficient of CO3 .- radical seem to be almost independent of temperature, G-values of OH and e- aq could be derived. Then, the absolute values of the absorption coefficients for the radicals could be calculated. The G-values of the radical products in water radiolysis tend to increase with increasing temperature up to 400°C. Based on the above observation, radiolysis of supercritical water is discussed. 相似文献
256.
Mase T Houpis IN Akao A Dorziotis I Emerson K Hoang T Iida T Itoh T Kamei K Kato S Kato Y Kawasaki M Lang F Lee J Lynch J Maligres P Molina A Nemoto T Okada S Reamer R Song JZ Tschaen D Wada T Zewge D Volante RP Reider PJ Tomimoto K 《The Journal of organic chemistry》2001,66(20):6775-6786
An efficient synthesis of a structurally unique, novel M(3) antagonist 1 is described. Compound 1 is conveniently disconnected retrosynthetically at the amide bond to reveal the acid portion 2 and the amine fragment 3. The synthesis of key intermediate 2 is highlighted by a ZnCl(2)-MAEP complex 19 catalyzed diastereoselective Michael reaction of dioxolane 7 with 2-cyclopenten-1-one (5) to establish the contiguous quaternary-tertiary chiral centers and a subsequent geminal difluorination of ketone 17 using Deoxofluor in the presence of catalytic BF(3).OEt(2). The synthesis of the amine moiety 3 is highlighted by the discovery of a novel n-Bu(3)MgLi magnesium-halogen exchange reaction for selective functionalization of 2,6-dibromopyridine. This new and practical metalation protocol obviated cryogenic conditions and upon quenching with DMF gave 6-bromo-2-formylpyridine (26) in excellent yield. Further transformations afforded the amine fragment 3 via reductive amination with 35, Pd-catalyzed aromatic amination, and deprotection. Finally, the highly convergent synthesis of 1 was accomplished by coupling of the two fragments. This synthesis has been used to prepare multi-kilogram quantities of the bulk drug. 相似文献
257.
Hitoshi Tanaka Tomomi Takeichi Takahiro Hongo 《Journal of polymer science. Part A, Polymer chemistry》1997,35(16):3537-3541
Radical homo- and copolymerizations of methyl α-trifluoroacetoxyacrylate (MTFAA) are studied by using azo initiators at 40 and 60°C. The rate of the homopolymerization of MTFAA was lower than that of methyl α-acetoxyacrylate. Monomer reactivity ratios (r), and Q and e values were estimated to be r1 = 0.03, r2 = 0.27, Q1 = 0.65, and e1 = 1.38 from the copolymerization of MTFAA (M1) and styrene (M2) at 60°C. Preferential crosspropagation was observed in particular in the copolymerization of MTFAA and α-methylstyrene. The influence of replacing the hydrogens of the acetoxy moiety of the acyloxyacrylate with the fluorines upon the copolymerization reactivity is discussed on the basis of the 13C-NMR chemical shift of various acyloxyacrylates. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3537–3541, 1997 相似文献
258.
Masaki Moritsugu Tomomi Shirota Shoichi Kubo Tomonari Ogata Osamu Sato Seiji Kurihara 《Journal of Polymer Science.Polymer Physics》2009,47(20):1981-1990
Photo‐chemically tunable photonic band gap materials are prepared by infiltration of liquid crystal polymers having azobenzene groups into voids of SiO2 inverse opal films. Linearly polarized (LP) light irradiation results in transformation from a random to an anisotropic molecular orientation of azobenzene side chains in the voids of the SiO2 inverse opal film, leading to the reversible and stable shift of the reflection peak to longer wavelength more than 15 nm. To improve switching properties, we use copolymers of azobenzene monomer and tolane monomer, which have higher birefringence, as infiltration materials into the voids. The azobenzene‐tolane copolymers are found to show higher birefringence than azobenzene homopolymers by the LP light irradiation at higher temperature. Consequently, the reflection band of the SiO2 inverse opal film infiltrated with the azobenzene‐tolane copolymer can be shifted to longer wavelength region more than 55 nm by the irradiation of LP light. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1981–1990, 2009 相似文献
259.
Wakahara T D'Angelo P Miyazawa K Nemoto Y Ito O Tanigaki N Bradley DD Anthopoulos TD 《Journal of the American Chemical Society》2012,134(17):7204-7206
A novel supramolecular nanoarchitecture, comprising C(60)/Co porphyrin nanosheets, was prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of optical microscopy, AFM, STEM, TEM, and XRD. It is established that the highly crystalline C(60)/Co porphyrin nanosheets have a simple (1:1) stoichiometry, and when incorporated in bottom-gate, bottom-contact field-effect transistors (FETs), they show ambipolar charge transport characteristics. 相似文献
260.
A 2.75-approximation algorithm is proposed for the unconstrained traveling tournament problem, which is a variant of the traveling tournament problem. For the unconstrained traveling tournament problem, this is the first proposal of an approximation algorithm with a constant approximation ratio. In addition, the proposed algorithm yields a solution that meets both the no-repeater and mirrored constraints. Computational experiments show that the algorithm generates solutions of good quality. 相似文献