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141.
Redox-photosensitized aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia 总被引:1,自引:0,他引:1
Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T Yamashita T 《The Journal of organic chemistry》2003,68(20):7618-7624
1,2,4-Triphenylbenzene and 2,2'-methylenedioxy-1,1'-binaphthalene successfully photosensitized the aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia and primary amines in the presence of m- or p-dicyanobenzene, which gave the 4-amino-1,2-benzocycloalkenes, 3-amino-1-arylpropanes, and 7-amino-5-(p-cyanophenyl)bicyclo[2.2.1]hept-2-ene, respectively. A key pathway for the photosensitized amination is the hole transfer from the cation radicals of the sensitizers that were generated by photoinduced electron transfer to the electron acceptors to the substrates. Therefore, it was found that the relationships in oxidation potentials between the sensitizers and the substrates and the positive charge distribution of the cation radicals of the substrates were important factors for the efficient amination. 相似文献
142.
Chiral calixarene analogs incorporating cystine peptide into their macrocyclic ring were easily prepared by the cyclization reactions of bis(chloromethyl)phenol-formaldehyde oligomers with cystine peptides in moderate yields. Circular dichroism (CD) spectra indicated the existence of the transmission of the chirality from peptide unit to phenol-formaldehyde oligomer moiety. 相似文献
143.
New thermal rearrangement of 2H-azirines: Formation of enamines and their cyclization into pyridines
Kazuaki Isomura Shin-ichi Noguchi Masumi Saruwatari Sumiko Hatano Hiroshi Taniguchi 《Tetrahedron letters》1980,21(40):3879-3882
Intermediary formation of enamines in the course of cyclization of vinyl nitrenes into 6-membered ring compounds showed that this reaction proceeded not by insertion but by consecutive hydrogen shift and electrocyclic reaction. 相似文献
144.
Yasuhiko Arai Hiroyo Segawa Kazuaki Yoshida 《Journal of Sol-Gel Science and Technology》2004,32(1-3):79-83
In order to produce an excellent abrasive, a fabrication method for cocoon shaped silica particles has been studied. The particles are prepared from TMOS, water, ammonia and methanol by a sol–gel method. The method is to add the methanol solution of TMOS at a constant supply rate to a mixture of water, ammonia and methanol. Effects of various reaction conditions such as temperatures, supply rates of TMOS, and amounts of TMOS are studied on the diameter and shape of the particles. The diameter and shape are resulted in depending strongly on temperatures. High temperature makes particles with the high aspect ratio and the small diameter. And the mechanism of forming the cocoon shaped particle is also discussed. It is concluded that the primary particles are generated at the beginning stage of reaction and two of them become the cocoon shaped particle. For the polishing efficiency, particles have high polishing efficiency with the diameter between 40 nm and 210 nm. As a result, best diameter of particles for abrasive is 40–100 nm with respect to polishing efficiency and surface finish. 相似文献
145.
N-Glycans in glycoprotein can be liberated either from glycoproteins or from their glycopeptides with glycoamidases. The latter approach is preferable, because it requires a smaller amount of the enzyme, and yields N-glycans in excellent yields. Moreover it alleviates the necessity of removing from the reaction mixture the detergents needed to denature the glycoproteins. On the other hand, this approach necessitates removal of interfering peptidic materials, because some of the peptide peaks often overlap with the peaks of carbohydrate chains in high-performance anion-exchange chromatography (HPAEC). These peptidic materials also hinder labeling of N-glycans by reductive amination. We have tried to remove the interfering peptidic materials by several different methods--octadecyl (C18) silica cartridge, cation-exchange resin column, and graphitized carbon cartridge. Unfortunately, none of these could completely remove the interfering peptidic materials. Therefore, we resorted to modify the amino groups of the peptidic materials with sodium 2,4,6-trinitro-benzene-1-sulfonate (TNBS) to render them more hydrophobic, so that they can be retained more strongly on the C18 or graphitized carbon cartridges. In the model study presented here, we were able to obtain N-glycans for HPAEC analyses without any interfering materials by a combination of TNBS reaction and graphitized carbon treatment. 相似文献
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148.
Tunable phase‐separation behavior of thermoresponsive polyampholytes through molecular design
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Esha Das Kazuaki Matsumura 《Journal of polymer science. Part A, Polymer chemistry》2017,55(5):876-884
Here, we report that carboxylated poly‐l ‐lysine, a polyampholyte, shows lower critical solution temperature (LCST)‐type temperature‐responsive liquid–liquid phase separation and coacervate formation in aqueous solutions. The phase‐separation temperature of polyampholytes is strongly affected by the polymer concentration, balance between the carboxyl and amino groups, hydrophobicity of the side chain, and NaCl concentration in the solution. We concluded that the phase separation was caused by both electrostatic interactions between the carboxyl and amino groups and intermolecular hydrophobic interactions. The addition of NaCl weakened the electrostatic interactions, causing the two phases to remix. The introduction of the hydrophobic moiety decreased the phase‐separation temperature by making the molecular interactions stronger. Finally, temperature‐responsive hydrogels were prepared from the polyampholytes to explore their applicability as biomaterials and in drug delivery systems. The fine‐tuning of the phase‐separation temperature of poly‐l ‐lysine‐based polyampholytes through molecular design should open new avenues for their use in precisely controlled biomedical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 876–884 相似文献
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150.
Maeda E Urakami K Shimura K Kinoshita M Kakehi K 《Journal of chromatography. A》2010,1217(45):7164-7171
A robust and highly reproducible capillary isoelectric focusing (cIEF) method for the evaluation of charge heterogeneity of monoclonal antibody (mAb) pharmaceutical which contains covalently bound antitumor compounds was developed using a combination of commercially available dimethylpolysiloxane-coated capillary and carrier ampholyte. In order to optimize major analytical parameters for robust mobilization, experimental responses from three pI markers were selected. The optimized method gave excellent repeatability and intermediate precision in estimated pI values of charge variants with relative standard deviations (RSDs) of not more than 0.06% and 0.95%, respectively, when using IgG(4) as a model. Furthermore, RSDs of charge variant compositions were less than 5.0%. These results suggest that the proposed method can be a powerful tool for reproducible evaluation of charge variants of both naked mAbs and their conjugates with high resolution, and it is applicable to quality testing and detailed characterization in the pharmaceutical industry. In addition, it should be noticed that the method provided non-linear pH gradient within the tested ranges, from pI 9.50 to 3.78, and the pH gradient caused the inconsistency of estimated pI ranges between cIEF and gel IEF. This result indicates that selecting appropriate pI markers based on the target pI ranges of charge variants for each mAb related pharmaceutical is highly recommended for the precise determination of pI values. 相似文献