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71.
In the presence of HMPA in THF, highly stereoselective SmI(2)-promoted substitutions of alkyl 1-chlorocyclopropanecarboxylates 1 using various ketones, aldehydes (Reformatsky-type reaction), and acyl chlorides (acylation) proceeded to give trans-adducts (2 or 5) in good to high yield with excellent trans-stereoselectivity (trans-add/cis-add = > 99/1). The Reformatsky-type reaction of 1 with aldehydes and unsymmetrical ketones proceeded with moderate diastereoselectivity (re-face-adduct/si-face-adduct = 60/40-75/25). 相似文献
72.
Chie Kojima Mei Sawada Ikuhiko Nakase Akikazu Matsumoto 《Macromolecular bioscience》2023,23(11):2300139
T-cells play critical roles in various immune reactions, and genetically engineered T-cells have attracted attention for the treatment of cancer and autoimmune diseases. Previously, it is shown that a polyamidoamine dendrimer of generation 4 (G4), modified with 1,2-cyclohexanedicarboxylic anhydride (CHex) and phenylalanine (Phe) (G4-CHex-Phe), is useful for delivery into T-cells and their subsets. In this study, an efficient non-viral gene delivery system is constructed using this dendrimer. Ternary complexes are prepared using different ratios of plasmid DNA, Lipofectamine, and G4-CHex-Phe. A carboxy-terminal dendrimer lacking Phe (G3.5) is used for comparison. These complexes are characterized using agarose gel electrophoresis, dynamic light scattering, and ζpotential measurements. In Jurkat cells, the ternary complex with G4-CHex-Phe at a P/COOH ratio of 1/5 shows higher transfection activity than other complexes, such as binary and ternary complexes with G3.5, without any significant cytotoxicity. The transfection efficiency of the G4-CHex-Phe ternary complexes decreases considerably in the presence of free G4-CHex-Phe and upon altering the complex preparation method. These results suggest that G4-CHex-Phe promotes the cellular internalization of the complexes, which is useful for gene delivery into T-cells. 相似文献
73.
Radical copolymerization of N‐phenylmaleimide and diene monomers in competition with diels–alder reaction 下载免费PDF全文
Akikazu Matsumoto Daisuke Yamamoto 《Journal of polymer science. Part A, Polymer chemistry》2016,54(22):3616-3625
Radical copolymerization of N‐phenylmaleimide (PhMI) is carried out with various diene monomers including naturally occurring compounds and the copolymers are efficiently produced by the suppression of Diels–Alder reaction as the competitive side reaction. Diene monomers with an exomethylene moiety and a fixed s‐trans diene structure, such as 3‐methylenecyclopentene and 4‐isopropyl‐1‐methyl‐3‐methylenecyclohexene, exhibit high copolymerization reactivity to produce a high‐molecular‐weight copolymer in a high yield. The copolymerization of sterically hindered noncyclic diene monomers, such as 2,4‐dimethyl‐1,3‐pentadiene and 2,4‐hexadiene, also results in the formation of a high‐molecular‐weight copolymer in a moderate yield. The NMR spectroscopy reveals that the obtained copolymers consist of predominant 1,4‐repeating structures for the corresponding diene unit. The copolymers have excellent thermal stability, that is, an onset temperature of decomposition over 330 °C and a glass transition temperature over 130 °C. The copolymerization reactivity of these diene monomers is discussed based on the results of the DFT calculations. The efficient copolymer formation in competition with Diels–Alder addition is investigated under various conditions of the temperature, solvents, and initiators used for the copolymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3616–3625. 相似文献
74.
A convenient gas chromatographic method has been devised for the analysis of hexosamines in the presence of neutral and acidic sugars, which involves sequential derivatization reactions of nitrous acid deamination, mercaptalation, and trimethylsilylation. This method allows rapid, simultaneous determination of 0.1-1 micromole samples of hexosamines with coefficients of variation of less than 3%. 相似文献
75.
76.
Fuyuki Ito Nobuaki Tanaka Akio Katsuki Akikazu Kakehi Tsuneo Fujii 《Research on Chemical Intermediates》2004,30(4-5):331-336
Three types of flavylium salts (FVs, yellow, green and red) have been synthesized and the colors depended on recrystallization conditions. The existence of these color states was confirmed by diffuse reflectance spectra. The spectra were almost the same as the absorption spectra in ethanol solution. The molecular state of FVs in crystals will be the same as that in solutions. The crystal colors of the FVs are controlled by the recrystallization conditions. 相似文献
77.
Determination of the association constant of monovalent mode protein-sugar interaction by capillary zone electrophoresis. 总被引:3,自引:0,他引:3
Protein-sugar interaction was observed by capillary zone electrophoresis, using a few beta-galactose-specific lectins and lactobionic acid as protein and sugar models, respectively. The lectin peaks were retarded in a concentration-dependent manner by addition of lactobionic acid in a carrier, and association constants of monovalent mode interactions could be obtained from t1 (migration time of protein), t2 (migration time of complex, obtainable as the migration time at the plateau) and the slope of the (t-t1)-1 vs. [S]-1 plots, where t and [S] are the migration of protein in the presence of lactobionic acid and the concentration of lactobionic acid, respectively. The values for Ricinus communis agglutinin, peanut agglutinin and soy bean agglutinin at pH 6.8 were 3.3 . 10(3), 9.1 . 10(2) and 1.1 . 10(2)1 mol-1, respectively. This method required only small amounts of protein samples and was reproducible. The amount of the sugar could be minimized under the conditions that the carrier was a buffer containing the sugar whereas the electrode solutions consisted only of the buffer. 相似文献
78.
Hideo Sawada Yasufumi Shikauchi Hiroshi Kakehi Yoshihiro Katoh Masashi Miura 《Colloid and polymer science》2007,285(5):499-506
Calcium chloride reacted with sodium carbonate in the presence of a variety of self-assembled molecular aggregates formed
by fluoroalkyl end-capped acrylic acid, 2-methacryloyloxyethane sulfonic acid, dimethylacrylamide, and acryloylmorpholine
oligomers in aqueous solutions to afford the corresponding fluorinated oligomers/calcium carbonate composites in excellent
to moderate isolated yields. These fluorinated calcium carbonate composites thus obtained were shown to have a good dispersibility
not only in water but also in traditional organic media including fluorinated solvents. Dynamic light scattering measurements
(DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that these fluorinated composites
are nanometer-size-controlled particles and well dispersed in these media. Cross-linked fluoroalkyl end-capped acrylic acid
co-oligomer containing poly(oxyethylene) units was also applied to the preparation of new cross-linked fluorinated calcium
carbonate nanocomposites under similar conditions. The obtained cross-linked fluorinated calcium carbonate nanocomposites
were found to have an extremely higher dispersibility in aqueous and organic media including fluorinated solvents, compared
to that of the corresponding fluoroalkyl end-capped oligomer nanocomposites. In particular, it was verified that these fluorinated
calcium carbonate nanocomposites are applicable to the dispersion above poly(methyl methacrylate) (PMMA) film surface. Interestingly,
field-emission SEM (FE-SEM) images of the cross-section of the modified PMMA films showed that calcium carbonate particles
dispersed into these PMMA films could be arranged regularly above the modified film surface. More interestingly, cross-linked
fluorinated oligomeric aggregates were able to provide suitable host moieties for the crystallization of calcium carbonate. 相似文献
79.
Akikazu Matsumoto Keiichiro Mizuta Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2531-2539
Radical polymerizations of some cycloalkyl methacrylates bearing bridged- and fused-ring structures, i.e., bornyl methacrylate (BoMA), isobornyl methacrylate (IBoMA), 2-decahydronaphthyl methacrylate (DNMA), and 3-tetracyclo [4.4.02,5.17,10] dodecyl methacrylate (TCDMA), were carried out. The radical polymerization reactivities of these monomers depended on the structure of the cycloalkyl ester groups in the following order: TCDMA > BoMA > DNMA > CHMA > IBoMA > MMA, where CHMA and MMA are cyclohexyl and methyl methacrylates, respectively. The propagation and termination rate constants of these monomers were evaluated from the polymer radical concentration determined by electron spin resonance spectroscopy. The solubilities and microstructures of the resulting polymers were examined. Thermal properties, i.e., glass transition temperatures and decomposition behaviors, of the polymers were also investigated and related to the structures of the polymer side chain. © 1993 John Wiley & Sons, Inc. 相似文献
80.
A simple procedure for the determination of glyoxal in dialdehyde fragments, formed from glycosides by periodate oxidation, is proposed. By heating sample solutions prepared by dilution of reaction mixtures for periodate oxidation, with an aqueous dimethylsulfoxide solution of 2,4-dinitrophenylhydrazine hydrochloride. followed by addition of an aqueous ethanolic solution of potassium hydroxide, intense color with an absorption maximum at 576 nm developed. The spectrophotoinetric method based on this color reaction makes it possible to determine selectively 1·10?2–2·10?1 μmole amounts of conjugated glyoxal without a prior liberation process. Data for glyoxal content obtained by this procedure are discussed in relation to overoxidation. 相似文献