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21.
Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (Rh=15-23 nm, where Rh represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The Rh of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis. 相似文献
22.
Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation. 相似文献
23.
Alkenylation reaction of alpha-halo carbonyl compounds with alkenylindiums proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties as well as a styryl group could be introduced by this method. The geometry of the carbon-carbon double bonds of the alkenylindiums was retained. Preparation of an alkenylindium via a hydroindation of 1-alkyne followed by radical alkenylation established an efficient one-pot strategy. [reaction: see text] 相似文献
24.
Cordonier CE Satake K Atarashi M Kawamoto Y Okamoto H Kimura M 《The Journal of organic chemistry》2005,70(9):3425-3436
[reaction: see text] The reaction of 2-methoxy-3H-azepines, in the presence or absence of a nucleophile, with N-bromosuccinimide (NBS) gave a regioselective 1,4-adduct from which the corresponding 2H-azepine derivatives were formed via base-promoted hydrogen bromide elimination, generally in moderate to quantitative yield. Competitive formation of 4-bromo-2-methoxy-3H-azepine by electrophilic substitutuion or 3H-azepin-2-yl 2H-azepin-2-yl ether by transetherification was minimized at lower reaction temperatures. Quantitative substitution of 2-(2',4',6'-trichlorophenoxy)-2H-azepine derivatives, formed in moderate yield from the respective 3H-azepine and NBS in the presence of 2,4,6-trichlorophenol (TCP), by various nucleophiles gave the corresponding 2-substituted 2H-azepine. Among these nucleophiles were alkanethiol and alkylamine that are not tolerated in the reaction of 3H-azepine and NBS. 相似文献
25.
Allylation of acetals with allylsilanes is catalyzed by iodotrimethylsilane to give the corresponding homoallyl ethers, with regiospecific transposition of the allyl group. 相似文献
26.
Wang ZS Hara K Dan-oh Y Kasada C Shinpo A Suga S Arakawa H Sugihara H 《The journal of physical chemistry. B》2005,109(9):3907-3914
A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface. 相似文献
27.
Tamás Veszprémi Yoshiya Harada Koichi Ohno Hideki Mutoh 《Journal of organometallic chemistry》1983,252(2):121-125
Penning ionization electron spectroscopy and CNDO/S calculations have been successfully applied to the analyses of the UV photoelectron spectra of 2- and 2,5-bistrimethylsilylthiophene and 2-t-butylthiophene. The relative intensities of the π type bands are greatly enhanced in the Penning spectra compared with those of the UV photoelectron spectra. 相似文献
28.
Kaewsaiha P Matsumoto K Matsuoka H 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6754-6761
We synthesized an ionic amphiphilic diblock copolymer, poly(hydrogenated isoprene)-b-poly(styrenesulfonic acid) (PIp-h2-b-PSS), by living anionic polymerization, and the nanostructure of its monolayer spread on a water surface was directly investigated by the in situ X-ray reflectivity technique. The monolayer of the diblock copolymer on a water surface had a smooth hydrophobic PIp-h2 layer on water and a "carpet"/polymer brush double layer in a hydrophilic sodium polystyrene sulfonate (PSSNa) layer under the water. The surface pressure dependence and PSSNa chain length dependence of the PIp-h2 layer thickness and the brush nanostructure were quantitatively studied. The effect of salt concentration in the subphase was also investigated in aqueous solutions containing 0-2 M NaCl. The salt effect on monolayer structure occurred at around 0.2 M. The thickness of the PSS brush layer decreased at salt concentrations above 0.2 M, while no structural change was observed below 0.2 M. This critical salt concentration is thought to be related to the balance of ionic concentrations inside the brush and in bulk solution. 相似文献
29.
Takami K Mikami S Yorimitsu H Shinokubo H Oshima K 《The Journal of organic chemistry》2003,68(17):6627-6631
Hydrogallation of carbon[bond]carbon multiple bonds proceeds in the presence of triethylborane as a radical initiator. Several functionalities do not interfere with this reaction. Resulting alkenyl- and alkylgallium species can be trapped by several electrophiles. Highly regioselective radical addition of an indium hydride reagent to alkynes is also achieved. Various functionalities are tolerant under the reaction conditions. The reaction proceeds with complete anti stereoselectivity. Alkenylindiums obtained via hydroindation can be employed for the following cross-coupling reaction with aryl halides in one pot. 相似文献
30.
Yoshio Tanaka Morishige Atsukawa Yukio Shimura Akira Okada Hideki Sakuraba Tokuji Sakata 《Journal of polymer science. Part A, Polymer chemistry》1975,13(5):1017-1028
A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M1) and 2-vinylpyridine (M2) or 2-vinyl-5-ethylpyridine (M2) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r1 = 0.510, r2 = 0.620 with 2-vinylpyridine and r1 = 0.57, r2 = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents. 相似文献