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151.
Kinetics of D-mannose oxidation by cerium (IV) was studied in a sulfuric acid medium at 40℃ both in absence and presence of ionic micelles. In both cases, the rate of the reaction was first-order in D-mannose and in cerium(Ⅳ), which decreased with increasing [H2SO4]. This suggested that the redox reaction followed the same mechanism. The reaction proceeded through formation of an intermediate complex, which was proved by kinetic method. The complex underwent slow unimolecular decomposition to a free radical that reacted with cerium (Ⅳ) to afford the product. The catalytic role of cationic cetyltrimethylammonium bromide (CTAB) micelles was best explained by the Menger-Portnoy model. The study of the effect of CTAB also indicated that a negatively charged species was reactive form of cerium (Ⅳ). From the kinetic data, micelle-cerium (Ⅳ) binding and rate constants in micellar medium were evaluated.The anionic micelle of sodium dodecyl sulfate plays no catalytic role. The oxidation has the rate expression: --d[Ce(Ⅳ)]= k1Kcl[D-mannose] [Ce(Ⅳ)]dt Different activation parameters for micelle catalyzed and uncatalyzed paths were also calculated and discussed. 相似文献
152.
Ren‐Shen Lee Yi‐Ting Huang 《Journal of polymer science. Part A, Polymer chemistry》2008,46(13):4320-4331
A straightforward strategy is proposed for the synthesis of novel, amphiphilic block–graft MPEG‐b‐(PαN3CL‐g‐alkyne) degradable copolymers. First, the ring‐opening polymerization of α‐chloro‐ε‐caprolactone (αClCL) was initiated by hydroxy‐terminated macroinitiator monomethoxy poly(ethylene glycol) (MPEG) with SnOct2 as the catalyst. In a second step, pendent chlorides were converted into azides by the reaction with sodium azide. Finally, various kinds of terminal alkynes were reacted with pendent azides by copper‐catalyzed Huisgen's 1,3‐dipolar cycloaddition, and thus a “click” reaction. These copolymers were characterized by differential scanning calorimetry (DSC), 1H NMR, IR, and gel permeation chromatography. By fixing the length of the MPEG block and increasing the length of PαClCL (or PαN3CL) block, an increase tendency in Tgs was observed. However, the copolymers of MPEG‐b‐PαClCL and MPEG‐b‐PαN3CL were semicrystalline when the Mn of MPEG was above 2000 g mol?1. The block–graft copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 1.4–12.0 mg L?1 depending on the composition of polymers. The lengths of hydrophilic segment influence the shape of the micelle. The mean hydrodynamic diameters of the micelles from dynamic light scattering were in the range of 90–160 nm. In vitro hydrolytic degradation of block–graft copolymers is faster than the corresponding block copolymers. The drug entrapment efficiency and the drug loading content of micelles depending on the composition of block–graft polymers were described. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4320–4331, 2008 相似文献
153.
L. Ya. Zakharova F. G. Valeeva R. A. Shagidullina L. A. Kudryavtseva 《Russian Chemical Bulletin》2000,49(8):1360-1364
The catalytic effect of the sodium dodecyl sulfate-hexanol-water ternary reverse micellar system in the alkaline hydrolysis
ofO-alkylO′-aryl chloromethylphosphonates as a function of the substrate structure was studied. The micellar effect is mainly determined
by a change in the electronic properties of the substituents, while the hydrophobicity plays a secondary role. The kinetic
data were examined in the framework of the pseudo-phase model of micellar catalysis. The rate constants of the reaction in
the surface layer and the partition constants of the reactants were calculated.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1366–1370., August, 2000. 相似文献
154.
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156.
Natthaporn Suchao‐In Hank De Bruyn Sébastien Perrier Suwabun Chirachanchai 《Journal of polymer science. Part A, Polymer chemistry》2009,47(24):6783-6788
An example case of selective morphology by simply varying pH and heating profile based on a diblock copolymer, i.e., poly(N‐isopropylacrylamide) (PNIPAAM) and poly[2‐(dimethylamino)ethyl acrylate] (PDMAEA) is reported. A variation of pH induces an aggregation of the block copolymers in either micelles or vesicles. In a subsequent step, temperature variation triggers the formation of vesicular structures. This demonstrates not only the temperature but also the heating rate that tunes the nanostructures from micelles to vesicles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009 相似文献
157.
Peng‐Fei Gou Wei‐Pu Zhu Ning Zhu Zhi‐Quan Shen 《Journal of polymer science. Part A, Polymer chemistry》2009,47(11):2905-2916
Novel amphiphilic eight‐arm star triblock copolymers, star poly(ε‐caprolactone)‐block‐poly(acrylic acid)‐block‐poly(ε‐caprolactone)s (SPCL‐PAA‐PCL) with resorcinarene as core moiety were prepared by combination of ROP, ATRP, and “click” reaction strategy. First, the hydroxyl end groups of the predefined eight‐arm SPCLs synthesized by ROP were converted to 2‐bromoesters which permitted ATRP of tert‐butyl acrylate (tBA) to form star diblock copolymers: SPCL‐PtBA. Next, the bromide end groups of SPCL‐PtBA were quantitatively converted to terminal azides by NaN3, which were combined with presynthesized alkyne‐terminated poly(ε‐caprolactone) (A‐PCL) in the presence of Cu(I)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine in DMF to give the star triblock copolymers: SPCL‐PtBA‐PCL. 1H NMR, FTIR, and SEC analyses confirmed the expected star triblock architecture. The hydrolysis of tert‐butyl ester groups of the poly(tert‐butyl acrylate) blocks gave the amphiphilic star triblock copolymers: SPCL‐PAA‐PCL. These amphiphilic star triblock copolymers could self‐assemble into spherical micelles in aqueous solution with the particle size ranging from 20 to 60 nm. Their micellization behaviors were characterized by dynamic light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2905–2916, 2009 相似文献
158.
Sebastian Mendrek Aleksandra Mendrek Hans‐Juergen Adler Andrzej Dworak Dirk Kuckling 《Journal of polymer science. Part A, Polymer chemistry》2009,47(7):1782-1794
Block copolymers of poly(glycidol)‐b‐poly(4‐vinylpyridine) were obtained by ATRP of 4‐vinylpyridine initiated by ω‐(2‐chloropropionyl) poly(glycidol) macroinitiators. By changing the monomer/macroinitiator ratio in the synthesis polymers with varied P4VP/PGl molar ratio were obtained. The obtained block copolymers showed pH sensitive solubility. It was found that the linkage of a hydrophilic poly(glycidol) block to a P4VP influenced the pKa value of P4VP. DLS measurements showed the formation of fully collapsed aggregates exceeding pH 4.7. Above this pH values the collapsed P4VP core of the aggregates was stabilized by a surrounding hydrophilic poly(glycidol) corona. The size of the aggregates depended significantly upon the composition of the block copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1782–1794, 2009 相似文献
159.
Shin‐Ichi Yamamoto Joanna Pietrasik Krzysztof Matyjaszewski 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):194-202
Statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO2MA) and tri(ethylene glycol) methyl ether methacrylate (MEO3MA) were synthesized by atom transfer radical polymerization (ATRP) providing copolymers with controlled composition and molecular weights ranging from Mn = 8,300–56,500 with polydispersity indexes (Mw/Mn) between 1.19 and 1.28. The lower critical solution temperature (LCST) of the copolymers increased with the mole fraction of MEO3MA in the copolymer over the range from 26 to 52 °C. The average hydrodynamic diameter, measured by dynamic light scattering, varied with temperature above the LCST. These two monomers were also block copolymerized by ATRP to form polymers with molecular weight of Mn = 30,000 and Mw/Mn from 1.12 to 1.21. The LCST of the block copolymers shifted toward the LCST of the major segment, as compared to the value measured for the statistical copolymers at the same composition. As temperature increased, micelles, consisting of aggregated PMEO2MA cores and PMEO3MA shell, were formed. The micelles aggregated upon further heating to precipitate as larger particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 194–202, 2008 相似文献
160.
Huan‐Bing Wang Xue‐Si Chen Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2008,46(4):1388-1401
Novel star‐like hyperbranched polymers with amphiphilic arms were synthesized via three steps. Hyperbranched poly(amido amine)s containing secondary amine and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3‐amino‐1,2‐propanediol (APD) with feed molar ratio of 1:2. 1H, 13C, and HSQC NMR techniques were used to clarify polymerization mechanism and the structures of the resultant hyperbranched polymers. Methoxyl poly(ethylene oxide) acrylate (A‐MPEO) and carboxylic acid‐terminated poly(ε‐caprolactone) (PCL) were sequentially reacted with secondary amine and hydroxyl group, and the core–shell structures with poly(1TT‐2APD) as core and two distinguishing polymer chains, PEO and PCL, as shell were constructed. The star‐like hyperbranched polymers have different sizes in dimethyl sulfonate, chloroform, and deionized water, which were characterized by DLS and 1H NMR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1388–1401, 2008 相似文献