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81.
G. T. Ruiz A. G. Lappin G. Ferraudi 《Journal of polymer science. Part A, Polymer chemistry》2012,50(12):2507-2515
The mechanisms of the redox reactions between a polymer containing Al(III) sulfonated phthalocyanine pendants, (AlIII(?NHS(O2)trspc)2?)2, and radicals have been investigated in this work. Pulse radiolysis and photochemical methods were used for these studies. Oxidizing radicals, OH?, HCO3?, (CH3)2COHCH2?, and N3?, as well as reducing radicals, eaq?, CO2??, and (CH3)2C?OH, respectively accept or donate one electron forming pendent phthalocyanine radicals, AlIII(?NHS(O2)trspc ?)? or 3?. The kinetics of the redox processes is consistent with a mechanism where the pendants react with radicals formed inside aggregates of five to six polymer strands. Electron donating radicals, that is, CO2?? and (CH3)2C?OH, produce one‐electron reduced phthalocyanine pendants that, even though they were stable under anaerobic conditions, donated charge to a Pt catalyst. While the polymer was regenerated in the Pt catalyzed processes, 2‐propanol and CO2 were respectively reduced to propane and CO. The reaction of SO3?? radicals with the polymer stood in contrast with the reactions of the radicals mentioned above. A first step of the mechanism, the coordination of the SO3?? radical to the Al(III), was subsequently followed by the formation of a SO3?? ‐ phthalocyanine ligand adduct. The decay of the SO3?? ‐ phthalocyanine ligand adduct in a ~102 ms time domain regenerates the polymer, and it was attributed to the dimerization/disproportionation of SO3?? radicals escaping from the aggregates of polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
82.
Jennifer N. Cambre Debashish Roy Brent S. Sumerlin 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3373-3382
A detailed study of the pH‐ and sugar‐responsive behavior of poly(3‐acrylamidophenylboronic acid pinacol ester)‐b‐poly(N,N‐dimethylacrylamide) (PAPBAE‐b‐PDMA) block copolymers is presented. Reversible addition‐fragmentation chain transfer (RAFT) polymerization of the pinacol ester of 3‐acrylamidophenylboronic acid resulted in homopolymers with molecular weights between 12,000 and 37,000 g/mol. The resulting homopolymers were employed as macro‐chain transfer agents during the polymerization of N,N‐dimethylacrylamide (DMA). Successful chain extension and removal of the pinacol protecting groups to yield poly(3‐acrylamidophenylboronic acid)‐b‐PDMA (PAPBA‐b‐PDMA) with free boronic acid moieties resulted in pH‐ and sugar‐responsive block copolymers that were subsequently investigated for their behavior in aqueous solution. The PAPBA‐b‐PDMA block copolymers were capable of solution self‐assembly due to the PAPBA block being water‐insoluble below its pKa. The resulting aggregates were demonstrated to solubilize and release model hydrophobic compounds, as demonstrated by fluorescence studies. Dissociation of the aggregates was induced by raising the pH above the pKa of the boronic acid residues or by adding sugars capable of forming boronate esters. Aggregate size, dissociation kinetics, and the effect of various sugars were considered. The critical sugar concentration needed to induce aggregate dissociation was tuned by incorporation of hydrophilic DMA units within the PAPBA responsive segment to yield PDMA‐b‐poly(3‐acrylamidophenylboronic acid‐co‐DMA) block copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
83.
《Journal of Coordination Chemistry》2012,65(18):3188-3204
Four organic–inorganic crystals, [(HL1)2(ZnCl4)]·H2O (1) (L1?=?2-methylquinoline), [(HL1)2(CuCl4)] (2), [(HL2)2SnCl6] (3) (L2?=?6-bromobenzo[d]thiazol-2-amine), and [(HL3)FeCl4] (4) (L3?=?5,7-dimethyl-1,8-naphthyridine-2-amine), derived from N-containing aromatic Brønsted bases and metal(II) chlorides (zinc(II) chloride, copper(II) chloride dihydrate, tin(II) chloride dihydrate, and iron(III) chloride hexahydrate) were prepared at room temperature and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The crystals are built up by perchlorometallates (Zn, Cu, Sn, and Fe) associated with organic cations through multiple non-covalent associations. X-ray diffraction analysis reveals that 1 and 2 have 3-D network structures built from hydrogen bonds between the cations and chlorometallates. Water molecules play an important role in structure extension in 1. Anhydrous 3 and 4 produced from 2-aminoheterocyclic derivatives display 2-D sheet structures. Arrangements of anions and cations are dominated by shape and size of cations, and also by the different structures of the chlorometallates as well as non-bonding interactions in the crystal structures. Except for 1, the other compounds are thermally stable below 240°C. 相似文献
84.
《Journal of Coordination Chemistry》2012,65(5):832-841
The liquid–liquid extraction of copper(II) with Schiff bases in chloroform from sulfate media is studied for pH and concentration of the extractant. Stoichiometry coefficients of the extracted species are determined by the slope analysis method. With salicylideneaniline, the copper(II) is extracted as a mixed chelate complex, CuL2HL. In the presence of substituent, the copper is extracted as simple chelates, CuL2. The trends in the values of extraction constants were explained in terms of the nature of the substituents. 相似文献
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ABSTRACTNewton trajectories are used for the Frenkel–Kontorova model of a finite chain with free-end boundary conditions. We optimise stationary structures, as well as barrier breakdown points for a critical tilting force were depinning of the chain happens. These special points can be obtained straight forwardly by the tool of Newton trajectories. We explain the theory and add examples for a finite-length chain of a fixed number of 2,?3,?4,?5 and 23 particles. 相似文献
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