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Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, 1H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.  相似文献   
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A series of novel polyisocyanide‐graft‐polystyrenes and polyisocyanide‐graft‐[polystyrene‐block‐poly(butyl acrylate)]s were synthesized through the grafting‐through and grafting‐from routes with two types of living polymerization techniques: polymerization with the Pd–Pt μ‐ethynediyl dinuclear complex as the initiator and catalyst for the polyisocyanide backbone and atom transfer radical polymerization for the grafted side chain. Through the introduction of a chiral center at the side chain of the polyisocyanide backbone, helical grafted and graft block polyisocyanides were prepared through the grafting‐from method. All of the obtained polymers exhibited polydispersities in the range of 1.07–1.41. This might have been the first time grafted polyisocyanides were prepared, especially helical grafted polyisocyanides, through the operation of two living polymerization techniques. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1871–1880, 2003  相似文献   
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Novel wormlike nanostructures were self‐assembled in bulk films of a well defined diblock copolymer with azobenzene moieties, which was prepared by atom transfer radical polymerization (ATRP). For comparison, a homopolymer with almost the same repeat units of azobenzene as those in the copolymer was also prepared. They both had well defined structures and exhibited a smectic liquid crystalline phase. Upon annealing the copolymer films, poly(methyl methacrylate) formed a matrix with excellent optical properties, and the azobenzene segment in the minority phase self‐assembled into a wormlike mesogenic domain in the bulk films. Such block copolymer films exhibited stability and transparency by eliminating the scattering of visible light, indicating their potential application as photoresponsive functional materials. Although wormlike morphologies have been obtained in micelles from block copolymer solutions, to the best of our knowledge, such wormlike nanostructures have never been explored in bulk films.

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We analyze a list heuristic for the vertex cover problem that handles the vertices in a given static order based on the degree sequence. We prove an approximation ratio of at most for a nonincreasing degree sequence, and show that no ordering can achieve an approximation ratio of less than .  相似文献   
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