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Miktoarms hyperbranched polymer brushes:One-step fast synthesis by parallel click chemistry and hierarchical self-assembly

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Science China Chemistry 2010年第12期53卷 2461-2471页

作者： HAN Yi & GAO Chao MOE key {1. of macromolecular synthesis and functionalization Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 31.027,China 1. MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

Spherical molecular brushes with amphiphilic heteroarms were facilely synthesized by grafting the arms of hydrophobic 2-azidoethyle palmitate and hydrophilic monoazide-terminated poly(ethylene glycol) onto the core of alkyne-modified hyperbranched polyglycerol (HPG) with high molecular weight (Mn=1.2 kDa) via one-pot parallel click *** parallel click grafting strategy was demonstrated to be highly efficient (～1.0%),very fast (～ 2 h) and well controllable to the amphilicity of molecular *** adjusting the feeding ratio of hydrophobic and hydrophilic arms,a series of brushes with different arm ratios were readily *** resulting miktoarms hyperbranched polymer brushes (HPG-g-C1./PEG350) were characterized by hydrogen-nuclear magnetic resonance (1. NMR),Fourier transform infrared (FT-IR) spectroscopy,gel permeation chromatography (GPC),and differential scanning calorimetry (DSC) *** spherical molecular brushes showed high molecular weights up to 230 kDa,and thus could be visualized by atomic force microscopy (AFM).AFM and dynamic laser light scattering (DLS) were employed to investigate the self-assembly properties of amphiphilic molecular brushes with closed proportion of hydrophobic and hydrophilic *** brushes could self-assemble hierarchically into spherical micelles,and network-like fibre structures,and again spherical micelles by addition of n-hexane into the dichloromethane or chloroform solution of *** addition,this kind of miktoarms polymer brush also showed the ability of dye loading via host-guest encapsulation,which promises the potential application of spherical molecular brushes in supramolecular chemistry.

关键词： miktoarms molecular brushes hyperbranched polyglycerol amphiphilic self-assembly

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Thermo-responsive stick-slip behavior of advancing water contact angle on the surfaces of poly(N-isopropylacrylamide)-grafted polypropylene membranes

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Science China Chemistry 2010年第1期53卷 183-189,289页

作者： WAN LingShu,MENG XiangLin,YANG YunFeng,TIAN Jing & XU ZhiKang key {1. of macromolecular synthesis and functionalization,Ministry of Education Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 31.027,China 1. Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive *** this paper,we describe a thermo-responsive stick-slip behavior of water droplets on the surfaces of poly(N-isopropylacrylamide)(PNIPAM)-grafted polypropylene *** emission scanning electron microscope(FESEM) images elucidate that the morphology of PNIPAM-grafted membrane surface is thermo-responsive,i.e.,the surface becomes rougher above the lower critical solution temperature(LCST) of *** the surface of nascent polypropylene membranes,the water droplet shows a smooth motion resulting in advancing and receding water contact angles of 1.1. and ～65°,*** the PNIPAM-grafted membrane surfaces,the water droplet shows a stick-slip pattern above the LCST,whereas it advances smoothly below the *** phenomenon is reproducible and can be ascribed to the energy barriers enhanced by the shrink of PNIPAM chains above the *** also find that the slip contact angle decreases from 1.2° to 92° after several stick-slip *** decrease is attributed to the water adsorption on the grafted PNIPAM layer,which is confirmed by the continuous decrease of the receding water contact angle.

关键词： stick-slip behavior water contact angle thermo-responsive surface poly(N-isopropylacrylamide) polypropylene membrane

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synthesis,structure and catalytic activity of complexes [Ln(EDBP)_2(DME)Na(DME)_3](Ln=Er,Yb,Sm) for ring-opening polymerization of ε-caprolactone

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Science China Chemistry 2009年第10期52卷 1711-1714页

作者： YU JianFang, WU GuangMing, HUANG Jing, SUN WeiLin & SHEN ZhiQuan key {1. of macromolecular synthesis and functionalization, Ministry of Education, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 31.027, China 1. Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

Discrete ion-pair complexes [Ln(EDBP)2(DME)Na(DME)3] [Ln=Er (1., Yb (2), Sm (3)] have been synthesized by the reaction between sodium salt of 2,2'-ethylidene-bis(4,6-di-tert-butylphenol)(EDBPH2) and Ln(BH4)3·3THF (Ln=Er, Yb, Sm) followed by centrifugation and recrystalization. The complexes were characterized by elemental analysis and FT-IR, and the bonding model of these compounds was confirmed by X-ray single crystal diffraction for complex 1. It was found that four O atoms in two biphenol ligands as well as two O atoms in one ethylene glycol dimethyl ether (DME) molecule connect to the center rare earth metal atom, while sodium exists as counterpart cation to balance the charge. Complexes 1.3 can all be used as single component initiators for the ring-opening polymerization of ε-caprolactone.

关键词： ring-opening polymerization ε-caprolactone X-ray single crystal biphenol

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Delivery of surface-mediated non-viral gene nanoparticles from ultrathin layer-by-layer multilayers

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Science China Chemistry 2010年第3期53卷 508-513页

作者： WANG XueFei,REN KeFeng,LIN QuanKui & JI Jian key {1. of Macromolecule synthesis and functionalization,Ministry of Education Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 31.027,China 1. Key Laboratory of Macromolecule Synthesis and Functionalization Ministry of Education Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China

An efficient and safe gene delivery system remains a challenge in the development of gene ***-based gene nanoparticles are a typical non-viral gene delivery system,which are able to transfect cells in vitro and in *** paper reported a facile method for constructing biodegradable multilayers via layer-by-layer self-assembly,in which the polycation-based gene nanoparticles were *** this surface-mediated delivery system,adherent cells on the multilayer could be transfected in *** nanoparticles-loaded multilayers transfect cells with higher efficiency than naked DNA-loaded multilayers because of the complex configuration of the *** nanoparticles/PGA multilayers constructed on the scaffold surface could also realize in situ transfection on the adherent *** well-structured,easy-processed multilayers may provide a novel approach to precisely controlled delivery of gene nanoparticles,which may have potential applications for gene therapy in tissue engineering and medical implants.

关键词： DNA nanoparticles layer-by-layer self-assembly biodegradability in situ transfection poly(lactic acid) scaffold

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Stimulus responsive fluorescent hyperbranched polymers and their applications

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Science China Chemistry 2010年第12期53卷 2409-2428页

作者： WANG Jian 1.MEI Ju 1.QIN AnJun 1.SUN JingZhi 1.& TANG Ben Zhong 1.2 1.MOE key {1. of macromolecular synthesis and functionalization Department of Polymer Science and Engineering,Institute of Biomedical Macromolecules,Zhejiang University,Hangzhou 31.027,China 2 Department of Chemistry,The Hong Kong University of Science & Technology,Hong Kong,China 1. MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Institute of Biomedical Macromolecules Zhejiang University Hangzhou 310027 China2. Department of Chemistry The Hong Kong University of Science & Technology Hong Kong China

Fluorescent hyperbranched polymers (FHBPs),which combine the versatile fluorescent property with unique characteristics of hyperbranched architecture,are desirable candidates for stimulus responsive *** review demonstrates the structure and environment-dependent emission behaviors of a series of *** active FHBPs showing opposite performance to ACQ effect are used to sensitively detect explosives and a superamplification effect is *** designed FHBPs can complex with metal ions,leading to fluorescence turn-off due to complex quenching *** protonation of amino-containing FHBPs exhibits pH-dependent fluorescence responses to solution *** FHBPs containing responsive moieties are photo-and thermo-sensitive,and show potential applications as smart materials.

关键词： fluorescent hyperbranched polymer explosives and metal ions detection pH responsive optical and thermal sensitive

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Correlation between rheological behavior and structure of multi-component polymer systems

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Science China Chemistry 2008年第1期51卷 1-12页

作者： ZUO Min1.2 ZHENG Qiang1.1.key {1. of macromolecular synthesis and functionalization, Ministry of Education, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 31.027, China 2 Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Bay, Kowloon, Hong Kong 1. Key Laboratory of Macromolecular Synthesis and Functionalization Ministry of Education Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China 2. Department of Chemical Engineering Hong Kong University of Science and Technology Clear Bay Kowloon Hong Kong China

Rheological measurement has been an effective method to characterize the structure and properties for multiphase/multi-component polymers, owing to its sensitivity to the structure change of hetero- geneous systems. In this article, recent progress in the studies on the morphology/structure and rheological properties of heterogeneous systems is summarized, mainly reporting the findings of the authors and their collaborators, involving the correlation between the morphology and viscoelastic relaxation of LCST-type polymer blends, the microstructure and linear/nonlinear viscoelastic behavior of block copolymers, time scaling of shear-induced crystallization and rheological response of poly- olefins, and the relationship between the structure/properties and rheological behavior of filled polymer blends. It is suggested that a thorough understanding of the characteristic rheological response to the morphology/structure evolution of multiphase/multi-component polymers facilitates researchers’ op- timizing the morphology/structure and ultimate mechanical properties of polymer materials.

关键词： heterogeneous polymer systems morphology and structure rheological properties viscoelastic relaxation

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synthesis of a novel perylene diimide derivative and its charge transfer interaction with C_(60)

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Science China Chemistry 2008年第2期51卷 152-157页

作者： LIU Bo1.2, SHI MinMin1.2, YANG LiGong1.2, CHEN HongZheng1.2 & WANG Mang1.2 1.State key Lab of Silicon Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 31.027, China 2 key laboratory of Macromolecule synthesis and functionalization of Ministry of Education, Zhejiang University, Hangzhou 31.027, China 1. State Key Lab of Silicon Materials Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 China 2. Key Laboratory of Macromolecule Synthesis and Functionalization of Ministry of Education Zhejiang University Hangzhou 310027 China

A novel organic electron acceptor, N,N′-dipyrimidinyl-3,4,9,1.-perylene-tetracarboxylic diimide (DMP), was designed and synthesized. The molecular structure was characterized by FTIR spectrum and elemental analysis. By cyclic voltammetry measurements, DMP was found to possess a lower LUMO energy level than N,N′-diphenyl-3,4,9,1.-perylene-tetracarboxylic diimide due to the stronger electron-withdrawing pyrimidinyl group than the phenyl group. Fluorescence quenching is observed in a dual-layer film consisting of a DMP layer and a C60 layer and was attributed to the charge transfer at the interface due to the energy level offset between DMP and C60.

关键词： perylene diimide LUMO charge transfer fluorescence quenching

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C-1.6 loaded Ce DNase nanoparticles synergistically inhibit the cGAS-STING pathway for ischemic stroke treatment

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Bioactive Materials 2023年第11期29卷 230-240页

作者： Zhixin Zhu Haipeng Lu Lulu Jin Yong Gao Zhefeng Qian Pan Lu Weijun Tong Pik Kwan Lo Zhengwei Mao Haifei Shi Department of Orthopedics 1st Affiliated Hospital of Zhejiang University School of MedicineQingchun Road 79Hangzhou31000China MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou310027China Department of Chemistry and State Key Laboratory of Marine Pollution City University of Hong KongTat Chee AvenueKowloonHong Kong

The neuroinflammatory responses following ischemic stroke cause irreversible nerve cell *** free-double strand DNA(dsDNA)segments from ischemic tissue debris are engulfed by microglia and sensed by their cyclic GMP-AMP synthase(cGAS),which triggers robust activation of the innate immune stimulator of interferon genes(STING)pathway and initiate the chronic inflammatory *** decomposition of immunogenic dsDNA and inhibition of the innate immune STING are synergistic immunologic targets for ameliorating *** combine the anti-inflammatory strategies of STING inhibition and dsDNA elimination,we constructed a DNase-mimetic artificial enzyme loaded with *** are self-assembled by amphiphilic copolymers(P[CL35-b-(OEGMA20.7-co-NTAMA1..3)]),C-1.6,and Ce^(4+)which is coordinated with nitrilotriacetic acid(NTA)group to form corresponding catalytic *** work developed a new nano-drug that balances the cGAS-STING axis to enhance the therapeutic impact of stroke by combining the DNase-memetic Ce^(4+)enzyme and STING inhibitor *** conclusion,it is a novel approach to modulating central nervus system(CNS)inflammatory signaling pathways and improving stroke prognosis.

关键词： Ischemic stroke Ce-based nano-nuclease The cGAS-STING signaling pathway Anti-inflammation

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Electron beam irradiated HDPE/EVA/Mg(OH)2 composites for flame-retardant electric cables

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中国高等学校学术文摘·材料科学 2008年第4期2卷 426-429页

作者： Hui Liu (1. Nabil A. Noman Alkadasi (1. Yan Zhu (1. Li-fang Tong (1. Zheng-ping Fang (1. (2) Yong-chang Wang (3) 1. Institute of Polymer Composites Zhejiang University/Key Laboratory of Macromolecular Synthesis and Functionalization Hangzhou 310027 China 2. Lab of Polymer Materials and Engineering Ningbo Institute of Technology Zhejiang University Ningbo 315100 China 3. Zhejiang Institute of Technical Physics Hangzhou 310012 China

The mechanical properties and flammability of high-density polyethylene (HDPE)/ethylene vinyl acetate (EVA) mixed with various amounts of magnesium hydroxide (Mg(OH)2) as the filler in composites, irra-diated with electron beam at an irradiation dose of 1.0 kGy, have been studied. It is found that high-energy electron beam irradiation has significant effects on the mechanical properties of the HDPE/EVA/Mg(OH)2 com-posites. The tensile strength and elastic modulus increased greater than in the unirradiated ones. Meanwhile, with increasing the content of Mg(OH)2 in the composites, the limiting oxygen index (LOI) value increased sharply. The microstructure of the caves of the unirradiated HDPE/EVA/Mg(OH)2 composites show poor interface of composites compared with the irradiated ones, as observed in SEM micrographs.

关键词： electron beam irradiation cross-linking mechanical properties Mg(OH)2 HDPE/EVA

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synthesis AND CHARACTERIZATION OF Fe(Ⅱ-COORDINATED PS-b-P[NIPAM-co-(VBC-Fe-DMAP)]BLOCK COPOLYMERS

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Chinese Journal of Polymer Science 2012年第5期30卷 674-681页

作者： Kai Cao 徐君庭王晓松 Department of Materials Science and Engineering East China University of Science and TechnologyShanghai200237China MOE key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou310027China Department of Chemistry Waterloo Institute of NanotechnologyUniversity of Waterloo200 University Avenue WestWaterlooONN2L 3G1Canada

In this work, a new type of block polymers, polystyrene-b-poly[（N-isopropyl acrylamide）-co-（vinyl benzyl chloride）] （PS-b-P（NIPAM-co-VBC））, was prepared via reversible addition fragmentation transfer polymerization, then pentacyano（4-（dimethylamino pyridine））ferrate （Fe-DMAP） was attached to VBC units through a quatemization process. The Fe（II）-coordinated PS-b-P[NIPAM-co-（VBC-Fe-DMAP）] block copolymers were characterized by 1.-NMR, FT-IR and TGA. The self-assembly behavior of the block copolymers was also investigated and the micelle morphology was characterized by TEM. It was found that the PS-b-P（NIPAM-co-VBC） block polymer and Fe-coordinated block copolymer could both form spherical micelles in DMF/MeOH mixed solvent.

关键词： Micelle Block copolymer Metallic organic polymer.

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