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Star-shaped and star-block polymers with a porphyrin core: from LCST-UCST thermoresponsive transition to tunable self-assembly behaviour and fluorescence performance

机译：具有卟啉芯的星形和星形聚合物：从LCST-UCST热反应转变为可调谐自组装行为和荧光性能

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摘要

Star-shaped copolymer poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) with a porphyrin core (THPP(-PDMAEMA-Br)(4)) was synthesized by atom transfer radical polymerization (ATRP). After reaction with excess NaN3, THPP(-PDMAEMA-Br)(4) was transformed to THPP(-PDMAEMA-N-3)(4). Star-block copolymer THPP(-PDMAEMA-b-PEG)(4) was obtained by click reaction of THPP(-PDMAEMA-N-3)(4) and alkynyl poly(ethylene glycol) (alkynyl PEG). After reaction of the PDMAEMA segment with excess 1,3-propane sultone, the quaternized THPP(-PDMAEMA-Br)(4) (THPP(-PDMAPS-Br)(4)) and quaternized THPP(-PDMAPS-b-PEG)(4) were obtained. These copolymers can self-assemble into spherical micelles by directly dissolving in water. The thermoresponsive micelle solutions showed transition from a lower critical solution temperature (LCST) of THPP(-PDMAEMA-Br)(4) and THPP(-PDMAEMA-b-PEG)(4) to an upper critical solution temperature (UCST) of THPP(-PDMAPS-Br)(4) and THPP(-PDMAPS-b-PEG)(4), indicating that the LCST-UCST transition of the micellar solutions can be accomplished by the transition of PDMAEMA to PDMAPS. Furthermore, the presence of permanent hydrophilic PEG chains in star-block copolymers changed the values of LCST, UCST and hydrodynamic radius (R-h) of micelles. The micelle solutions presented obvious fluorescence performance. The fluorescence intensity decreased with the increase of temperature, indicating that the variation of temperature could alter the fluorescence intensity of these copolymer micelle solutions.
机译：星形共聚物的聚（N，N-二甲氨基乙基甲基丙烯酸酯）（PDMAEMA）与卟啉核（THPP（-PDMAEMA - 溴）（4））是通过原子转移自由基聚合（ATRP）合成。用过量的NaN 3反应后，THPP（-PDMAEMA - 溴）（4），转化THPP（-PDMAEMA-N-3）（4）。星形嵌段共聚物THPP（-PDMAEMA-B-PEG）（4）通过THPP的点击反应（-PDMAEMA-N-3）（4）和炔的聚（乙二醇）（PEG炔基）获得。用过量的1,3-丙烷磺内酯，季铵化THPP（-PDMAEMA - 溴）（4）（THPP（-PDMAPS - 溴）（4））的PDMAEMA段的反应之后和季铵化THPP（-PDMAPS-B-PEG） （4）获得。通过在水中直接溶解这些共聚物可以自组装成球形胶束。所述温敏胶束溶液表明从THPP（-PDMAEMA - 溴）（4）和THPP（-PDMAEMA-B-PEG）（4）的低临界溶解温度（LCST），以THPP的上限临界溶解温度（UCST）过渡（-PDMAPS - 溴）（4）和THPP（-PDMAPS-b-PEG）（4），表明胶束溶液的LCST-UCST过渡可以通过PDMAEMA至PDMAPS过渡来实现。此外，在星形嵌段共聚物的亲水性永久PEG链的存在而改变LCST，UCST和胶束的流体动力学半径（R-H）的值。胶束的解决方案呈现明显的荧光性能。荧光强度随温度的增加而降低，这表明温度的变化可能改变这些共聚物胶束溶液的荧光强度。

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  • 来源
    《RSC Advances》 |2016年第8期|共9页
  • 作者

    Yuan Weizhong; Chen Xiangnan;

  • 作者单位

    Tongji Univ Minist Educ Sch Mat Sci &

    Engn Key Lab Adv Civil Mat Shanghai 201804 Peoples R China;

    Tongji Univ Minist Educ Sch Mat Sci &

    Engn Key Lab Adv Civil Mat Shanghai 201804 Peoples R China;

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  • 正文语种 eng
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