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Dual thermoresponsive homopolypeptide with LCST-type linkages and UCST-type pendants: Synthesis, characterization, and thermoresponsive properties
Polymer ( IF 4.6 ) Pub Date : 2017-11-08 , DOI: 10.1016/j.polymer.2017.11.016
Minjie Li , Xiongliang He , Ying Ling , Haoyu Tang

Water-soluble homopolypeptides bearing di(ethylene glycol) (DEG) linkages and various ionic liquid (IL) pendants with both lower and upper critical solution temperature (LCST and UCST) or a UCST were prepared and systematically investigated. Poly (γ-2-(2-chloroethoxy)ethyl l-glutamate) (PCEELG) with DEG linkage and reactive chloro groups can be readily prepared from ring-opening polymerization of γ-2-(2-chloroethoxy)ethyl l-glutamic acid based N-carboxyanhydride. Homopolypeptides were conjugated with various IL pendants and counteranions by nucleophilic substitutions and subsequent ion-exchange reactions. Homopolypeptide with DEG linkages and tributylphosphonium iodide (PEELG-TBP-I) showed interesting LCST < UCST (i.e., soluble-insoluble-soluble) dual thermoresponsive behavior in DI-H2O and NaI aqueous solutions. The LCST-type and UCST-type phase transition temperatures (Tpts) were tunable by polymer concentration, molar mass, and NaI concentration. Homopolypeptide with DEG linkages and tributylphosphonium tetrafluoroborate showed a UCST both in DI-H2O and PBS buffer while homopolypeptide with DEG linkages and triphenylphosphonium iodide (or tetrafluoroborate) or with alkyl linkages and tributylphosphonium iodide (or tetrafluoroborate) showed a UCST in PBS buffer. The UCST-type Tpt in PBS buffer was in a broad temperature range of 20–90 °C which was tunable by adjusting the polymer concentration, molar mass, IL moieties, and counteranions.



中文翻译:

具有LCST型连接和UCST型侧基的双热响应性同多肽:合成,表征和热响应性

制备了带有双(乙二醇)(DEG)键和具有上下临界溶液温度(LCST和UCST)或UCST的各种离子液体(IL)侧基的水溶性均多肽,并进行了系统的研究。聚(γ -2-(2-氯乙氧基)乙基-谷氨酸)(PCEELG)与DEG键和反应性氯基团可以从开环聚合而容易地制备γ -2-(2-氯乙氧基)乙基谷氨酸基于N-羧基酐。通过亲核取代和随后的离子交换反应,将同多肽与各种IL侧基和抗衡阴离子缀合。具有DEG键的同多肽和碘化三丁基with(PEELG-TBP-1)在DI-H 2 O和NaI水溶液中显示出有趣的LCST <UCST(即,可溶-不溶-可溶)双重热响应行为。LCST型和UCST型的相变温度(T pt s)可通过聚合物浓度,摩尔质量和NaI浓度进行调节。具有DEG键的同多肽和四氟硼酸三丁基phosph在DI-H 2中均显示UCSTO和PBS缓冲液,而带有DEG键和碘化三苯基phosph(或四氟硼酸酯)或带有烷基键和碘化三丁基phosph(或四氟硼酸酯)的同多肽在PBS缓冲液中显示UCST。PBS缓冲液中的UCST型T pt在20-90°C的较宽温度范围内,可通过调节聚合物浓度,摩尔质量,IL部分和抗衡阴离子来调节。

更新日期:2017-11-08
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