Core-crosslinked diblock terpolymer micelles – taking a closer look on crosslinking efficiency

Core-crosslinked diblock terpolymer micelles – taking a closer look on crosslinking efficiency
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DOI:
10.1039/c8py00126j
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发表时间:
2018-05
期刊:
影响因子:
4.6
通讯作者:
Johanna K. Elter;Gabriele Sentis;Peter Bellstedt;P. Biehl;M. Gottschaldt;F. Schacher
Johanna K. Elter;Gabriele Sentis;Peter Bellstedt;P. Biehl;M. Gottschaldt;F. Schacher
中科院分区:
化学2区
文献类型:
--
作者:
Johanna K. Elter;Gabriele Sentis;Peter Bellstedt;P. Biehl;M. Gottschaldt;F. Schacher

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本文主要介绍了两亲性嵌段共聚物的合成、表征和胶束化。以聚氧化乙烯(PEO)大分子引发剂为起始剂,通过阴离子开环聚合(AROP)合成了含有10wt%可交联单体的不同摩尔质量疏水嵌段的聚氧化乙烯-烯丙基缩水甘油醚-叔丁基缩水甘油醚嵌段共聚物PEO-b-P(AGE-co-tBGE)和聚氧化乙烯-糠基缩水甘油醚-叔丁基缩水甘油醚嵌段共聚物PEO-b-P(FGE-co-tBGE)。胶束的形成和交联在水溶液中通过Diels-Alder反应或硫醇-烯化学,分别。使用不同量的交联剂,并且先进的HR-MAS 1H NMR光谱允许随后对发生的交联反应进行半定量评价。因此,将相应的交联剂交联和单加成至二嵌段双嵌段侧链以及鉴定胶束核内的任何未反应的交联剂允许评价反应效率。胶束在非选择性溶剂中的结构稳定性证明使用DLS测量。交联反应的这种深入分析可以允许微调纳米结构材料中的交联过程,以控制未来客体分子的溶胀能力或吸收和释放。
Herein, we present the synthesis, characterization and micellization of amphiphilic diblock terpolymers. Poly(ethylene oxide)-block-poly(allyl glycidyl ether-co-tert-butyl glycidyl ether) PEO-b-P(AGE-co-tBGE) and poly(ethylene oxide)-block-poly(furfuryl glycidyl ether-co-tert-butyl glycidyl ether) PEO-b-P(FGE-co-tBGE) with hydrophobic blocks of different molar masses containing 10 wt% of a crosslinkable monomer were synthesized by anionic ring opening polymerization (AROP) starting from a PEO macroinitiator. Micelles were formed and crosslinked in aqueous solution via either a Diels–Alder reaction or thiol–ene chemistry, respectively. Different amounts of crosslinker were used and advanced HR-MAS 1H NMR spectroscopy allowed subsequent semi-quantitative evaluation of the crosslinking reactions occurring. Hereby, crosslinking and monoaddition of the respective crosslinker to the diblock terpolymer side chain as well as the identification of any unreacted crosslinker within the micellar core allowed the evaluation of the reaction efficiency. Structural stability of the micelles in non-selective solvents was demonstrated using DLS measurements. Such in-depth analysis of crosslinking reactions may allow the fine-tuning of crosslinking processes in nanostructured materials to control swelling abilities or uptake and release of guest molecules in the future.