在无外部催化剂或引发剂的情况下可见光介导的聚合诱导自组装
Visible Light-Mediated Polymerization-Induced Self-Assembly in the Absence of External Catalyst or Initiator.
作者信息
Yeow Jonathan, Sugita Odilia R, Boyer Cyrille
机构信息
Centre for Advanced Macromolecular Design (CAMD) and Australian Centre for NanoMedicine (ACN), School of Chemical Engineering, UNSW Australia, Sydney, NSW 2052, Australia.
出版信息
ACS Macro Lett. 2016 May 17;5(5):558-564. doi: 10.1021/acsmacrolett.6b00235. Epub 2016 Apr 12.
We report the use of visible light to mediate a RAFT dispersion polymerization in the absence of external catalyst or initiator to yield nanoparticles of different morphologies according to a polymerization-induced self-assembly (PISA) mechanism. A POEGMA macro-chain transfer agent (macro-CTA) derived from a 4-cyano-4-((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid (CDTPA) RAFT agent can be activated under blue (460 nm, 0.7 mW/cm) or green (530 nm, 0.7 mW/cm) light and act simultaneously as a radical initiator, chain transfer agent, and particle stabilizer under ethanolic dispersion conditions. In particular, the formation of worm-like micelles was readily monitored by the increase of reaction viscosity during the polymerization; this method was shown to be particularly robust to different reaction parameters such as macro-CTAs of varying molecular weight. Interestingly, at high monomer conversion, different morphologies were formed depending on the wavelength of light employed, which may be due to differing degrees of polymerization control. Finally, the in situ encapsulation of the model hydrophobic drug, Nile Red, was demonstrated, suggesting applications of this facile process for the synthesis of nanoparticles for drug delivery applications.
我们报道了在不存在外部催化剂或引发剂的情况下,利用可见光介导可逆加成-断裂链转移(RAFT)分散聚合反应,根据聚合诱导自组装(PISA)机制生成不同形态的纳米颗粒。源自4-氰基-4-((十二烷基硫烷基硫代羰基)硫烷基)戊酸(CDTPA)RAFT试剂的聚乙二醇甲基丙烯酸酯(POEGMA)大分子链转移剂(macro-CTA)在蓝色(460 nm,0.7 mW/cm)或绿色(530 nm,0.7 mW/cm)光下可被激活,并在乙醇分散条件下同时充当自由基引发剂、链转移剂和颗粒稳定剂。特别地,在聚合过程中通过反应粘度的增加可以很容易地监测到蠕虫状胶束的形成;该方法被证明对不同的反应参数(如不同分子量的macro-CTA)具有特别强的适应性。有趣的是,在高单体转化率下,根据所采用光的波长会形成不同的形态,这可能是由于聚合控制程度不同所致。最后,证明了模型疏水性药物尼罗红的原位包封,表明该简便方法在合成用于药物递送应用的纳米颗粒方面的应用前景。