Crosslinked p(MMA) particles by RAFT emulsion polymerisation: tuning size and stability
Crosslinked p(MMA) particles by RAFT emulsion polymerisation: tuning size and stability
复制标题
DOI：
10.1039/d2py00337f
复制
发表时间：
2022-06-01
影响因子：
4.6
通讯作者：
Willcock, Helen
中科院分区：
文献类型：
--
作者：
Marsden, Catherine J.;Breen, Colum;Willcock, Helen
两亲性二嵌段共聚物的受控合成允许产生大量纳米结构，包括嵌段共聚物颗粒，其已被证明对生物医学应用有价值。尽管在靶向特定嵌段共聚物结构方面取得了进展，但对球形颗粒的尺寸和稳定性的控制还没有得到很好的探索。在这里，我们报告使用RAFT乳液聚合来合成一个库的p（MMA）颗粒，与乙二醇二甲基丙烯酸酯交联和稳定刷状聚（乙二醇）为基础的聚合物。我们成功地合成了一系列嵌段共聚物颗粒，提供高达p（MMA）（1000）的稳定性，DLS报告稳定的粒径为33-176 nm，PDI < 0.2。DLS和AFM研究表明，随着p（MMA）的量的增加，粒径普遍增加。使用具有甲基醚端基的PEG甲基丙烯酸酯单体产生比具有羟基端基的那些更好限定和稳定的颗粒。适当官能化的Gd（iii）配合物到球形p（MMA）颗粒的壳中的共聚导致Gd负载的颗粒，通过H-1 NMR弛豫法详细研究，表明Gd配合物成功地掺入到颗粒中。这项研究将为具有优化的稳定性和目标尺寸的核壳颗粒的合成提供信息，并展示了一种简单的方法来结合分子传感器，产生大分子成像剂。
The controlled synthesis of amphiphilic di-block copolymers allows a large array of nanostructures to be created, including block copolymer particles, which have proved valuable for biomedical applications. Despite progress in targeting specific block copolymer architectures, control over the size and stability of spherical particles is less well explored. Here, we report the use of RAFT emulsion polymerisation to synthesise a library of p(MMA) particles, crosslinked with ethylene glycol dimethacrylate and stabilised by brush-like poly(ethylene glycol)-based polymers. We successfully synthesised a range of block copolymer particles, offering stability up to p(MMA)(1000), with DLS reporting stable particle diameters of 33-176 nm and PDI < 0.2. DLS and AFM studies showed a general increase in particle diameter with increasing amounts of p(MMA). The use of a PEG methacrylate monomer with a methyl ether end group resulted in more well defined and stable particles than those with hydroxyl end groups. The copolymerisation of a suitably functionalized Gd(iii) complex into the shell of the spherical p(MMA) particles resulted in Gd-loaded particles that were investigated in detail by H-1 NMR relaxometry, demonstrating that the Gd complex was successfully incorporated into the particles. This study will inform the synthesis of core-shell particles with optimised stability and targeted sizes, and show a simple method to incorporate a molecular sensor, generating a macromolecular imaging agent.