Varlas Spyridon, Foster Jeffrey C, Arkinstall Lucy A, Jones Joseph R, Keogh Robert, Mathers Robert T, O'Reilly Rachel K
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, U.K.
ACS Macro Lett. 2019 Apr 16;8(4):466-472. doi: 10.1021/acsmacrolett.9b00117. Epub 2019 Apr 3.
Aqueous polymerization-induced self-assembly (PISA) is a well-established methodology enabling synthesis of polymeric nanoparticles of controllable morphology. Notably, PISA ring-opening metathesis polymerization (ROMPISA) is an emerging technology for block copolymer self-assembly, mainly due to its high versatility and robustness. However, a limited number of monomers suitable for core-forming blocks in aqueous ROMPISA have been reported to date. In this work, we identified seven monomers for use as either corona- or core-forming blocks during aqueous ROMPISA by calculation of relative hydrophobicity for corresponding oligomeric models. The predicted monomers were validated experimentally by conducting ROMPISA using our previously reported two-step approach. In addition to predictive data, our computational model was exploited to identify trends between polymer hydrophobicity and the morphology of the self-assembled nano-objects they formed. We expect that this methodology will greatly expand the scope of aqueous ROMPISA, as monomers can be easily identified based on the structure-property relationships observed herein.
水相聚合诱导自组装（PISA）是一种成熟的方法，能够合成形态可控的聚合物纳米颗粒。值得注意的是，PISA开环易位聚合（ROMPISA）是一种新兴的嵌段共聚物自组装技术，主要因其具有高度的通用性和稳健性。然而，迄今为止，报道的适用于水相ROMPISA中形成核的嵌段的单体数量有限。在这项工作中，我们通过计算相应低聚物模型的相对疏水性，确定了七种单体，可在水相ROMPISA过程中用作冠层或核形成嵌段。通过使用我们先前报道的两步法进行ROMPISA实验验证了预测的单体。除了预测数据外，我们还利用计算模型来确定聚合物疏水性与其形成的自组装纳米物体形态之间的趋势。我们预计，这种方法将极大地扩展水相ROMPISA的范围，因为基于本文观察到的结构-性质关系可以很容易地识别单体。
