Yong Huaisong, Snoeijer Jacco H, de Beer Sissi
Department of Molecules & Materials, MESA+ Institute, Faculty of Science and Technology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands.
Institute Theory of Polymers, Leibniz-Institut für Polymerforschung Dresden e.V., D-01069 Dresden, Germany.
ACS Macro Lett. 2025 Jun 17;14(6):816-821. doi: 10.1021/acsmacrolett.5c00153. Epub 2025 May 28.
When the topology of polymer brushes is changed from linear to cyclic or looped, many of the brush properties will be improved. Yet, whether such a topology variation also affects the (vapor-)solvation and swelling of brushes has remained unclear. In fact, in a recent publication, Vagias and co-workers ( , (9), 2300035) reported an unequal swelling for linear and cyclic brushes and challenged theoreticians to develop a new Flory-Huggins theory that includes topology effects. In this letter, we address this challenge and employ molecular dynamics simulations to study the vapor swelling of linear, looped, and cyclic brushes. We find that the emergence of equal or unequal swelling for different topologies depends on the definition of the grafting density that is kept constant in the comparison. When suitably defined, the degree of swelling is independent of the topology, and the Flory-Huggins theory for brushes will describe brush swelling for all topologies in the present study.
当聚合物刷的拓扑结构从线性变为环状或带环时,刷的许多性质将会得到改善。然而,这种拓扑结构的变化是否也会影响刷的(蒸汽)溶剂化和溶胀仍不明确。事实上,在最近的一篇出版物中,瓦吉亚斯及其同事(文献编号,(9),2300035)报道了线性和环状刷的溶胀不均等情况,并向理论学家提出挑战,要求他们开发一种包含拓扑效应的新的弗洛里 - 哈金斯理论。在这封信中,我们应对这一挑战,并采用分子动力学模拟来研究线性、带环和环状刷的蒸汽溶胀。我们发现,不同拓扑结构的刷出现等溶胀或不等溶胀取决于在比较中保持恒定的接枝密度的定义。当定义适当时,溶胀程度与拓扑结构无关,并且本研究中用于刷的弗洛里 - 哈金斯理论将描述所有拓扑结构的刷的溶胀情况。