Collaborative Research: Role of Polymer Sequence on Penetrant Transport in Charged Brushes

合作研究：聚合物序列对带电刷中渗透剂传输的作用

• 批准号: 2113767
• 负责人: Amanda Marciel
• 金额: $ 28.63万
• 依托单位: William Marsh Rice University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2113767&HistoricalAwards=false
• 关键词: Collaborative; Research; Role; Polymer; Sequence

Molecular-scale brushes, created by grafting polymers to surfaces, can be used to control the properties of the surface, including its charge, wettability, permeability, and response to environmental conditions such as salt concentration. In principle, polymer brush-coated surfaces are potentially transformative technologies for important applications in drug delivery, chemical separation processes, and water purification. Selectively controlling the transport of small molecules and particles into and out of the brush is necessary for these applications, but the ability to do so remains a persistent challenge because it is difficult to tune the structure of the brush. This research project will develop a route to control brush conformation and its response to environmental conditions by engineering the sequence of monomers that compose the polymer brush. The team will relate the structure of the engineered brushes to how small molecules and particles move through them under static and flow conditions. This research will address a critical knowledge gap by providing understanding of how the sequence of charged monomers affect the transport of penetrants, leading to improved membrane coatings for water and biologic drug purification. The project team will disseminate these results to scientists and engineers in Houston’s petrochemical, biomedical, and materials industries through local meetings, including the Texas Soft Matter Meeting. In parallel, they will develop educational outreach videos on water purification in multiple languages spoken in the Houston metro area, and present hands-on demonstrations for the general public at the Houston Energy Festival.The objective of this project is to develop a fundamental understanding of the influence of polymer sequence on transport within charged polymer brushes. Team members from two nearby universities in Houston will integrate complementary expertise in sequence-controlled polymer synthesis (Marciel – Rice University), neutron scattering applied to brushes (Conrad – University of Houston), and state-of-the-art microscopy techniques (Marciel and Conrad) to address three specific aims: (1) determine the role of polymer sequence on brush properties, (2) identify mechanisms that dictate coupling between penetrant and charged polymer brush dynamics, and (3) understand the effects of flow on out-of-equilibrium penetrant transport in charged polymer brushes. Protein engineering methodologies will be used to synthesize sequence-controlled charged polymers with isotopic labelling for grazing-incidence small angle neutron scattering (GI-SANS) and neutron reflectivity (NR) experiments to measure brush conformation and height in equilibrium and out-of-equilibrium conditions. Penetrant transport coefficients will be measured using confocal and total internal reflection fluorescence correlation spectroscopy (TIR-FCS), exploiting vertical sensitivity to distinguish transport inside and outside brushes and tested against theories for diffusion and dispersion within polymer matrices and in porous media. Together, these studies will provide new insight into the role of charge fraction and spacing on the diffusive and flow-driven transport of penetrants in charged brushes, which will pave the way for the design of advanced responsive surfaces.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

通过将聚合物接枝到表面上而产生的分子规模的刷子可以用来控制表面的性质，包括它的电荷、润湿性、渗透性和对环境条件(如盐浓度)的响应。原则上，聚合物刷涂表面是潜在的变革性技术，在药物输送、化学分离过程和水净化中有重要应用。有选择地控制小分子和粒子进出刷子的传输对于这些应用是必要的，但做到这一点的能力仍然是一个持久的挑战，因为很难调整刷子的结构。这项研究项目将开发一种方法，通过设计组成聚合物刷子的单体序列来控制刷子的构象及其对环境条件的响应。该团队将把经过改造的刷子的结构与小分子和粒子在静态和流动条件下如何通过它们联系起来。这项研究将通过了解带电单体的顺序如何影响渗透剂的传输来解决一个关键的知识缺口，从而改进水和生物药物净化的膜涂层。该项目团队将通过当地会议，包括德克萨斯州软物质会议，向休斯顿石化、生物医学和材料行业的科学家和工程师传播这些成果。与此同时，他们将用休斯顿大都市区所说的多种语言制作关于水净化的教育外展视频，并在休斯顿能源节上为普通公众提供实践演示。该项目的目标是加深对聚合物序列对带电聚合物刷子内传输的影响的基本了解。来自附近休斯顿两所大学的团队成员将整合顺序控制聚合物合成(Marciel-莱斯大学)、用于刷子的中子散射(Conrad-University of Houston)和最先进的显微技术(Marciel和Conrad)方面的互补专业知识，以解决三个具体目标：(1)确定聚合物序列对刷子性能的作用；(2)确定决定渗透剂和带电聚合物刷子动力学之间耦合的机制；(3)了解流动对带电聚合物刷子中非平衡渗透输运的影响。蛋白质工程方法将被用来合成具有同位素标记的顺序控制带电聚合物，用于掠入射小角中子散射(GI-SANS)和中子反射率(NR)实验，以测量平衡和非平衡条件下的刷子构象和高度。渗透传输系数将使用共焦和全内反射荧光相关光谱(TIR-FCS)测量，利用垂直灵敏度来区分刷子内部和外部的传输，并对照聚合物基质和多孔介质中的扩散和弥散理论进行测试。总而言之，这些研究将提供新的见解，了解电荷分数和间距在带电刷子中渗透剂的扩散和流动驱动传输中的作用，这将为先进响应表面的设计铺平道路。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Electrostatic Repulsion Slows Relaxations of Polyelectrolytes in Semidilute Solutions

• DOI: 10.1021/acsmacrolett.2c00213
• 发表时间: 2022-06-27
• 期刊: ACS MACRO LETTERS
• 影响因子: 7.015
• 作者: Slim，Ali H.;Shi，Winnie H.;Conrad，Jacinta C.
• 通讯作者: Conrad，Jacinta C.

Imaging Heterogeneous 3D Dynamics of Individual Solutes in a Polyelectrolyte Brush

聚电解质刷中单个溶质的异质 3D 动力学成像

• DOI: 10.1021/acs.langmuir.3c00868
• 发表时间: 2023
• 期刊: Langmuir
• 影响因子: 3.9
• 作者: Fan, Dongyu;Bajgiran, Shahryar Ramezani;Samghabadi, Farshad Safi;Dutta, Chayan;Gillett, Emil;Rossky, Peter J.;Conrad, Jacinta C.;Marciel, Amanda B.;Landes, Christy F.
• 通讯作者: Landes, Christy F.