GOALI: Multiscale Modeling of Adsorption Equilibrium and Dynamics in Polymer Chromatography

1064170 Neimark该项目将研究吸附的临界条件，该条件允许相对于其化学组成，微观结构和拓扑结构的大分子的分子量无关的分离。新的建模方法的基础上规范细胞蒙特卡罗模拟，自洽场理论，随机福克-普朗克扩散方程，将阐述和测试的聚合物吸附平衡和动力学的研究。这些方法将适用于和验证的实验数据收集在杜邦公司的线性均聚物和共聚物的分子量无关的分离的苯乙烯-丁二烯系统的例子分离的未改性和改性的二氧化硅基板上的不同的孔结构，在典型的色谱二元溶剂。链状分子在纳米结构表面和纳米级孔内的吸附是色谱分离和表征聚合物的关键机制，其通常用于化学和石油工业的几乎所有分支以及生物学和医学。目前，用于新应用的分离方法通过试错法开发。在开发新的色谱过程中的主要障碍是缺乏一个适当的理论来描述大分子在具有吸附表面的限制性多孔介质中的行为，并且因此，缺乏对保留机制和孔结构效应（例如孔径和形状）的基本理解。该计划的目的是设计新型的分子模拟工具，能够预测纳米多孔基底上的链分子的平衡分配和动力学，并推进对聚合物色谱中保留的物理化学机制的基本理解。拟议项目的成功将使战略方法的发展，以指导优化聚合物色谱条件。新的模拟方法可能会发现各种应用在建模复杂的大分子系统超出聚合物色谱。它们可以通过生物和固态纳米孔、生物聚合物测序和噬菌体中的DNA包装扩展到DNA和蛋白质易位的问题。提高对大分子与纳米结构和多孔基质相互作用的物理化学机制的理解是合理设计新型纳米复合材料、表面聚合物改性、药物片剂和薄膜的关键。这项研究的结果将有一个重大的变革性的跨学科的影响，因为它解决了目前尚未解决的热点问题，是共同的不同的化学和生物医学技术，并侧重于开发和测试创新的建模工具，可以适应和用于模拟和优化的各种过程，其中涉及聚合物和生物聚合物的吸附和扩散的纳米结构基板和膜，比如DNA测序和包装。该研究项目和少数民族学生的招聘将与目前的NSF IGERT计划纳米药物和NSF ERC项目结构化有机颗粒系统（ERC-SOPS）协调; PI是这些项目的教师研究员。少数民族本科生将通过REU倡议招募; PI有监督REU少数民族学生的既定记录。将为就读于新泽西州长工程技术学院和教育培训学院的K-12学生和教师准备一个关于“聚合物和纳米颗粒”的特别学习模块。这项工作的成果将通过同行审查的出版物、在国家和国际会议上的介绍以及为教育目的建立一个提供项目报告和介绍的专门网页来传播。新的模拟方法和案例研究系统将被纳入新的研究生课程“纳米尺度热力学和运输”由PI为IGERT课程开发。学生将受益于杜邦实验站的工业培训和研究设施。在工业Co-PI的指导下，他们将制作实用的计算机程序，并获得色谱实验的实践经验。

1064170NeimarkThis project will research critical conditions of adsorption, which allow for molecular weight-independent separation of macromolecules with respect to their chemical composition, microstructure, and topology. Novel modeling methods based on gauge cell Monte Carlo simulation, selfconsistent field theory, and stochastic Fokker-Plank diffusion equation, will be elaborated and tested for studies of polymer adsorption equilibrium and dynamics. These methods will be applied to and verified with experimental data collected at DuPont on molecular weight-independent separation of linear homopolymers and copolymers with the example of styrene-butadiene systems separated on unmodified and modified silica substrates of different pore structure in typical chromatographic binary solvents. Adsorption of chain molecules on nanostructured surfaces and within nanoscale pores is the key mechanism of chromatographic separation and characterization of polymers, which is commonly employed in almost all branches of chemical and petroleum industries, as well as in biology and medicine. Currently, separation methods for new applications are developed by trial-and-error approaches. The main obstacle in developing new chromatographic processes is the absence of an adequate theory describing the behavior of macromolecules within confining porous medium with adsorbing surfaces, and, as the result, the lack of a fundamental understanding of the mechanism of retention and the pore structure effects, such as pore size and shape. The objective of the proposed program is to design novel molecular simulation tools capable of predicting equilibrium partitioning and dynamics of chain molecules on nanoporous substrates and to advance fundamental understanding of the physico-chemical mechanisms of retention in polymer chromatography. The success of the proposed project will enable the development of a strategic approach to guided optimization of the conditions of polymer chromatography. The novel simulation methods may find various applications in modeling of complex macromolecular systems beyond polymer chromatography. They can be extended to the problems of DNA and protein translocation through biological and solid state nanopores, biopolymer sequencing, and DNA packaging in bacretiophages. Improved understanding of the physico-chemical mechanisms of interactions of macromolecules with nanostructured and porous substrates is the key for a rational design of novel nanocomposites, polymer modification of surfaces, pharmaceutical tablets, and films. The results of this research will have a significant transformative interdisciplinary impact since it addresses currently unresolved topical problems that are common across different chemical and biomedical technologies, and focuses on developing and testing innovative modeling tools that can be adapted and employed for simulation and optimization of various processes which involve polymer and biopolymer adsorption and diffusion on nanostructured substrates and membranes, such DNA sequencing and packaging. The research project and minority student recruitment will be coordinated with the current NSF IGERT program on Nano-Pharmaceuticals and NSF ERC project on Structured Organic Particulate Systems (ERC-SOPS); the PI is a faculty researcher in these projects. Minority undergraduate students will be recruited through the REU initiative; the PI has an established record of supervising REU minority students. A special study module on "Polymers and Nanoparticles" will be prepared for students and teachers from K-12 attending the New Jersey Governor's School of Engineering and Technology and the Education and Training Institute facilitated by ERC-SOPS. The results of this work will be disseminated through peer reviewed publications, presentations at national and international meetings, and by creating a dedicated webpage for making project reports and presentations available for educational purposes. The novel simulation methods and case-study systems will be included into the new graduate course on "Nanoscale Thermodynamics and Transport" developed by PI for the IGERT curriculum. The students will benefit from industrial training and research facilities of DuPont Experimental Station. Guided by the industrial Co-PI, they will produce computer programs of practical relevance and get a hands-on experience in chromatographic experimentation.