Theory of Polymer鈥揘anopore Interactions Refined Using Molecular Dynamics Simulations

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• 作者：Arvind Balijepalli ; Joseph W. F. Robertson ; Joseph E. Reiner ; John J. Kasianowicz ; Richard W. Pastor
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：May 8, 2013
• 年：2013
• 卷：135
• 期：18
• 页码：7064-7072
• 全文大小：515K
• 年卷期：v.135,no.18(May 8, 2013)
• ISSN：1520-5126

文摘

Molecular dynamics simulations were used to refine a theoretical model that describes the interaction of single polyethylene glycol (PEG) molecules with 伪-hemolysin (伪HL) nanopores. The simulations support the underlying assumptions of the model, that PEG decreases the pore conductance by binding cations (which reduces the number of mobile ions in the pore) and by volume exclusion, and provide bounds for fits to new experimental data. Estimation of cation binding indicates that four monomers coordinate a single K⁺ in a crown-ether-like structure, with, on average, 1.5 cations bound to a PEG 29-mer at a bulk electrolyte concentration of 4 M KCl. Additionally, PEG is more cylindrical and has a larger cross-section area in the pore than in solution, although its volume is similar. Two key experimental quantities of PEG are described by the model: the ratio of single channel current in the presence of PEG to that in the polymer鈥檚 absence (blockade depth) and the mean residence time of PEG in the pore. The refined theoretical model is simultaneously fit to the experimentally determined current blockade depth and the mean residence times for PEGs with 15 to 45 monomers, at applied transmembrane potentials of 鈭?0 to 鈭?0 mV and for three electrolyte concentrations. The model estimates the free energy of the PEG鈥揷ation complexes to be 鈭?.3 k_BT. Finally the entropic penalty of confining PEG to the pore is found to be inversely proportional to the electrolyte concentration.