Li Zhidong, Wu Jianzhong
Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521-0425, USA.
J Chem Phys. 2007 Apr 14;126(14):144904. doi: 10.1063/1.2715595.
The authors investigated the polymer-mediated colloidal interactions in a good solvent wherein the particle size varies from that much smaller than the polymer radius of gyration up to macroscopic and the polymer concentration varies from that corresponding to a dilute solution to that close to a melt. At conditions directly accessible to molecular simulations, the theoretical predictions agree favorably with the simulation results for the distributions of polymer segments and for the polymer-mediated colloidal interactions. The theoretical methods were then exploited to examine the polymer structure and colloidal interactions when the particle/polymer size ratio changes from the "protein" limit to the "colloid" limit at different regimes of the polymer concentration (i.e., dilute, semidilute, and concentrated). The authors found that the surface curvature plays a significant role on the distribution of polymer segments near the particle surface at low polymer concentration, but this effect diminishes as the polymer concentration increases. The Derjaguin approximation works reasonably well at high polymer concentration even in the protein limit, but it may fail qualitatively at low polymer concentration where the polymer-induced colloidal force becomes long range.
作者研究了在良溶剂中聚合物介导的胶体相互作用,其中颗粒尺寸从远小于聚合物回转半径到宏观尺寸不等,聚合物浓度从对应稀溶液的浓度到接近熔体的浓度不等。在分子模拟可直接达到的条件下,理论预测与聚合物链段分布以及聚合物介导的胶体相互作用的模拟结果吻合良好。然后利用理论方法研究了在不同聚合物浓度范围(即稀溶液、半稀溶液和浓溶液)下,当颗粒/聚合物尺寸比从“蛋白质”极限变化到“胶体”极限时的聚合物结构和胶体相互作用。作者发现,在低聚合物浓度下,表面曲率对颗粒表面附近聚合物链段的分布起着重要作用,但随着聚合物浓度的增加,这种效应会减弱。即使在蛋白质极限下,德亚金近似在高聚合物浓度时也能较好地发挥作用,但在聚合物诱导的胶体力变为长程的低聚合物浓度下,它可能在定性上失效。