Critical Conditions of Adhesion and Separation of Functionalized Nanoparticles on Polymer Grafted Substrates
Critical Conditions of Adhesion and Separation of Functionalized Nanoparticles on Polymer Grafted Substrates
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功能化纳米粒子在聚合物接枝基底上粘附和分离的临界条件
DOI：
10.1021/acs.jpcc.9b01219
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Neimark, Alexander V.
中科院分区：
文献类型：
--
作者：
Santo, Kolattukudy P.;Vishnyakov, Aleksey;Brun, Yefim;Neimark, Alexander V.
功能化纳米颗粒（NP）的生产和加工的新兴技术需要先进的NP表征和分离方法。虽然有各种各样的方法可以通过大小来分离NP，但没有有效的表面化学方法来分离NP。利用广泛的耗散粒子动力学模拟，本工作研究了NP在聚合物刷（PB）接枝的孔通道中的粘附和流动机制，寻找与聚合物液相色谱的临界条件相似的NP与尺寸无关的分离条件。我们研究了亲疏水配体功能化的NPs与PBs的相互作用，其中的构象和粘附性能受溶剂质量的控制，溶剂质量随溶剂组分的组成而变化。利用模拟光镊实验技术的幽灵镊子模拟方法计算出的自由能图来表征NP-PB的粘附特性。根据不同溶剂质量下的NP大小和配体组成，计算NP亨利常数和相应的分配系数。研究结果表明，随着溶剂质量的降低，NP的洗脱经历了从粒径排除模式（NP较大，保留时间较短）到洗脱顺序相反的吸附模式的转变。这种转变发生在一个狭窄的溶剂组成范围内，标志着所谓的“临界”吸附点，它强烈依赖于NP功能化。采用对流扩散模型表征了NP在等温和梯度洗脱模式下的轴向弥散动力学。研究表明，通过控制溶剂组成变化的相互作用NP色谱梯度模式，可以在吸附临界点上有效地分离NPs。
Emerging technologies of production and processing of functionalized nanoparticles (NP) require advanced methods of NP characterization and separation. While various methods are available for NP separation by size, there are no efficient methods for NP separation by surface chemistry. Using extensive dissipative particle dynamics simulations, this work investigates the mechanisms of NP adhesion and flow in polymer brush (PB)-grafted pore channels searching for the conditions for size-independent separation of NPs that are similar to the critical conditions of liquid chromatography of polymers. We consider interactions of NPs functionalized by hydrophilic and hydrophobic ligands with PBs, in which conformation and adhesion properties are controlled by the solvent quality varied with the composition of thermodynamically good and poor solvent components. The NP-PB adhesion is characterized by the free energy landscape calculated by the ghost tweezers simulation method that mimics the experimental technique of optical tweezers. The NP Henry constant and the respective partition coefficient are calculated depending on the NP size and ligand composition at varying solvent quality. Our findings demonstrate that, with the decrease of solvent quality, the NP elution undergoes a transition from the size-exclusion mode with larger NPs having shorter retention time to the adsorption mode with the reverse order of elution. This transition, which occurs in a narrow range of solvent composition, signifies the so-called “critical” point of adsorption that strongly depends on the NP functionalization. The dynamics of NP axial dispersion in the isocratic and gradient elution modes is characterized employing a convective-diffusion model. We show that the NPs can be effectively separated by surface chemistry at the critical points of adsorption, using the gradient mode of interaction NP chromatography with controlled variation of the solvent composition.
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影响因子：
18.3
作者：
Kim, Sung Tae;Saha, Krishnendu;Kim, Chaekyu;Rotello, Vincent M.
通讯作者：
Rotello, Vincent M.
聚合物色谱的交互模式
DOI：
--
发表时间：
2013
期刊：
影响因子：
--
作者：
H. Pasch;B. Trathnigg
通讯作者：
B. Trathnigg
在整体硅胶毛细管柱上对分子量范围高达 7.45×106 的标准聚苯乙烯进行尺寸排阻色谱分析
DOI：
--
发表时间：
2006
期刊：
影响因子：
--
作者：
K. Ute;Saori Yoshida;T. Kitayama;T. Bamba;Kazuo Harada;E. Fukusaki;A. Kobayashi;N. Ishizuka;H. Minakuchi;K. Nakanishi
通讯作者：
K. Nakanishi
无孔基质上聚合物吸附和色谱的临界条件。
影响因子：
9.9
作者：
R. Cimino;C. J. Rasmussen;Ye.Ye. Brun;A. Neimark
通讯作者：
A. Neimark
DOI：
10.1063/1.4905894
发表时间：
2015-01
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Jianli Cheng;A. Vishnyakov;A. Neimark
通讯作者：
Jianli Cheng;A. Vishnyakov;A. Neimark