双响应性嵌段聚合物的纳米孔开关效应的计算机模拟

doi:10.11949/j.issn.0438-1157.20180596

摘要/Abstract

摘要：

利用计算机模拟方法(耗散粒子动力学)研究了双响应性嵌段聚合物修饰的纳米孔的开关效应。通过在纳米孔内接枝具有温度和pH响应的嵌段聚合物(N-异丙基丙烯酰胺和丙烯酸)，研究不同嵌段序列(即wall-PNIPAM-PAA或wall-PAA-PNIPAM)对纳米孔开关效应的影响，结果表明，只有wall-PNIPAM-PAA嵌段序列可以实现纳米孔在不同条件下的开关效应。同时还探究了接枝密度、链长和嵌段比例对纳米孔开关效应的影响，结果表明，中高等接枝密度、适合的链长和中等比例的嵌段比可以实现不同特征的纳米孔，用于控制纳米孔的开关效应。

关键词: 计算机模拟, 纳米孔, 聚合物, pH响应性, 温度响应性, 开关效应

Abstract:

The switching effect of the dual-responsive block polymer modified nanopore was studied by computer simulation method (dissipative particle dynamics). The dual-responsive block polymers were grafted into nanopores with temperature responsive (N-isopropylacrylamide, PNIPAM) and pH responsive (acrylic acid, PAA).The effect of different block sequences (wall-PNIPAM-PAA or wall-PAA-PNIPAM) on the nanopore switching was studied. The results show that only the wall-PNIPAM-PAA block sequence can realize the different switching effects of nanopores under different conditions. Meanwhile, the effects of different grafting density, chain length and different block ratio on the nanopore switching effect were also investigated. The results show that different nanopores can be realized at the moderate to high grafting density, the suitable chain length and the medium block ratio, which can be used to control the size of the switch.

Key words: computer simulation, nanopore, polymers, pH-responsive, temperature-responsive, switching effect

中图分类号:

O 641.3

陈政, 王莉, 周健. 双响应性嵌段聚合物的纳米孔开关效应的计算机模拟[J]. 化工学报, 2019, 70(1): 271-279.

Zheng CHEN, Li WANG, Jian ZHOU. Computer simulations on switching effect of nanopores modified by dual-responsive block polymers[J]. CIESC Journal, 2019, 70(1): 271-279.

图/表 12

图1 PAA(a), PNIPAM(b)分子的结构及粗粒化模型；聚合物(c)和纳米孔(d)的模型示意图

Fig.1 Molecular structure and coarse-grained models of PAA(a), PNIPAM(b); schematic representation of polymer(c) and nanopore models(d)

表1 不同珠子之间的排斥参数aij

Table 1 Repulsive parameters aij between different beads

Bead	a_ij
Bead	A	I	W	P
A	25.00
I	43.42	25.00
W	39.09	28.60(45.34)	25.00
P	80.00	80.00	80.00	25.00

表2 不同pH下PAA的解离度

Table 2 Dissociation degrees of PAA at different pH

pH	Dissociation degree of PAA/%
2.3	0
3	5
4	35
5	85
6	98
6.3	100

图2 在不同的温度条件下，PAA在完全去质子化和完全质子化时，不同嵌段序列在纳米孔内形成的形貌图

Fig.2 Morphologies of different diblock sequences grafted from nanopore in completely deprotonated and protonated PAA under different temperature conditions

图3 不同的嵌段序列条件下纳米孔的尺寸

Fig.3 Size of nanopores under different block sequences

图4 在不同的温度下，PAA完全去质子化和完全质子化，wall-PNIPAM-PAA 嵌段序列在不同接枝密度下的形貌图

Fig.4 Morphologies of wall-PNIPAM-PAA with different grafting densities in completely deprotonated and protonated PAA under different temperature conditions

图5 在298 K和313 K下，PAA完全去质子化和完全质子化，wall-PNIPAM-PAA嵌段序列在不同链长下的形貌图

Fig.5 Morphologies of wall-PNIPAM-PAA with different grafting lengths when PAA is completely deprotonated and protonated at 298 K and 313 K

图6 在不同的链长下纳米孔尺寸的大小

Fig.6 Size of nanopores under different chain lengths

图7 在不同的温度下，PAA完全去质子化和完全质子化时，纳米孔在不同嵌段比下的形貌图

Fig.7 Morphologies of nanopores with different block ratios in completely deprotonated and protonated PAA under different temperatures

图8 在不同的嵌段比下纳米孔的尺寸

Fig.8 Sizes of nanopores under different block ratios

图9 不同pH和不同温度条件下，嵌段序列为PNIPAM-PAA时，纳米孔的形貌图

Fig.9 Morphologies of nanopores grafted with PNIPAM-PAA at different pH and different temperatures

图10 在不同pH和不同温度条件下，嵌段序列为PNIPAM-PAA时，纳米孔尺寸的大小

Fig.10 Sizes of nanopores with PNIPAM-PAA at different pH values and different temperatures.

参考文献 38

1	Xie R , Li Y , Chu L Y . Preparation of thermo-responsive gating membranes with controllable response temperature[J]. J. Membrane Sci., 2007, 289(1/2): 76-85.
2	Chen W L , Menzel M , Prucker O , et al . Morphology of nanostructured polymer brushes dependent on production and treatment[J]. Macromolecules, 2017, 50(12): 4715- 4724.
3	Emilsson G , Schoch R L , Oertle P , et al . Surface plasmon resonance methodology for monitoring polymerization kinetics and morphology changes of brushes—evaluated with poly(N-isopropylacrylamide)[J]. Appl. Surf. Sci., 2017, 396: 384-392.
4	De Groot G W , Santonicola M G , Sugihara K , et al . Switching transport through nanopores with pH- responsive polymer brushes for controlled ion permeability[J]. ACS Appl. Mater. Interfaces, 2013, 5(4): 1400-1407.
5	Gajda M , Ulbricht M . Capillary pore membranes with grafted diblock copolymers showing reversibly changing ultrafiltration properties with independent response to ions and temperature[J]. J. Membrane Sci., 2016, 514: 510-517.
6	Zhai Q , Jiang H , Zhang X , et al . Smart modification of the single conical nanochannel to fabricate dual-responsive ion gate by self-initiated photografting and photopolymerization [J]. Talanta, 2016, 149: 280-284.
7	Friebe A , Ulbricht M . Cylindrical pores responding to two different stimuli via surface-initiated atom transfer radical polymerization for synthesis of grafted diblock copolymers[J]. Macromolecules, 2009, 42: 1838-1848.
8	Zhang L X , Cai S L , Zheng Y B , et al . Smart homopolymer modification to single glass conical nanopore channels: dual-stimuli-actuated highly efficient ion gating[J]. Adv. Funct. Mater., 2011, 21(11): 2103-2107.
9	Tagliazucchi M , Azzaroni O , Szleifer I . Responsive polymers end-tethered in solid-state nanochannels: when nanoconfinement really matters[J].
	Am J. . Chem. Soc., 2010, 132(35): 12404-12411.
10	Barsbay M , Guven O . Grafting in confined spaces: functionalization of nanochannels of track-etched membranes [J]. Radiat. Phys. Chem., 2014, 105: 26-30.
11	Shibayama M . Volume phase transition and related phenomena of polymer gels[M]//Tanaka T. Responsive Gels: Volume Transitions I. Berlin Heidelberg: Springer, 1993:1-62.
12	Kieviet B D , Schon P M , Vancso G J . Stimulus-responsive polymers and other functional polymer surfaces as components in glass microfluidic channels[J]. Lab Chip, 2014, 14(21): 4159-4170.
13	Tokarev I , Minko S . Multiresponsive, hierarchically structured membranes: new, challenging, biomimetic materials for biosensors, controlled release, biochemical gates, and nanoreactors[J]. Adv. Mater., 2009, 21(2): 241-247.
14	Chu L Y , Li Y , Zhu J H , et al . Control of pore size and permeability of a glucose-responsive gating membrane for insulin delivery[J]. J. Control Release, 2004, 97(1): 43-53.
15	Lewis S R , Datta S , Gui M , et al . Reactive nanostructured membranes for water purification[J].
	P.Natl . Acda. Sci. USA, 2011, 108(21): 8577-8582.
16	Groot R D , Warren P B . Dissipative particle dynamics: bridging the gap between atomistic and mesoscopic simulation[J].
	J. Chem. Phys., 1997, 107(11): 4423-4435.
17	Groot R D . Electrostatic interactions in dissipative particle dynamics-simulation of polyelectrolytes and anionic surfactants[J]. J. Chem. Phys., 2003, 118(24): 11265-11277.
18	Gonzalez-Melchor M , Mayoral E , Velazquez M E , et al . Electrostatic interactions in dissipative particle dynamics using the Ewald sums[J].
	J. Chem. Phys., 2006, 125(22): 224107.
19	Mai J L , Sun D L , Quan X B , et al . Mesoscopic structure of nafion-ionic liquid membrane using dissipative particle dynamics simulations[J]. Acta Phys.-Chim. Sin., 2016, 32(7): 1649-1657.
20	Mai J L , Sun D L , Li L B , et al . Phase behavior of an amphiphilic block copolymer in ionic liquid: a dissipative particle dynamics study[J].
	Chem J. . Eng. Data, 2016, 61(12): 3998-4005.
21	Wang C , Quan X B , Liao M R , et al . Computer simulations on the channel membrane formation by nonsolvent induced phase separation[J]. Macromol. Theor. Simul., 2017, 26(5): 1700027.
22	王莉, 王楚, 周健 . 耗散粒子动力学模拟嵌段聚合物刷修饰纳米孔的 pH 响应门控[J]. 高等学校化学学报, 2018, 39(1): 85-94.
	Wang L , Wang C , Zhou J . Dissipative particle dynamics simulations on the pH-responsive gating of block copolymer brush modified nanopores[J]. Chem. J. Chinese U., 2018, 39(1): 85-94.
23	Byun H , Hong B , Nam S Y , et al . Swelling behavior and drug release of poly(vinyl alcohol) hydrogel cross-linked with poly(acrylic acid)[J]. Macromol. Res., 2008, 16(3): 189-193.
24	Posel Z , Svoboda M , Colina C M , et al . Flow and aggregation of rod-like proteins in slit and cylindrical pores coated with polymer brushes: an insight from dissipative particle dynamics[J]. Soft Matter, 2017, 13(8): 1634-1645.
25	Groot R D , Madeen T J . Dynamic simulation of diblock copolymer microphase separation[J].
	Phys J. . Chem. C, 1998, 108(20): 8713-8724.
26	Groot R D , Rabone K L . Mesoscopic simulation of cell membrane damage, morphology change and rupture by nonionic surfactants[J]. Biophys. J., 2001, 81(2): 725-736.
27	Min W F , Zhao D H , Quan X B , et al . Computer simulations on the pH-sensitive tri-block copolymer containing zwitterionic sulfobetaine as a novel anti-cancer drug carrier[J]. Colloids Surf. B Biointerfaces, 2017, 152: 260-268.
28	Luo T , Lin S , Xie R , et al . pH-responsive poly(ether sulfone) composite membranes blended with amphiphilic polystyrene-block-poly(acrylic acid) copolymers[J]. J. Membrane Sci., 2014, 450: 162-173.
29	尤莉艳, 赵英, 王帅, 等 . 顶盖驱动流中胶束形态变化的耗散粒子动力学研究[J]. 高等学校化学学报, 2009, 30(9): 1784-1788.
	You L Y , Zhao Y , Wang S , et al . Morphology of linear diblock copolymer micelle under lid-driven flow[J]. Chem. J. Chinese U., 2009, 30(9): 1784-1788.
30	李延春, 刘鸿, 黄旭日, 等 . 均聚物链吸附在胶束表面上的非平衡态耗散粒子动力学[J]. 高等学校化学学报, 2011, 32(8): 1845-1848.
	Li Y C , Liu H , Huang X R , et al . Dissipative particle dynamics study of homopolymer adsorb on micelle in non-equilibrium state[J]. Chem. J. Chinese U., 2011, 32(8): 1845-1848.
31	Guo H Y , Qiu X B , Zhou J . Self-assembled core-shell and janus microphase separated structures of polymer blends in aqueous solution[J].
	J. Chem. Phys., 2013, 139(8): 084907.
32	郭泓雨, 崔洁铭, 孙德林, 等 . 温敏性两亲嵌段共聚物相行为的耗散粒子动力学模拟[J]. 化工学报, 2012, 63(11): 3707-3715.
	Guo H Y , Cui J M , Sun D L , et al . Dissipative particle dynamics simulation on phase behavior of thermo-responsive amphiphilic copolymer PCL-PNIPAM-PCL[J]. CIESC Journal, 2012, 63(11): 3707-3715.
33	Seaton M A , Anderson R L , Metz S , et al . Dl_meso: highly scalable mesoscale simulations[J]. Mol. Simulat., 2013, 39(10): 796-821.
34	Su Y X , Quan X B , Li L B , et al . Computer simulation of DNA condensation by PAMAM dendrimer[J]. Macromol. Theor. Simul., 2018, 27(2): 1700070.
35	苏运祥, 全学波, 闵文凤, 等 . PAMAM 树状大分子负载和释放阿霉素的耗散粒子动力学模拟[J]. 化工学报, 2017, 68(5): 1757-1766.
	Su Y X , Quan X B , Min W F , et al . Dissipative particle dynamics simulations on loading and release of doxorubicin by PAMAM dendrimers[J]. CIESC Journal, 2017, 68(5): 1757-1766.
36	Sarkisov L , Harrison A . Computational structure characterisation tools in application to ordered and disordered porous materials[J]. Mol. Simulat., 2011, 37(15): 1248-1257.
37	Chu L Y , Xie R , Ju X J . Stimuli-responsive membranes: smart tools for controllable mass-transfer and separation processes[J]. Chin.
	J. Chem. Eng., 2011, 19(6): 891-903.
38	Weidman J L , Mulvenna R A , Boudouris B W , et al . Unusually stable hysteresis in the pH-response of poly(acrylic acid) brushes confined within nanoporous block polymer thin films[J].
	Am J. . Chem. Soc., 2016, 138(22): 7030-7039.

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