Transport behavior of Janus graphene quantum dots in biomembrane: a molecular dynamics simulation

doi:10.11949/0438-1157.20220330

CIESC Journal ›› 2022, Vol. 73 ›› Issue (7): 2835-2843.DOI: 10.11949/0438-1157.20220330

• Thermodynamics • Previous Articles Next Articles

Transport behavior of Janus graphene quantum dots in biomembrane: a molecular dynamics simulation

Hongchao LIU¹(),Suhang CHEN¹,Xianli DUAN¹,Fan WU¹,Xiaofei XU²,Xianyu SONG¹(),Shuangliang ZHAO³(),Honglai LIU⁴

^1.Chongqing Key Laboratory of Water Environment Evolution and Pollution Control in Three Gorges Reservoir, School of Environmental and Chemical Engineering, Chongqing Three Gorges University, Chongqing 404020, China
^2.State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^3.Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004, Guangxi, China
^4.State Key Laboratory of Chemical Engineering, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2022-03-03 Revised:2022-05-06 Online:2022-08-01 Published:2022-07-05
Contact: Xianyu SONG,Shuangliang ZHAO

Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟

刘洪超¹(),陈苏航¹,段先力¹,吴凡¹,徐小飞²,宋先雨¹(),赵双良³(),刘洪来⁴

^1.重庆三峡学院环境与化学工程学院，三峡库区水环境演变与污染防治重庆市重点实验室，重庆 404020
^2.华东理工大学化工学院，化学工程联合国家重点实验室，上海 200237
^3.广西大学化学化工学院，广西石化资源加工与过程强化技术重点实验室，广西南宁 530004
^4.华东理工大学化学与分子工程学院，化学工程联合国家重点实验室，上海 200237

通讯作者: 宋先雨,赵双良
作者简介:刘洪超（1994—），男，硕士研究生，liuhongchao118@163.com
基金资助:
国家自然科学基金项目(22108022);重庆市自然科学基金面上项目(cstc2021jcyj-msxmX0005);万州市科技创新计划项目(wzstc20210310)

Abstract

Abstract:

Graphene quantum dots (GQDs) are widely used in biomedicine as nanocarriers. However, there has been insufficient research conducted on the cellular internalization pathway of graphene quantum dots with heterostructures. Based on the spatial heterogeneity structure design, Janus GQDs with varying oxidation levels and spatial heterogeneity distributions are constructed. Through molecular dynamics simulations, the transmembrane transport behavior of Janus GQDs with different structures was studied by analyzing configuration changes, intermolecular interactions, and solvent-accessible surfaces during transmembrane transport. According to simulation results, the transmembrane transport behavior of Janus graphene quantum dots is determined by the hydrophilic-lipophilic balance and spatially heterogeneous distribution, also showing the pull force-dependent change. This paper systematically studies the interaction between Janus graphene quantum dots and cell membranes at the molecular level, and provides theoretical guidance for their structural design and biomedical applications.

Key words: transmembrane transport, Janus graphene quantum dots, molecular dynamics, thermodynamics

摘要：

作为纳米载体，石墨烯量子点已广泛应用于生物医药领域，然而对于异质结构的石墨烯量子点细胞膜内化路径研究不足。从空间异质性结构设计出发，构建了一系列不同氧化程度与空间异质分布的Janus石墨烯量子点。基于分子动力学模拟研究了不同结构的Janus石墨烯量子点跨膜输运行为，通过分析跨膜输运过程中的构型变化、分子间作用能量、溶剂可及面积等参数，发现Janus石墨烯量子点跨膜输运行为由亲水-亲油平衡、空间异质分布控制，且呈现外力牵引依赖性变化。本文在分子水平上系统研究了Janus石墨烯量子点与细胞膜相互作用规律，对其结构设计及生物医药应用提供理论指导。

关键词: 跨膜输运, Janus石墨烯量子点, 分子动力学, 热力学

CLC Number:

TQ 028.8

Hongchao LIU, Suhang CHEN, Xianli DUAN, Fan WU, Xiaofei XU, Xianyu SONG, Shuangliang ZHAO, Honglai LIU. Transport behavior of Janus graphene quantum dots in biomembrane: a molecular dynamics simulation[J]. CIESC Journal, 2022, 73(7): 2835-2843.

刘洪超, 陈苏航, 段先力, 吴凡, 徐小飞, 宋先雨, 赵双良, 刘洪来. Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟[J]. 化工学报, 2022, 73(7): 2835-2843.

Figures/Tables 6

Fig.1 Schematics of mimicked system and structure comparison of Janus graphene quantum dots derived from simulation and experiment (Fig. 1 (b) is reproduced with permission from Ref. [24], copyright 2020 Elsevier Ltd.)

Table 1 Oxidation characteristics of Janus graphene quantum dots

序号	羟基数目 R—OH	羧基数目 R—COOH	环氧基数目 R—O—R′	氧化程度/%	备注
JGQD₁	7	8	7	7.213	方形空间异质氧化
JGQD₂	10	10	10	10.06
JGQD₃	14	12	14	13.17
GO	28	24	28	25.74	氧化石墨烯
JGQD₄	4	7	4	9.554	三角形空间异质氧化
JGQD₅	6	10	6	12.27
JGQD₆	8	14	8	15.29

Fig.2 Membrane internalization of Janus graphene quantum dots under different external forces

Fig.3 Structural characterizations of Janus graphene quantum dots in biomembrane

Fig.4 Membrane internalization of heterogeneously square-shaped oxidized Janus graphene quantum dots with various oxidation degrees

Fig.5 Membrane internalization of heterogeneously triangle-shaped oxidized Janus graphene quantum dots under different external forces

References 33

1	Brotchie A. Graphene quantum dots: it's all in the twist[J]. Nature Reviews Materials, 2016, 1: 16006.
2	胡超, 穆野, 李明宇, 等. 纳米碳点的制备与应用研究进展[J]. 物理化学学报, 2019, 35(6): 572-590.
	Hu C, Mu Y, Li M Y, et al. Recent advances in the synthesis and applications of carbon dots[J]. Acta Physico-Chimica Sinica, 2019, 35(6): 572-590.
3	孙墨杰, 赵志海, 陈红梅, 等. 碳量子点的合成研究进展与展望[J]. 化学通报, 2016, 79(8): 691-698.
	Sun M J, Zhao Z H, Chen H M, et al. Research progress and prospective of synthesizing carbon quantum dots[J]. Chemistry, 2016, 79(8): 691-698.
4	Li Y F, Yuan H Y, von dem Bussche A, et al. Graphene microsheets enter cells through spontaneous membrane penetration at edge asperities and corner sites[J]. Proceedings of the National Academy of Sciences of the United States of America, 2013, 110(30): 12295-12300.
5	Chen J L, Zhou G Q, Chen L, et al. Interaction of graphene and its oxide with lipid membrane: a molecular dynamics simulation study[J]. Journal of Physical Chemistry C, 2016, 120(11): 6225-6231.
6	Lv K, Li Y F. Indentation of graphene-covered atomic force microscopy probe across a lipid bilayer membrane: effect of tip shape, size, and surface hydrophobicity[J]. Langmuir, 2018, 34(26): 7681-7689.
7	岳华, 马光辉. 基于石墨烯独特生物界面效应的功能化载体研究进展[J]. 化学学报, 2021, 79(10): 1244-1256.
	Yue H, Ma G H. Advances in functionalized carriers based on graphene's unique biological interface effect[J]. Acta Chimica Sinica, 2021, 79(10): 1244-1256.
8	周梦迪, 沈嘉炜, 梁立军, 等. 石墨烯生物毒性的计算机模拟研究进展[J]. 化工学报, 2020, 71(1): 148-165.
	Zhou M D, Shen J W, Liang L J, et al. Advances in computer simulation of graphene biotoxicity[J]. CIESC Journal, 2020, 71(1): 148-165.
9	张国俊, 付雪峰, 郑企雨, 等. 转型中的中国化学: 基金委化学部十三五规划实施纪行[J]. 中国科学: 化学, 2020, 50(6): 681-686.
	Zhang G J, Fu X F, Zheng Q Y, et al. Chemical sciences transformation in China—review of the 13th Five-Year Plan of Department of Chemical Sciences, NSFC[J]. Scientia Sinica Chimica, 2020, 50(6): 681-686.
10	Faria M, Björnmalm M, Thurecht K J, et al. Minimum information reporting in bio-nano experimental literature[J]. Nature Nanotechnology, 2018, 13(9): 777-785.
11	Zhu G L, Xu Z Y, Yan L T. Entropy at bio-nano interfaces[J]. Nano Letters, 2020, 20(8): 5616-5624.
12	Wang Y L, Cai R, Chen C Y. The nano-bio interactions of nanomedicines: understanding the biochemical driving forces and redox reactions[J]. Accounts of Chemical Research, 2019, 52(6): 1507-1518.
13	陆小华, 董依慧, 安蓉, 等. 复杂流体-固体界面相互作用热力学机制[J]. 化工学报, 2019, 70(10): 3677-3689.
	Lu X H, Dong Y H, An R, et al. Thermodynamic mechanism of complex fluids-solids interfacial interaction[J]. CIESC Journal, 2019, 70(10): 3677-3689.
14	朱宇, 陆小华, 丁皓, 等. 分子模拟在化工应用中的若干问题及思考[J]. 化工学报, 2004, 55(8): 1213-1223.
	Zhu Y, Lu X H, Ding H, et al. Molecular simulation in chemical engineering[J]. Journal of Chemical Industry and Engineering (China), 2004, 55(8): 1213-1223.
15	赵道辉, 彭春望, 廖晨伊, 等. 面向生物能源的酶固定化的计算机模拟[J]. 化工学报, 2014, 65(5): 1828-1834.
	Zhao D H, Peng C W, Liao C Y, et al. Computer simulation of bioenergy-oriented enzyme immobilization[J]. CIESC Journal, 2014, 65(5): 1828-1834.
16	李嘉辰, 俞斌, 王琦, 等. 分子模拟研究壳聚糖-氮化硼纳米管封装及输运阿霉素[J]. 化工学报, 2020, 71(1): 354-360.
	Li J C, Yu B, Wang Q, et al. Molecular simulation on doxorubicin encapsulation and transport by chitosanboron nitride nanotubes[J]. CIESC Journal, 2020, 71(1): 354-360.
17	陆小华, 陈义峰, 董依慧, 等. 纳微界面增强CO₂吸收及机理分析[J]. 化工学报, 2020, 71(1): 34-42.
	Lu X H, Chen Y F, Dong Y H, et al. Nano-interface enhanced CO₂ absorption and mechanism analysis[J]. CIESC Journal, 2020, 71(1): 34-42.
18	陆小华, 蒋管聪, 朱育丹, 等. 受限界面处流体分子行为的调控及相关分子热力学模型初探: 基于高比表面氧化钛的研究进展[J]. 化工学报, 2018, 69(1): 1-8.
	Lu X H, Jiang G C, Zhu Y D, et al. Preliminary study on controlling nanoconfined fluid behavior and modelling molecular thermodynamics: progress in development of high-specific surface area TiO₂ [J]. CIESC Journal, 2018, 69(1): 1-8.
19	Chen P Y, Yue H, Zhai X B, et al. Transport of a graphene nanosheet sandwiched inside cell membranes[J]. Science Advances, 2019, 5(6): eaaw3192.
20	Song X Y, Ma J L, Long T, et al. Mechanochemical cellular membrane internalization of nanohydrogels: a large-scale mesoscopic simulation[J]. ACS Applied Materials & Interfaces, 2021, 13(1): 123-134.
21	Liang L J, Kong Z, Kang Z Z, et al. Theoretical evaluation on potential cytotoxicity of graphene quantum dots[J]. ACS Biomaterials Science & Engineering, 2016, 2(11): 1983-1991.
22	Xue Z Y, Sun Q, Zhang L, et al. Graphene quantum dot assisted translocation of drugs into a cell membrane[J]. Nanoscale, 2019, 11(10): 4503-4514.
23	Dallavalle M, Bottoni A, Calvaresi M, et al. Functionalization pattern of graphene oxide sheets controls entry or produces lipid turmoil in phospholipid membranes[J]. ACS Applied Materials & Interfaces, 2018, 10(18): 15487-15493.
24	Zhang Z J, Qin J L, Diao H L, et al. Janus-like asymmetrically oxidized graphene: facile synthesis and distinct liquid crystal alignment at the oil/water interface[J]. Carbon, 2020, 161: 316-322.
25	Jorgensen W L, Maxwell D S, Tirado-Rives J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids[J]. Journal of the American Chemical Society, 1996, 118(45): 11225-11236.
26	Dodda L S, Cabeza de Vaca I, Tirado-Rives J, et al. LigParGen web server: an automatic OPLS-AA parameter generator for organic ligands[J]. Nucleic Acids Research, 2017, 45(W1): W331-W336.
27	Yabe M, Mori K, Ueda K, et al. Development of PolyParGen software to facilitate the determination of molecular dynamics simulation parameters for polymers[J]. Journal of Computer Chemistry, Japan -International Edition, 2019, 5: 2018-0034.
28	Li X, Hede T, Tu Y Q, et al. Surface-active cis-pinonic acid in atmospheric droplets: a molecular dynamics study[J]. Journal of Physical Chemistry Letters, 2010, 1(4): 769-773.
29	Tang H, Zhao Y, Shan S J, et al. Wrinkle- and edge-adsorption of aromatic compounds on graphene oxide as revealed by atomic force microscopy, molecular dynamics simulation, and density functional theory[J]. Environmental Science & Technology, 2018, 52(14): 7689-7697.
30	Song X Y, Guo H, Tao J B, et al. Encapsulation of single-walled carbon nanotubes with asymmetric pyrenyl-gemini surfactants[J]. Chemical Engineering Science, 2018, 187: 406-414.
31	Chen Y, Xie B Q, Ren Y T, et al. Designed nitrogen doping of few-layer graphene functionalized by selective oxygenic groups[J]. Nanoscale Research Letters, 2014, 9(1): 646.
32	Zhang Q, Gao Y Y, Xu Z L, et al. The effects of oxygen functional groups on graphene oxide on the efficient adsorption of radioactive iodine[J]. Materials (Basel, Switzerland), 2020, 13(24): 5770.
33	Duan X L, Song X Y, Shi R F, et al. A theoretical perspective on the structure and thermodynamics of secondary organic aerosols from toluene: molecular hierarchical synergistic effects[J]. Environmental Science: Nano, 2022, 9(3): 1052-1063.

[1]	Lisen BI, Bin LIU, Hengxiang HU, Tao ZENG, Zhuorui LI, Jianfei SONG, Hanming WU. Molecular dynamics study on evaporation modes of nanodroplets at rough interfaces [J]. CIESC Journal, 2023, 74(S1): 172-178.
[2]	Hongxin YU, Shuangquan SHAO. Simulation analysis of water crystallization process [J]. CIESC Journal, 2023, 74(S1): 250-258.
[3]	Xin YANG, Wen WANG, Kai XU, Fanhua MA. Simulation analysis of temperature characteristics of the high-pressure hydrogen refueling process [J]. CIESC Journal, 2023, 74(S1): 280-286.
[4]	Minghui CHANG, Lin WANG, Jiajia YUAN, Yifei CAO. Study on the cycle performance of salt solution-storage-based heat pump [J]. CIESC Journal, 2023, 74(S1): 329-337.
[5]	Jianbo HU, Hongchao LIU, Qi HU, Meiying HUANG, Xianyu SONG, Shuangliang ZHAO. Molecular dynamics simulation insight into translocation behavior of organic cage across the cellular membrane [J]. CIESC Journal, 2023, 74(9): 3756-3765.
[6]	Rubin ZENG, Zhongjie SHEN, Qinfeng LIANG, Jianliang XU, Zhenghua DAI, Haifeng LIU. Study of the sintering mechanism of Fe₂O₃ nanoparticles based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3353-3365.
[7]	Manzheng ZHANG, Meng XIAO, Peiwei YAN, Zheng MIAO, Jinliang XU, Xianbing JI. Working fluid screening and thermodynamic optimization of hazardous waste incineration coupled organic Rankine cycle system [J]. CIESC Journal, 2023, 74(8): 3502-3512.
[8]	Xueyan WEI, Yong QIAN. Experimental study on the low to medium temperature oxidation characteristics and kinetics of micro-size iron powder [J]. CIESC Journal, 2023, 74(6): 2624-2638.
[9]	Yongquan ZHANG, Weiwei XUAN. Mechanism of alkali metal/(FeO+CaO+MgO) influence on the structure and viscosity of silicate ash slag [J]. CIESC Journal, 2023, 74(4): 1764-1771.
[10]	Yuanjing MAO, Zhi YANG, Songping MO, Hao GUO, Ying CHEN, Xianglong LUO, Jianyong CHEN, Yingzong LIANG. Estimation of SAFT-VR Mie equation of state parameters and thermodynamic properties of C₆—C₁₀ alcohols [J]. CIESC Journal, 2023, 74(3): 1033-1041.
[11]	Nini YUAN, Tuo GUO, Hongcun BAI, Yurong HE, Yongning YUAN, Jingjing MA, Qingjie GUO. Reaction process of CH₄ on the surface of Fe₂O₃/Al₂O₃ oxygen carrier in chemical looping combustion: ReaxFF-MD simulation [J]. CIESC Journal, 2022, 73(9): 4054-4061.
[12]	Yujun MA, Xiangjun LIU. Theoretical studies of water recovery from flue gas by using ceramic membrane [J]. CIESC Journal, 2022, 73(9): 4103-4112.
[13]	Yugong CHEN, Hao CHEN, Yaosong HUANG. Study on pyrolysis mechanism of hexamethyldisiloxane using reactive molecular dynamics simulations [J]. CIESC Journal, 2022, 73(7): 2844-2857.
[14]	Jian CAO, Nannan YE, Guancong JIANG, Yao QIN, Shibo WANG, Jiahua ZHU, Xiaohua LU. Mass transfer resistance analysis of the interaction between porous carbon and hydrogen peroxide based on microcalorimetry [J]. CIESC Journal, 2022, 73(6): 2543-2551.
[15]	Xue FU, Tingting CHEN, Tingting CHEN, Yingjie XU. Research progress on the conductivity properties of ionic liquids [J]. CIESC Journal, 2022, 73(5): 1883-1893.

Transport behavior of Janus graphene quantum dots in biomembrane: a molecular dynamics simulation

Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 33

Related Articles 15

Recommended Articles

Metrics

Comments