Simulation Study of the Phase Separation and Self-assembly of Nanoparticles Coated with Ligands†

doi:10.7503/cjcu20160086

Abstract

Abstract:

A simulation study was focused on the phase separation of binary ligands coated on the nanoparticle via the dissipative particle dynamics. After comparing with available simulation and experimental works in literatures, the results support the viewpoint that the driving force comes from the conformational entropy arisen due to a mismatch of ligand chains. A further investigation is conducted on the self-assembly of Janus or triblock Janus nanoparticles in selective solvents. The simulations show that the Janus particles tend to assemble into double-layered vesicle structure, while the triblock Janus particles can form single-layered vesicle structure. This study supplies the theoretical guideline for the design of functional vesicle material via the polymer coated nanoparticles.

Key words: Nanoparticles, Phase separation, Self-assembly, Dissipative particle dynamics, Vesicle

CLC Number:

O641
O631

TrendMD:

XU Fanhua, HENG Xiao, REN Jianxue, ZHOU Hengwei. Simulation Study of the Phase Separation and Self-assembly of Nanoparticles Coated with Ligands^†[J]. Chem. J. Chinese Universities, 2016, 37(6): 1115.

Figures/Tables 8

Fig.1 Initial configuration of the nanoparticle grafted with binary ligands

Table 1 DPD interaction parameters between different types of beads during the ligand phase separation on the nanoparticles

Species	α_ij
Species	A	B	S	N
A	18.75	33.75	18.75	18.75
B		18.75	18.75	18.75
S			18.75	18.75
N				18.75

Fig.2 Phase separation on the nanoparticle grafted by binary ligands(A1), (A2): NA∶NB=4∶4 ; (B1), (B2): NA∶NB=4∶6 ; (C1), (C2): NA∶NB=4∶10 ; (D1), (D2): NA∶NB=4∶13. (A1—D1) Show only the arrangements of head groups of ligands, in which the pink and purple beads represent head groups of A and B ligands, respectively; (A2—D2) show the corresponding arrangements of the whole ligands, in which the pink and blue beads represent A and B ligands, respectively.

Table 2 DPD interaction parameters between different types of beads during the self-assembly of nanoparticles

Species	α_ij
Species	A	B	S	N
A	25	35	25	50
B		25	60	50
S			25	50
N				25

Fig.3 Double-layered vesicle structures self-assembled by Janus nanoparticles as the building blocks(A) Scheme of Janus particle. (B1) and (B2) mA∶mB=18∶24; (C1) and (C2) mA∶mB=24∶18. (B1) and (C1) show the structure of only the nanoparticle framework, in which pink and blue represent the surface parts of nanoparticles grafted with hydrophilic and hydrophobic ligands, respectively; (B2) and(C2) show the overall structure involving ligands, in which the dark blue represents the nanoparticle, while the pink and blue represent the hydrophilic and hydrophobic ligands.

Fig.4 Morphology evolution during the formation of double-layered vesicleFrom (A) to (I), it indicates the time evolution. The representations are the same as those in the bottom row of Fig.3.

Fig.5 Single-layered vesicle structures self-assembled by triblock Janus nanoparticles as the building blocks (A) Scheme of triblock Janus particle. (B1) and (B2) mA∶mB=8∶34; (C1) and (C2) mA∶mB=13∶29; (D1) and (D2) mA∶mB=18∶24. The representations of the (B1—D1) and (B2—D2) are the same as those in Fig.3.

Fig.6 Morphology evolution during the formation of single-layered vesicleFrom (A) to (I), it indicates the time evolution. The representations are the same as those in the bottom row of Fig.3.

References 35

[1]	Huynh W. U., Dittmer J. J., Alivisatos A. P., Science, 2002, 295(5564), 2425—2427
[2]	Ferrari M., Nat. Rev. Cancer, 2005, 5(3), 161—171
[3]	Kim J., van der Bruggen B., Environ. Pollut., 2010, 158(7), 2335—2349
[4]	Martin T. B., Jayaraman A., Macromolecules, 2013, 46(22), 9144—9150
[5]	Akcora P., Liu H., Kumar S. K., Moll J., Li Y., Benicewicz B. C., Schadler L. S., Acehan D., Panagiotopoulos A. Z., Pryamitsyn V., Ganesan V., Ilavsky J., Thiyagarajan P., Colby R. H., Douglas J. F., Nat. Mater., 2009, 8(4), 354—359
[6]	Jackson A. M., Myerson J. W., Stellacci F., Nat. Mater., 2004, 3(5), 330—336
[7]	Jackson A. M., Hu Y., Silva P. J., Stellacci F., J. Am. Chem. Soc., 2006, 128(34), 11135—11149
[8]	Centrone A., Hu Y., Jackson A. M., Zerbi G., Stellacci F., Small, 2007, 3(5), 814—817
[9]	Singh C., Ghorai P. K., Horsch M. A., Jackson A. M., Larson R. G., Stellacci F., Glotzer S. C., Phys. Rev. Lett., 2007, 99(22), 226106
[10]	Liu Y. T., Zhao Y., Liu H., Liu Y. H., Lu Z. Y., J. Phys. Chem. B, 2009, 113(46), 15256—15262
[11]	Xu B. S., Zhao Y., Shen X. L., Cong Y., Yin X. M., Wang X. P., Yuan Q., Yu N. S., Dong B., Acta Phys. Chim. Sin., 2014, 30(4), 646—653
	(徐博深, 赵英, 沈显良, 丛悦, 殷秀梅, 王新鹏, 苑青, 于乃森, 董斌. 物理化学学报, 2014, 30(4), 646—653)
[12]	Niikura K., Iyo N., Higuchi T., Nishio T., Jinnai H., Fujitani N., Ijiro K., J. Am. Chem. Soc., 2012, 134(18), 7632—7635
[13]	Lin J., Wang S., Huang P., Wang Z., Chen S., Niu G., Li W., He J., Cui D., Lu G., Chen X., Nie Z., ACS Nano, 2013, 7(6), 5320—5329
[14]	He J., Huang X., Li Y. C., Liu Y., Babu T., Aronova M. A., Wang S., Lu Z., Chen X., Nie Z., J. Am. Chem. Soc., 2013, 135(21), 7974—7984
[15]	He J., Liu Y., Babu T., Wei Z., Nie Z., J. Am. Chem. Soc., 2012, 134(28), 11342—11345
[16]	Huang P., Lin J., Li W., Rong P., Wang Z., Wang S., Wang X., Sun X., Aronova M., Niu G., Leapman R. D., Nie Z., Chen X., Angew. Chem. Int. Ed., 2013, 52(52), 13958—13964
[17]	Bian T., Shang L., Yu H., Perez M. T., Wu L. Z., Tung C. H., Nie Z., Tang Z., Zhang T., Adv. Mater., 2014, 26(32), 5613—5618
[18]	Arai N., Yasuoka K., Zeng X. C., Nanoscale, 2013, 5(19), 9089—9100
[19]	Zou Q. Z., Li Z. W., Lu Z. Y., Sun Z. Y., Nanoscale, 2016, 8(7), 4070—4076
[20]	Xu J., Wang Y. L., He X. H., Soft Matter, 2012, 11(37), 7433—7439
[21]	Li Z. W., Lu Z. Y., Sun Z. Y., An L. J., Soft Matter, 2012, 8(25), 6693—6697
[22]	Yamamoto S., Maruyama Y., Hyodo S. A., J. Chem. Phys., 2002, 116(13), 5842—5849
[23]	Yang K., Ma Y. Q., J. Phys. Chem. B, 2009, 113(4), 1048—1057
[24]	Caragheorgheopol A., Chechik V., Phys. Chem. Chem. Phys., 2008, 10(33), 5029—5041
[25]	Ionita P., Volkov A., Jeschke G., Chechik V., Analyt. Chem., 2008, 80(1), 95—106
[26]	Li Z. W., Lu Z. Y., Zhu Y. L., Sun Z. Y., An L. J., RSC Advances, 2013, 3(3), 813—822
[27]	Lo Verso F., Egorov S. A., Milchev A., Binder K., J. Chem. Phys., 2010, 133(18), 184901
[28]	Pivkin I. V., Karniadakis G. E., J. Comput. Phys., 2005, 207(1), 114—128
[29]	Groot R. D., Warren P. B., J. Chem. Phys., 1997, 107(11), 4423—4435
[30]	Allen M.P., Tildesley D. J., Computer Simulation of Liquids Clarendon, Oxford Press, Oxford, 1987
[31]	Hoogerbrugge P. J., Koelman J. M. V. A., Europhys. Lett., 1992, 19(3), 155—160
[32]	Koelman J. M. V. A., Hoogerbrugge P. J., Europhys. Lett., 1993, 21(3), 363—368
[33]	Liu H., Qian H. J., Zhao Y., Lu Z. Y., J. Chem. Phys., 2007, 127(14), 144903
[34]	Liu H., Li M., Lu Z. Y., Zhang Z. G., Sun C. C., Macromolecules, 2009, 42(7), 2863—2872
[35]	Li X. J., Liu Y., Wang L., Deng M. G., Liang H. J., Phys. Chem. Chem. Phys., 2009, 11(20), 4051—4059