Citation: Qing-xiao Li, Zheng Wang, Yu-hua Yin, Run Jiang, Bao-hui Li. Self-assembly of Polymer-grafted Nanoparticle Amphiphiles in Selective Solvents[J]. Acta Polymerica Sinica, ;2018, 0(10): 1351-1358. doi: 10.11777/j.issn1000-3304.2018.18072 shu

Self-assembly of Polymer-grafted Nanoparticle Amphiphiles in Selective Solvents

School of Physics, Nankai University, Tianjin 300071

Corresponding author: Bao-hui Li, baohui@nankai.edu.cn
Received Date: 2 March 2018
Revised Date: 3 April 2018
Available Online: 9 July 2018

We performed Brownian dynamics simulations with implicit solvent to study the self-assembly of polymer-grafted nanoparticle amphiphiles in selective solvents. Each model amphiphile consists of one hydrophobic nanoparticle (H) bead and one hydrophilic polymer chain composed of P-beads. The diameter of each H-bead is varied from one to several times that of each P-bead. The influences of experimental conditions on the self-assembled morphologies are investigated. The experimental conditions studied include the amphiphile concentration, the size of the hydrophobic head, the interaction parameters between the hydrophilic bead and hydrophobic bead, the polymer chain length and the solvent. Various self-assembled morphologies are obtained, including conventional spherical micelles, cylindrical micelles, cylindrical networks, large compound micelles, thin sheets, spherical vesicles, and novel ones of tubular vesicles, cylindrical multicompartment vesicles, and spherical multicompartment vesicles. The morphological phase diagrams are constructed as a function of different parameters. Mechanisms of morphological formation are discussed. Two pathways, mechanisms I and II, of vesicle formation are identified. In mechanism I, the model amphiphiles first self-assemble into spherical micelles, which transform into cylindrical micelles, further into bilayer-sheets, and finally the sheets bend around and close up to form vesicles. In mechanism II, in the initial stage of simulation, the model amphiphiles first self-assemble into many small spherical aggregates, inside which the hydrophilic P-beads are mixing with hydrophobic H-beads. Subsequently, neighboring aggregates coalesce together, and microphase separation between H and P beads occurs in the interior of the aggregates, resulting in a concentration of P-beads at the center of the aggregates, i.e., the formation of semivesicles. As simulation proceeds further, the semivesicles grow larger, and more and more P-beads enter into the inner of the semivesicles, and finally semivesicles expand outward, forming vesicles. Furthermore, transition from mechanism II to mechanism I can occur by increasing amphiphile concentration. At low amphiphile concentration, the attractions among the hydrophobic H-beads are dominant in the system. In this case, mechanism II occurs during vesicle formation. At high amphiphile concentration, repulsion among the hydrophilic P-beads dominates the system where bilayer-sheets occur as an intermediate state of the vesicle formation and thus mechanism I occurs. The simulation results are compared with available experimental and simulation results obtained from related systems.
- Polymer-grafted nanoparticle amphiphiles,
- Self-assembly,
- Selective solvents,
- Pathway of vesicle formation
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