Precise Mesoscopic Model Providing Insights into Polymerization-Induced Self-Assembly

Abstract

Self-assembly of copolymer is an important approach to obtain multifarious nanostructures. Polymerization-induced self-assembly (PISA) is a recently developed and powerful copolymer self-assembly strategy. However, some researchers have reported a different morphology prepared by PISA and the traditional copolymer self-assembly using the same copolymer system. In this work, to explore the mystery, we develop a precise mesoscopic dissipative particle dynamics (DPD) model to reveal insights into the PISA of poly­(4-vinylpyridine)-b-polystyrene (P4VP-b-PS). It is observed that P4VP-b-PS nanotubes can be obtained via TSA rather than PISA, which is consistent with reported experimental results. By carefully investigating the dynamics of PISA under specific solvent and monomer conditions and different polymerization rates, we propose that combining excessive monomers with multistep PISA can help to enhance the morphological regulation ability of PISA and retain a high solid content simultaneously. The findings in this study not only provide a precise modeling method for investigating copolymer self-assembly but also serve as a rational guide for future studies toward optimization of the PISA strategy.

Biological nanoscale fluorescent probes: From structure and performance to bioimaging

“…The development and research of low-toxicity, high-targeting, and high-selectivity drugs have become a hotspot for many scientists [1,2]. Nanoparticles have a unique size and shape-dependent physical and chemical properties [3,4]. They can be combined with targeting ligands to enter the body, target specific tumor cells, and realize cell imaging in vivo [5].…”

Self‐Stabilized Supramolecular Assemblies Constructed from PEGylated Dendritic Peptide Conjugate for Augmenting Tumor Retention and Therapy

“…We first used DPD simulations to study the supramolecular assembly behavior of PDPP at different volume fractions in H 2 O, as DPD simulation is currently recognized as a viable approach to intuitively study the polymeric supramolecular self‐assembly (SSA) process with evolving morphologies (Scheme S1, Supporting Information). [ 12 ] With an increase in the volume fraction, PDPP undergoes morphological transition from unimolecular micelles (0.5%) to nanospheres (5–10%), cylinders (20–25%), and multigeometrical aggregates (30–35%) in sequence, and the size of these assemblies also increases ( Figure , Figure S1 and Videos S1–S8, Supporting Information). The radial distribution function (RDF) plot shows that PDPP could encapsulate hydrophobic Ppa inside the hydrophilic PEGylated dendritic peptide conjugate at any volume fraction (Figure S2, Supporting Information).…”

Polymerization-Induced Self-Assembly of Comb-like Amphiphilic Copolymers into Onion-like Vesicles

“…In our work, we also compare the differences of the self-assembly morphology by PISA and TSA. It is noted that even though there is a successful example that the simulation results on TSA are well consistent with experimental results, we still need to be careful with the simulation results on the traditional self-assembly because of the dilution of comb-like polymers and the influence of the periodic boundary condition in the simulation. However, there is still some valuable information for reference.…”

“…If one random number is smaller than the reaction possibility Pr, the active ends will be bonded with the closest monomers, so that the Pr can reflect the polymerization rate. Although the polymerization rate can influence the final self-assembly morphology in some special system, , the polymerization rate can only regulate the self-assembly process and has little influence on the final morphology in most common systems. ,, Therefore, the common polymerization rate used in previous work is adopted in our work, which is Pr = 0.0001. ,, In all our simulations, the conversion of monomers is larger than 99%.…”

“…If one random number is smaller than the reaction possibility Pr, the active ends will be bonded with the closest monomers, so that the Pr can reflect the polymerization rate. Although the polymerization rate can influence the final self-assembly morphology in some special system, 59,60 the polymerization rate can only regulate the selfassembly process and has little influence on the final morphology in most common systems. 50,60,61 Therefore, the common polymerization rate used in previous work is adopted in our work, which is Pr = 0.0001.…”