Harnessed Dopant Block Copolymers Assist Decorating Membrane Pores: A Dissipative Particle Dynamics Study

Abstract

Self‐assembly of asymmetric block copolymers (BCPs) around active pore edges has emerged as an important strategy to produce smart membranes with tunable pathways for solute transport. However, thus far, it is still challenging to manipulate pore shape and functionality for directional transformation under external stimuli. Here, a versatile strategy by mesoscale simulations to design stimuli‐responsive pores with various edge decorations in hybrid membranes is reported. Dopant BCPs are used as decorators to stabilize pore edges and extend their function in reconfiguring pores in response to repeated membrane stretching/shrinking caused by external stimuli. The decoration morphologies are predictable since the assemblies of dopant BCPs around pore edges are closely related to their self‐assemblies in solution. The coassembly between different BCPs in the hybrid membrane for the control of pore morphology is featured, and the parameter settings, including block incompatibility and molecular architecture for the construction of a specific pore, are determined. Results show that harnessed dopant BCPs in the hybrid membrane can enhance pore formation and induce directional pore shape and functionality transformation. Diversified pore decorations exhibit potential that can be further explored in selective solute transport and the design of stimuli‐responsive smart nanodevices.

Designing polymersomes with inhomogeneous membranes by co-assembly of block copolymers for controlled morphological reversibility

“…The length of the flexible block was set to 1 distance unit. 35,45 The length of the rigid block was set to 0.7 distance unit 35,45 and was kept unstretchable using the ''fix rigid/nve'' command. This allows us to compute the total force and torque on each rigid block as the sum of that on its constituent beads, and to update the coordinates, velocities, and orientations of the beads in each rigid block so that the block moves and rotates as a single entity.…”

“…The contact statistics were determined by the Voronoi tessellation algorithm described in our previous work. 29,35 Here, CP B-C/D and CP B-W reflect the contact probabilities between responsive block B and other hydrophobic blocks C/D, and solvent beads W, respectively. The smaller the CP B-C/D value (or the larger the CP B-W value), the easier the polymersome is to ''open'' or decompose into scattering clusters.…”

“…Of note is the co-assembly of mixed copolymers with discrepant rigidity or flexibility of the blocks, which has proven to have potential in tuning the reversibility of polymersome membranes. 34,35 The rigid polymer blocks have higher self-cohesion and therefore tend to form crystalline domains, resulting in phase separation from the self-assembly of the flexible polymer blocks. [36][37][38] The key design principle of such inhomogeneous membranes is to strike a balance between the miscibility and immiscibility of different membrane-forming components.…”

Synergistic Disruption of Metabolic Homeostasis through Hyperbranched Poly(ethylene glycol) Conjugates as Nanotherapeutics to Constrain Cancer Growth

“…Dissipative particle dynamics (DPD) simulations have been successfully used to study the self-assembly behavior of complicated polymeric systems and the structure-function relationship of nanoparticles in mesoscopic scale. [13] In this work, DPD simulations were used to investigate the co-assembly mechanism and obtain the best ratio of HP-P to HP-D for co-delivery of Ppa and DOX. Due to their amphiphilic structures, both HP-P and HP-D could self-assemble into different morphologies at different volume fractions from 1% to 30% (Figures S1A-D and S2A-D, Supporting Information).…”

“…C) Illustration of the carbon atom transition map in the [U-13 C 6 ]glucose metabolic pathway in 4T1 cells. Red circles for13 C carbons; blue circles for 12 C carbons. D) Plots of alterations in the metabolite level via log 2 (fold change) in cells treated with HP-PD NPs (at a HP-P/HP-D ratio of 3:1) compared to the untreated control.…”