Mapping the Morphological Landscape of Oligomeric Di‐block Peptide–Polymer Amphiphiles**

Abstract

Peptide-polymer amphiphiles (PPAs) are tunable hybrid materials that achieve complex assembly landscapes by combining the sequence-dependent properties of peptides with the structural diversity of polymers. Despite their promise as biomimetic materials, determining how polymer and peptide properties simultaneously affect PPA self-assembly remains challenging. We herein present a systematic study of PPA structure-assembly relationships. PPAs containing oligo(ethyl acrylate) and random-coil peptides were used to determine the role of oligomer molecular weight, dispersity, peptide length, and charge density on self-assembly. We observed that PPAs predominantly formed spheres rather than anisotropic particles. Oligomer molecular weight and peptide hydrophilicity dictated morphology, while dispersity and peptide charge affected particle size. These key benchmarks will facilitate the rational design of PPAs that expand the scope of biomimetic functionality within assembled soft materials.

Effect of solvent on the emulsion and morphology of polyfluorene films: all-atom molecular dynamics approach

“…All-atom molecular dynamics (MD) simulations were performed following the protocols developed by Taylor et al , 58 and Allen et al 59 The AMBER 2018 60 software package was used for the simulations using the General AMBER Force Field (GAFF2), 61,62 TIP3P water model, 63 and Joung-Cheatham monovalent ion parameters for TIP3P. 64…”

“…All-atom molecular dynamics (MD) simulations were performed following the protocols developed by Taylor et al, 58 and Allen et al 59 The AMBER 2018 60 software package was used for the simulations using the General AMBER Force Field (GAFF2), 61,62 TIP3P water model, 63 and Joung-Cheatham monovalent ion parameters for TIP3P. 64 Atomic partial charges for the primary solvents, secondary solvent, and PFO monomer were calculated using Gaussian 16 65 and fitted with the Restrained Electrostatic Potential (RESP) method and RESP-A1 charge model 66 via R.E.D.…”

Correlation of Emulsion Chemistry, Film Morphology, and Device Performance in Polyfluorene LEDs Deposited by RIR-MAPLE

“…MD simulations were performed using previously developed protocols explained in detail in Taylor et al and Allen et al Additional system preparation, simulation, and analysis details are in the Supporting Information. Briefly, the systems were first minimized, followed by gradual NVT heating over 150 ps, 1 ns NVT equilibration, 10 ns NPT equilibration, and finally an NVT production simulation for at least 150 ns at 300 K and 1 atm.…”

Self-Assembly of Repetitive Segment and Random Segment Polymer Architectures

“…The synthetic toolbox for controlling monomer sequences in non-natural polymers has recently expanded, enabling new opportunities to prepare synthetic materials with a high level of structural and functional diversity. − Unlike small molecules, the primary monomer sequence in synthetic macromolecules leads to complex chemical assembly landscapes that are dictated by multiple inter- and intrachain interactions . Despite recent advances, the ability to rationally design monomer sequences to control macromolecular assembly remains a key challenge in the field due to limited knowledge on sequence–structure–property relationships in synthetic polymers. , …”

“…1−6 Unlike small molecules, the primary monomer sequence in synthetic macromolecules leads to complex chemical assembly landscapes that are dictated by multiple inter-and intrachain interactions. 7 Despite recent advances, the ability to rationally design monomer sequences to control macromolecular assembly remains a key challenge in the field due to limited knowledge on sequence−structure−property relationships in synthetic polymers. 2,8 The link between sequence, structure, and function in proteins over evolutionary history provides a strategy to identify predictable sequence−property relationships in synthetic polymers.…”