Controlling Comonomer Distribution in Random Copolymers by Chemical Coloring of Surface-Tethered Homopolymers: An Insight from Discontinuous Molecular Dynamics Simulation

Strickland, L. Anderson; Hall, Carol K.; Genzer, Jan

doi:10.1021/la9045513

Cited by 7 publications

(3 citation statements)

References 35 publications

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“…More recently, MD simulations have been applied to structural studies of polymer brushes including PS, , PMMA, block copolyelectrolytes, PAAEE, and PEG-based brushes. , More advanced simulations have been developed to study the structure of “hairy” particles, , capillary rise in brush-modified nanotubes, diffusion of colloids within polymer brush films, , and brush-modified nanochannels. − Furthermore, MD models of frictional forces between opposing polymer brushes, compression-induced phase transitions, liquid flow over polymer brush films, and even postpolymerization modification reactions have been realized. Elliott et al have recently reviewed the consistencies between MD simulations and neutron reflectivity experiments.…”

Section: Polymer Brush Theorymentioning

confidence: 99%

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

et al. 2017

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The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ever increasing set of computational and simulation tools that allow understanding and predictions of these surface-grafted polymer architectures. The aim of this contribution is to provide a comprehensive review that critically assesses recent advances in the field and highlights the opportunities and challenges for future work.

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Section: Polymer Brush Theorymentioning

confidence: 99%

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

et al. 2017

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“…Controlling the sequences of synthetic copolymers remains an important goal in polymer science. , Just as the functions of critical biological copolymers depend directly upon their sequences, the material properties and functional abilities of synthetic copolymers are similarly dependent upon the order in which monomers are connected one to another. Significant effort is currently aimed at developing effective and innovative ways to control sequence. − At the same time, questions remain regarding the variety of sequences produced and the factors governing them in even relatively simple copolymerization processes.…”

Section: Introductionmentioning

confidence: 99%

The Sequence of a Step-Growth Copolymer Can Be Influenced by Its Own Persistence Length

Zhang

DuBay

2021

J. Phys. Chem. B

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Synthetic copolymer sequences remain challenging to control, and there are features of even simple one-pot, solution-based copolymerizations that are not yet fully understood. In previous simulations on step-growth copolymerizations in solution, we demonstrated that modest variations in the attractions between type A and B monomers could significantly influence copolymer sequence through an emergent aggregation and phase separation initiated by the lengthening of nascent oligomers. Here we investigate how one aspect of a copolymer’s geometryits flexibilitycan modulate those effects. Our simulations show the onset of strand alignment within the polymerization-induced aggregates as chain stiffness increases and demonstrate that this alignment can influence the resulting copolymer sequences. For less flexible copolymers, with persistence lengths ≥10 monomers, modest nonbonded attractions of ∼k B T between monomers of the same type yield A and B blocks of a characteristic length and result in a polydispersity index that grows rapidly, peaks, and then diminishes as the reaction proceeds. These results demonstrate that for copolymer systems with modest variations in intermonomer attractions and physically realistic flexibilities a nascent copolymer’s persistence length can influence its own sequence.

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“…Modulations in the sequence of monomers can change the interfacial properties by altering the number of binding sites available to interact with the surface. For example, increasing the sequence dispersity of a random diblock copolymer results in an increased adhesion strength compared to an AB diblock copolymer. − However, challenges in synthesizing polymers with well-controlled monomer sequences have largely limited systematic investigations into the effects of monomer sequence on adsorption behavior to molecular simulations. − Experimental investigations have been restricted to exploring the effects of overall “blockiness” without providing precise control over the monomer sequence at the monomer unit level. ,, Improved polymer synthesis methods that provide monodisperse, well-controlled polymer sequences would allow for systematic investigations into the effects that specific changes in polymer sequence have on the adsorption behavior …”

Section: Introductionmentioning

confidence: 99%

Investigating the Sequence Specific Adsorption Behavior of Polypeptides at the Solid/Liquid Interface

et al. 2023

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Polymer adsorption at the solid/liquid interface depends not only on the chemical composition of the polymer but also on the specific placement of the monomers along the polymer sequence. However, challenges in designing polymers with well-controlled sequences have limited explorations into the role of polymer sequence on adsorption behavior to molecular simulations. Here, we demonstrate how the sequence control offered by polypeptide synthesis can be utilized to study the effects small changes in polymer sequence have on polymer adsorption behavior at the solid/liquid interface. Through a combination of quartz crystal microbalance with dissipation monitoring and total internal reflection ellipsometry, we study the adsorption behavior of three polypeptides, consisting of 90% lysine and 10% cysteine, onto a gold surface. We find different mechanisms are responsible for the adsorption of polypeptides and the resulting conformation on the surface. The initial adsorption of the polypeptides is driven by electrostatic interactions between the polylysine and the gold surface. Once adsorbed, the cysteine undergoes a thiol–Au reaction with the surface, altering the conformation of the polymer layer. Our findings suggest the conformation of the polypeptide layer is dependent on the placement of the cysteines within the sequence; polypeptide chains with evenly spaced cysteine groups adopt a more tightly bound “train” conformation as compared to polypeptides with closely grouped cysteine groups. We envision that the methodologies presented here to study sequence specific adsorption behaviors using polypeptides could be a valuable tool to complement molecular simulations studies.

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Controlling Comonomer Distribution in Random Copolymers by Chemical Coloring of Surface-Tethered Homopolymers: An Insight from Discontinuous Molecular Dynamics Simulation

Cited by 7 publications

References 35 publications

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

The Sequence of a Step-Growth Copolymer Can Be Influenced by Its Own Persistence Length

Investigating the Sequence Specific Adsorption Behavior of Polypeptides at the Solid/Liquid Interface

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