Selective Adsorption of Confined Polymers: Self-Consistent Field Theory Studies

Huang, Changhang; Podgornik, Rudolf; Man, Xingkun

doi:10.1021/acs.macromol.1c01785

Cited by 4 publications

(2 citation statements)

References 39 publications

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“…The sequence regulation of monomers may affect the micro- and macroscopic properties of polymers such as adsorption, conductivity, and degradability. − A molecular dynamics simulation based genetic algorithm has demonstrated the sequence-specific effects in compatibilization, where highly nonregular sequences allowed the potential to yield larger reductions in interfacial tension between two species than either blocky or alternating sequence. PEs and polyampholytes (PAs) complexation and adsorption are also sensitive to monomer sequencing.…”

Section: Introductionmentioning

confidence: 99%

Sequence Effects on the Salt-Enhancement Behavior of Polyelectrolytes Adsorption

Chang

Jiang

2022

Macromolecules

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The comonomer sequence tunes the chain conformation and adsorption, suggesting that sequence design could be used to target the desired properties and morphologies in block copolymer materials. In this work, designing a series of sequence-defined polyelectrolytes (SDPEs), we studied the sequence effect on the salt-enhancement behavior of polyelectrolytes (PEs) adsorption on a negatively charged surface using density functional theory, where the salt-enhancement behavior shows that the adsorption amount (ζ) of PEs on the oppositely charged surface increases with salt concentrations and it cannot be captured by mean-field theories such as self-consistent field theory because of the neglect of electrostatic correlations. Among tapered (T), reversely tapered (R), and alternating (A) sequence-defined PEs, the strength of the salt-enhancement effect of the R-sequence PEs is significantly elevated at a high surface charge density (σb = −0.06 C/m2) because the long middle neutral blocks can form loop conformations. Moreover, R-sequence PEs show the largest adsorption amounts and the strongest salt response of PE adsorptions. Because of similar structural characteristics to the diblock PEs (DPEs), the T-sequence PEs show similar adsorption behavior to DPEs under the conditions with different salt concentrations. The electrostatic attractions between surface and charged blocks are decentralized in A-sequence PE systems, resulting in the smallest adsorption amounts and the weakest salt-enhancement effect and salt response. Additionally, because the decentralization effect of the electrostatic attraction is enhanced with blocks number N b, the salt-enhancement effect of adsorption amounts is significantly weakened with N b in R- and A-sequence PE systems.

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Section: Introductionmentioning

confidence: 99%

Sequence Effects on the Salt-Enhancement Behavior of Polyelectrolytes Adsorption

Chang

Jiang

2022

Macromolecules

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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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