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Phase Transitions in Concentrated Solution Self-Assembly of Globular Protein-Polymer Block Copolymers

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TLDR
The phase behavior of mCherry-b-PNIPAM (mChP) block copolymers with four different PNIPAM coil fractions was investigated in concentrated aqueous solution as a function of both concentration and temperature.
Abstract
The phase behaviour of mCherry-b-PNIPAM (mChP) block copolymers with four different PNIPAM coil fractions is investigated in concentrated aqueous solution as a function of both concentration and temperature, demonstrating both order–order transitions (OOTs) and order–disorder transitions (ODTs) in globular protein–polymer block copolymers. Independent of coil volume fraction from 0.25 to 0.70, the temperature–concentration phase diagrams share several common features. At low concentrations, mCherry-b-PNIPAM forms a homogeneous disordered phase, and macrophase separation into an ordered conjugate-rich phase and a solvent-rich phase is observed at temperatures above the PNIPAM thermoresponsive transition temperature. mChP solutions are also observed to undergo a low-temperature ODT driven by increasing concentration. The order–disorder transition concentration (ODTC) behaviour of mChP is minimized for symmetric conjugates, suggesting that repulsive solvent-mediated protein–polymer interactions provide a driving force for self-assembly. Both coil fraction and solvent selectivity have large effects on the morphologies formed—disordered micelles, hexagonally packed cylinders, lamellae, and perforated lamellae are identified with the combination of small-angle X-ray scattering (SAXS), depolarized light scattering (DPLS), turbidimetry, and differential scanning calorimetry (DSC). An OOT is observed upon increasing temperature for three of the studied coil fractions at concentrations of 40–50 wt% due to changing solvent selectivity. SANS contrast-matching experiments show that water is weakly selective for PNIPAM at low temperatures and strongly selective for mCherry at high temperatures.

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References
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Journal ArticleDOI

Depolarized Scattering from Block Copolymer Grains Using Circularly Polarized Light

TL;DR: In this article, the relationship between grain structure and depolarized light scattering from ordered block copolymer samples performed with crossed circular polarizers has been demonstrated using both theory and experiments, and it has been shown that the integrated scattered power in the CP case is twice as large as that in the LP case.
Book ChapterDOI

Design of Self-Assembling Protein-Polymer Conjugates

TL;DR: This chapter focuses on the design principles and applications of self-assembling protein-polymer conjugate materials, and addresses the general design methodology, from both synthetic and genetic perspective, conjugation strategies, protein vs. polymer driven self-assembly and finally, emerging applications for conjugates.
Journal ArticleDOI

Coiled-Coil Domains for Self-Assembly and Sensitivity Enhancement of Protein–Polymer Conjugate Biosensors

TL;DR: Three fusion protein conjugates are developed, from which two distinct heterodimeric coiled-coil conjugate are formed, but only one of theseheterodimer conjugating significantly improves the ordering quality of 2x.SA.
Journal Article

SANS Partial Structure Factor Analysis for Determining Protein-Polymer Interactions in Semidilute Solution

TL;DR: In this paper, three different polymers-PNIPAM, POEGA, and PDMAPS-were each blended with a model protein mCherry and studied using contrast variation small angle neutron scattering (SANS).
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