Lattice cluster theory of associating polymers. IV. Phase behavior of telechelic polymer solutions

Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.

doi:10.1063/1.4714563

Cited by 5 publications

(3 citation statements)

References 25 publications

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“…Compensation has also been derived using analytic theories based on statistical mechanical models for solutions of self-assembling telechelic molecules 72 and for systems undergoing crowding-induced self-assembly. 73 Based on such prior results and the new ones presented here, we expect the entropy-enthalpy compensation with variation of chain stiffness to be a widely occurring phenomenon in polymer binding and phase transition phenomena, with relevance as well to general molecular association.…”

Section: Resultsmentioning

confidence: 99%

The fundamental role of flexibility on the strength of molecular binding

Forrey

Douglas

Gilson³

2012

Soft Matter

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Non-covalent molecular association underlies a diverse set of biologically and technologically relevant phenomena, including the action of drugs on their biomolecular targets and self- and supra-molecular assembly processes. Computer models employed to model binding frequently use interaction potentials with atomistic detail while neglecting the thermal molecular motions of the binding species. However, errors introduced by this simplification and, more broadly, the thermodynamic consequences of molecular flexibility on binding, are little understood. Here, we isolate the fundamental relationship of molecular flexibility to binding thermodynamics via simulations of simplified molecules with a wide range of flexibilities but the same interaction potential. Disregarding molecular motion is found to generate large errors in binding entropy, enthalpy and free energy, even for molecules that are nearly rigid. Indeed, small decreases in rigidity markedly reduce affinity for highly rigid molecules. Remarkably, precisely the opposite occurs for more flexible molecules, for which increasing flexibility leads to stronger binding affinity. We also find that differences in flexibility suffice to generate binding specificity: for example, a planar surface selectively binds rigid over flexible molecules. Intriguingly, varying molecular flexibility while keeping interaction potentials constant leads to near-linear enthalpy-entropy compensation over a wide range of flexibilities, with the unexpected twist that increasing flexibility produces opposite changes in entropy and enthalpy for molecules in the flexible versus the rigid regime. Molecular flexibility is thus a crucial determinant of binding affinity and specificity and variations in flexibility can lead to strong yet non-intuitive consequences.

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Section: Resultsmentioning

confidence: 99%

The fundamental role of flexibility on the strength of molecular binding

Forrey

Douglas

Gilson³

2012

Soft Matter

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“…Generalizations were made to describe polyelectrolytes cross-linked by multivalent counterions . The contributions of Cates, Freed, Halperin, Joanny, Khokhlov, Rubinstein, , Semenov, Tanaka, ,, Wertheim, ,, Witten, and many others have inspired computational and theoretical approaches , aimed at explaining a growing corpus of experimental data in the condensate field and regarding observations made for soft materials …”

Section: Coupling Of Associative and Segregative Transitionsmentioning

confidence: 99%

Phase Transitions of Associative Biomacromolecules

et al. 2023

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Multivalent proteins and nucleic acids, collectively referred to as multivalent associative biomacromolecules, provide the driving forces for the formation and compositional regulation of biomolecular condensates. Here, we review the key concepts of phase transitions of aqueous solutions of associative biomacromolecules, specifically proteins that include folded domains and intrinsically disordered regions. The phase transitions of these systems come under the rubric of coupled associative and segregative transitions. The concepts underlying these processes are presented, and their relevance to biomolecular condensates is discussed.

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“…Moreover, the LCT can also deal with more complex lattice models for polymer systems. For example, the LCT has been used to study and explain the effects of monomer structure and compressibility on the thermodynamic properties of homopolymers, random and diblock copolymers, and telechelic polymer systems [ 58 , 63 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 ].…”

Section: Appendix A1 Fh Theory For Solutions Of Linear Homopolymers W...mentioning

confidence: 99%

Effect of End Groups on the Cloud Point Temperature of Aqueous Solutions of Thermoresponsive Polymers: An Inside View by Flory–Huggins Theory

Dang,

Nies

2024

Polymers

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In an effort to gain insight into the origin of the effects of end groups on the cloud point temperature (Tcp) as a function of the polymer molar mass of thermoresponsive polymers with lower critical solution behavior in dilute aqueous solutions, we use the Flory–Huggins (FH) theory amended for end groups. The theory was applied to available experimental data sets of poly(N-isopropylacrylamide) (PNIPAM), poly(4-vinylbenzyl methoxytris(oxyethylene) ether) (PTEGSt), and poly(α-hydro-ω-(4-vinylbenzyl)tetrakis(oxyethylene) ether) (PHTrEGSt). The theory relates the variations in TcpM,ϕcp for different end groups to the effective FH χ parameter of the end groups and explains the qualitative notion that the influence of the end groups is related to the hydrophobicity/hydrophilicity of the end groups relative to that of the so called intrinsic TcpM,ϕcp response of a polymer without end groups. The limits to the applicability of the FH theory are established, and a set of possible theoretical improvements is considered. The ultimate scrutiny of the simple FH theory and suggested improved theories must await the measurement of truly thermodynamic cloud points; the available cloud points are merely estimations of the thermodynamic cloud point, for which the deviation to the true cloud point cannot be established with sufficient accuracy.

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Lattice cluster theory of associating polymers. IV. Phase behavior of telechelic polymer solutions

Cited by 5 publications

References 25 publications

The fundamental role of flexibility on the strength of molecular binding

The fundamental role of flexibility on the strength of molecular binding

Phase Transitions of Associative Biomacromolecules

Effect of End Groups on the Cloud Point Temperature of Aqueous Solutions of Thermoresponsive Polymers: An Inside View by Flory–Huggins Theory

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