Unusual Aspects of Charge Regulation in Flexible Weak Polyelectrolytes

Overview

Journal Polymers (Basel)

Publisher MDPI

Date 2023 Jun 28

PMID 37376324

Authors

Pablo M Blanco

Claudio F Narambuena

Sergio Madurga

Francesc Mas

Josep L Garces

Affiliations

Soon will be listed here.

Abstract

This article reviews the state of the art of the studies on charge regulation (CR) effects in flexible weak polyelectrolytes (FWPE). The characteristic of FWPE is the strong coupling of ionization and conformational degrees of freedom. After introducing the necessary fundamental concepts, some unconventional aspects of the the physical chemistry of FWPE are discussed. These aspects are: (i) the extension of statistical mechanics techniques to include ionization equilibria and, in particular, the use of the recently proposed Site Binding-Rotational Isomeric State (SBRIS) model, which allows the calculation of ionization and conformational properties on the same foot; (ii) the recent progresses in the inclusion of proton equilibria in computer simulations; (iii) the possibility of mechanically induced CR in the stretching of FWPE; (iv) the non-trivial adsorption of FWPE on ionized surfaces with the same charge sign as the PE (the so-called "wrong side" of the isoelectric point); (v) the influence of macromolecular crowding on CR.

Citing Articles

Charge Regulation Triggers Condensation of Short Oligopeptides to Polyelectrolytes.

Pineda S, Stano R, Murmiliuk A, Blanco P, Montes P, Tosner Z JACS Au. 2024; 4(5):1775-1785.

PMID: 38818083 PMC: 11134362. DOI: 10.1021/jacsau.3c00668.

References

Lund M, Jonsson B . Charge regulation in biomolecular solution. Q Rev Biophys. 2013; 46(3):265-81. DOI: 10.1017/S003358351300005X. View

Ellis R . Macromolecular crowding: obvious but underappreciated. Trends Biochem Sci. 2001; 26(10):597-604. DOI: 10.1016/s0968-0004(01)01938-7. View

Li Y, Zhao T, Wang C, Lin Z, Huang G, Sumer B . Molecular basis of cooperativity in pH-triggered supramolecular self-assembly. Nat Commun. 2016; 7:13214. PMC: 5095283. DOI: 10.1038/ncomms13214. View

Rathee V, Sidky H, Sikora B, Whitmer J . Role of Associative Charging in the Entropy-Energy Balance of Polyelectrolyte Complexes. J Am Chem Soc. 2018; 140(45):15319-15328. DOI: 10.1021/jacs.8b08649. View

Mella M, Tagliabue A, Mollica L, Izzo L . Monte Carlo study of the effects of macroion charge distribution on the ionization and adsorption of weak polyelectrolytes and concurrent counterion release. J Colloid Interface Sci. 2019; 560:667-680. DOI: 10.1016/j.jcis.2019.10.051. View

Yigit C, Heyda J, Dzubiella J . Charged patchy particle models in explicit salt: Ion distributions, electrostatic potentials, and effective interactions. J Chem Phys. 2015; 143(6):064904. DOI: 10.1063/1.4928077. View

Konopka M, Shkel I, Cayley S, Record M, Weisshaar J . Crowding and confinement effects on protein diffusion in vivo. J Bacteriol. 2006; 188(17):6115-23. PMC: 1595386. DOI: 10.1128/JB.01982-05. View

Balbo J, Mereghetti P, Herten D, Wade R . The shape of protein crowders is a major determinant of protein diffusion. Biophys J. 2013; 104(7):1576-84. PMC: 3617426. DOI: 10.1016/j.bpj.2013.02.041. View

Marszalek P, Oberhauser A, Pang Y, Fernandez J . Polysaccharide elasticity governed by chair-boat transitions of the glucopyranose ring. Nature. 1999; 396(6712):661-4. DOI: 10.1038/25322. View

10.

Landsgesell J, Nova L, Rud O, Uhlik F, Sean D, Hebbeker P . Simulations of ionization equilibria in weak polyelectrolyte solutions and gels. Soft Matter. 2019; 15(6):1155-1185. DOI: 10.1039/c8sm02085j. View

11.

Saxton M . Anomalous diffusion due to obstacles: a Monte Carlo study. Biophys J. 1994; 66(2 Pt 1):394-401. PMC: 1275707. DOI: 10.1016/s0006-3495(94)80789-1. View

12.

Madurga S, Rey-Castro C, Pastor I, Vilaseca E, David C, Garces J . A semi-grand canonical Monte Carlo simulation model for ion binding to ionizable surfaces: proton binding of carboxylated latex particles as a case study. J Chem Phys. 2011; 135(18):184103. DOI: 10.1063/1.3658484. View

13.

Radiom M, Kong P, Maroni P, Schafer M, Kilbinger A, Borkovec M . Mechanically induced cis-to-trans isomerization of carbon-carbon double bonds using atomic force microscopy. Phys Chem Chem Phys. 2016; 18(45):31202-31210. DOI: 10.1039/c6cp05696b. View

14.

Jurij R, Per L . MOLSIM: A modular molecular simulation software. J Comput Chem. 2015; 36(16):1259-74. PMC: 5033024. DOI: 10.1002/jcc.23919. View

15.

Garces J, Madurga S, Borkovec M . Coupling of conformational and ionization equilibria in linear poly(ethylenimine): a study based on the site binding/rotational isomeric state (SBRIS) model. Phys Chem Chem Phys. 2014; 16(10):4626-38. DOI: 10.1039/c3cp54211d. View

16.

Pastor I, Vilaseca E, Madurga S, Garces J, Cascante M, Mas F . Effect of crowding by dextrans on the hydrolysis of N-Succinyl-L-phenyl-Ala-p-nitroanilide catalyzed by α-chymotrypsin. J Phys Chem B. 2010; 115(5):1115-21. DOI: 10.1021/jp105296c. View

17.

Cai W, Bullerjahn J, Lallemang M, Kroy K, Balzer B, Hugel T . Angle-dependent strength of a single chemical bond by stereographic force spectroscopy. Chem Sci. 2022; 13(19):5734-5740. PMC: 9117962. DOI: 10.1039/d2sc01077a. View

18.

Blanco P, Garces J, Madurga S, Mas F . Macromolecular diffusion in crowded media beyond the hard-sphere model. Soft Matter. 2018; 14(16):3105-3114. DOI: 10.1039/c8sm00201k. View

19.

Zhukouskaya H, Blanco P, Cernochova Z, ctverackova L, Stano R, Pavlova E . Anionically Functionalized Glycogen Encapsulates Melittin by Multivalent Interaction. Biomacromolecules. 2022; 23(8):3371-3382. DOI: 10.1021/acs.biomac.2c00400. View

20.

de Oliveira V, Liu R, Shen J . Constant pH molecular dynamics simulations: Current status and recent applications. Curr Opin Struct Biol. 2022; 77:102498. PMC: 9933785. DOI: 10.1016/j.sbi.2022.102498. View