Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates

Polyelectrolyte coacervates, with their greater-than-water density, low interfacial energy, shear thinning viscosity, and ability to undergo structural arrest, mediate the formation of diverse load-bearing macromolecular materials in living organisms as well as in industrial material fabrication. Co...

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Main Authors: Li, Meng, Mirshafian, Razieh, Wang, Jining, Mohanram, Harini, Ahn, Kollbe Ando, Hosseinzadeh, Shayan, Pervushin, Konstantin, Waite, J. Herbert, Yu, Jing
Other Authors: School of Materials Science and Engineering
Format: Article
Language:English
Published: 2023
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Online Access:https://hdl.handle.net/10356/171276
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1712762024-04-05T15:47:21Z Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates Li, Meng Mirshafian, Razieh Wang, Jining Mohanram, Harini Ahn, Kollbe Ando Hosseinzadeh, Shayan Pervushin, Konstantin Waite, J. Herbert Yu, Jing School of Materials Science and Engineering School of Biological Sciences Institute for Digital Molecular Analytics and Science Nanyang Environment and Water Research Institute Singapore Membrane Technology Centre Engineering Phase-behavior Adhesion Polyelectrolyte coacervates, with their greater-than-water density, low interfacial energy, shear thinning viscosity, and ability to undergo structural arrest, mediate the formation of diverse load-bearing macromolecular materials in living organisms as well as in industrial material fabrication. Coacervates, however, have other useful attributes that are challenging to study given the metastability of coacervate colloidal droplets and a lack of suitable analytical methods. We adopt solution electrochemistry and nuclear magnetic resonance measurements to obtain remarkable insights about coacervates as solvent media for low-molecular-weight catechols. When catechols are added to dispersions of coacervated polyelectrolytes, there are two significant consequences: (1) catechols preferentially partition up to 260-fold into the coacervate phase, and (2) coacervates stabilize catechol redox potentials by up to +200 mV relative to the equilibrium solution. The results suggest that the relationship between phase-separated polyelectrolytes and their client molecules is distinct from that existing in aqueous solution and has the potential for insulating many redox-unstable chemicals. Ministry of Education (MOE) National Research Foundation (NRF) Submitted/Accepted version This work was supported by National Institutes of Health Grant R01-DE018468 and by NSF Materials Research Science & Engineering Center Grant DMR 1720256. M.L., J.W., and J.Y. thank the Singapore National Research Fellowship (NRF-NRFF11-2019-0004) and the Singapore Ministry of Education (MOE) Academic Research Fund (AcRF) Tier 2 Grant (MOE-T2EP30220-0006). M.L. acknowledges the Fundamental Research Funds for the Central Universities (GK202207016). S.H. and K.P. acknowledge the Singapore Ministry of Education Academic Research Fund Tier 3 grant (grant no. MOE 2019-T3-1-012). 2023-10-18T04:04:13Z 2023-10-18T04:04:13Z 2023 Journal Article Li, M., Mirshafian, R., Wang, J., Mohanram, H., Ahn, K. A., Hosseinzadeh, S., Pervushin, K., Waite, J. H. & Yu, J. (2023). Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates. Biomacromolecules, 24(9), 4190-4198. https://dx.doi.org/10.1021/acs.biomac.3c00519 1525-7797 https://hdl.handle.net/10356/171276 10.1021/acs.biomac.3c00519 37603820 2-s2.0-85169880971 9 24 4190 4198 en NRF-NRFF11-2019-0004 MOE-T2EP30220-0006 MOE2019-T3-1-012 Biomacromolecules © 2023 American Chemical Society. All rights reserved. This article may be downloaded for personal use only. Any other use requires prior permission of the copyright holder. The Version of Record is available online at http://doi.org/10.1021/acs.biomac.3c00519. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering
Phase-behavior
Adhesion
spellingShingle Engineering
Phase-behavior
Adhesion
Li, Meng
Mirshafian, Razieh
Wang, Jining
Mohanram, Harini
Ahn, Kollbe Ando
Hosseinzadeh, Shayan
Pervushin, Konstantin
Waite, J. Herbert
Yu, Jing
Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
description Polyelectrolyte coacervates, with their greater-than-water density, low interfacial energy, shear thinning viscosity, and ability to undergo structural arrest, mediate the formation of diverse load-bearing macromolecular materials in living organisms as well as in industrial material fabrication. Coacervates, however, have other useful attributes that are challenging to study given the metastability of coacervate colloidal droplets and a lack of suitable analytical methods. We adopt solution electrochemistry and nuclear magnetic resonance measurements to obtain remarkable insights about coacervates as solvent media for low-molecular-weight catechols. When catechols are added to dispersions of coacervated polyelectrolytes, there are two significant consequences: (1) catechols preferentially partition up to 260-fold into the coacervate phase, and (2) coacervates stabilize catechol redox potentials by up to +200 mV relative to the equilibrium solution. The results suggest that the relationship between phase-separated polyelectrolytes and their client molecules is distinct from that existing in aqueous solution and has the potential for insulating many redox-unstable chemicals.
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Li, Meng
Mirshafian, Razieh
Wang, Jining
Mohanram, Harini
Ahn, Kollbe Ando
Hosseinzadeh, Shayan
Pervushin, Konstantin
Waite, J. Herbert
Yu, Jing
format Article
author Li, Meng
Mirshafian, Razieh
Wang, Jining
Mohanram, Harini
Ahn, Kollbe Ando
Hosseinzadeh, Shayan
Pervushin, Konstantin
Waite, J. Herbert
Yu, Jing
author_sort Li, Meng
title Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
title_short Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
title_full Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
title_fullStr Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
title_full_unstemmed Compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
title_sort compliant clients: catechols exhibit enhanced solubility and stability in diverse complex coacervates
publishDate 2023
url https://hdl.handle.net/10356/171276
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