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Title: Unconventional Complex Coacervation between Neutral Polymer and Inorganic Polyoxometalate in Aqueous Solution via Direct Water Mediation

Abstract

Water, specifically in a hydration shell, is critical for many biological supramolecular aggregations in nature, where water can directly mediate intermolecular association via hydrogen bonding and is regarded as “structured water”. Conversely, little has been reported on the biomimetic water-mediated supramolecular assembly with adequately high water content to date, because of the competing thermodynamic processes of water hydration and water as a building block to participate in self-assembly. In this work, we explore water-mediated complexation based on entropy-driven biphasic coacervate formation using highly hydrophilic neutral polymer and inorganic mineral-analogous nanoclusters. For the first time (to the best of our knowledge), nonelectrostatic liquid–liquid separating coacervate formation is demonstrated between polyethylene glycol (PEG) and polyoxometalate (POM) nanoclusters in aqueous solutions of varied PEG and POM concentrations, POM types, and aqueous medium conditions. Comprehensive characterization using fluorescence microscopy, small-angle X-ray scattering, calorimetry, and other techniques has confirmed that the compositions, microstructure, and thermodynamics of PEG–POM complex coacervation are highly similar to entropy-driven complex coacervation between oppositely charged polyelectrolytes in aqueous solution. However, the effect of heavy water on critical POM concentration for the onset of coacervate formation suggests that water, instead of the counter ions as commonly debated for polyelectrolyte complex coacervation, ismore » responsible for PEG–POM coacervate formation. Specifically, structured water works as a hydrogen bond donor for both highly hydrated PEG and POM to directly mediate the PEG–water–POM association, resulting in the release of excess hydrated water for entropy-driven PEG–POM complex coacervation. Furthermore, water-mediated complex coacervation could be developed as a general and simple strategy to build biomimetic hybrid nanomaterials with high water content for various applications from energy-related functional nanomaterials to biomedical ramification.« less

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Wayne State Univ., Detroit, MI (United States)
  2. The Univ. of Akron, Akron, OH (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1579499
Report Number(s):
BNL-212409-2019-JAAM
Journal ID: ISSN 0024-9297
Grant/Contract Number:  
SC0012704; NSF DMR-1743041; CHE-1607138
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 21; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Jing, Benxin, Ferreira, Manuela, Gao, Yunyi, Wood, Christopher, Li, Ruipeng, Fukuto, Masafumi, Liu, Tianbo, and Zhu, Yingxi. Unconventional Complex Coacervation between Neutral Polymer and Inorganic Polyoxometalate in Aqueous Solution via Direct Water Mediation. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.macromol.9b01091.
Jing, Benxin, Ferreira, Manuela, Gao, Yunyi, Wood, Christopher, Li, Ruipeng, Fukuto, Masafumi, Liu, Tianbo, & Zhu, Yingxi. Unconventional Complex Coacervation between Neutral Polymer and Inorganic Polyoxometalate in Aqueous Solution via Direct Water Mediation. United States. https://doi.org/10.1021/acs.macromol.9b01091
Jing, Benxin, Ferreira, Manuela, Gao, Yunyi, Wood, Christopher, Li, Ruipeng, Fukuto, Masafumi, Liu, Tianbo, and Zhu, Yingxi. Fri . "Unconventional Complex Coacervation between Neutral Polymer and Inorganic Polyoxometalate in Aqueous Solution via Direct Water Mediation". United States. https://doi.org/10.1021/acs.macromol.9b01091. https://www.osti.gov/servlets/purl/1579499.
@article{osti_1579499,
title = {Unconventional Complex Coacervation between Neutral Polymer and Inorganic Polyoxometalate in Aqueous Solution via Direct Water Mediation},
author = {Jing, Benxin and Ferreira, Manuela and Gao, Yunyi and Wood, Christopher and Li, Ruipeng and Fukuto, Masafumi and Liu, Tianbo and Zhu, Yingxi},
abstractNote = {Water, specifically in a hydration shell, is critical for many biological supramolecular aggregations in nature, where water can directly mediate intermolecular association via hydrogen bonding and is regarded as “structured water”. Conversely, little has been reported on the biomimetic water-mediated supramolecular assembly with adequately high water content to date, because of the competing thermodynamic processes of water hydration and water as a building block to participate in self-assembly. In this work, we explore water-mediated complexation based on entropy-driven biphasic coacervate formation using highly hydrophilic neutral polymer and inorganic mineral-analogous nanoclusters. For the first time (to the best of our knowledge), nonelectrostatic liquid–liquid separating coacervate formation is demonstrated between polyethylene glycol (PEG) and polyoxometalate (POM) nanoclusters in aqueous solutions of varied PEG and POM concentrations, POM types, and aqueous medium conditions. Comprehensive characterization using fluorescence microscopy, small-angle X-ray scattering, calorimetry, and other techniques has confirmed that the compositions, microstructure, and thermodynamics of PEG–POM complex coacervation are highly similar to entropy-driven complex coacervation between oppositely charged polyelectrolytes in aqueous solution. However, the effect of heavy water on critical POM concentration for the onset of coacervate formation suggests that water, instead of the counter ions as commonly debated for polyelectrolyte complex coacervation, is responsible for PEG–POM coacervate formation. Specifically, structured water works as a hydrogen bond donor for both highly hydrated PEG and POM to directly mediate the PEG–water–POM association, resulting in the release of excess hydrated water for entropy-driven PEG–POM complex coacervation. Furthermore, water-mediated complex coacervation could be developed as a general and simple strategy to build biomimetic hybrid nanomaterials with high water content for various applications from energy-related functional nanomaterials to biomedical ramification.},
doi = {10.1021/acs.macromol.9b01091},
journal = {Macromolecules},
number = 21,
volume = 52,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: (a) Molecular structures of PEG and lithium metatungstate, {W12}, (b) digital photograph (i) and fluorescence micrograph (ii) of PEG− {W12} complex coacervate formed at $c$$i$ {W12} = 200 mM, $c^{i}_{EG}$ = 1.135 M and $c^{i}_{LiCl}$ = 2.0 M, for which 10 wt % f-PEG over total PEG weightmore » is added to the PEG-100k aqueous solution before mixing with {W12} aqueous solution. The micrograph was acquired by CLSM with an Airy detector. The scale bar is 20 $μ$m as shown in (ii). (c) Effect of PEG molecular weight ($M_w$) on the phase diagram of PEG−{W12} complex formation as characterized by CLSM. At constant initial $c^{i}_{EG}$ = 1.135 M and $c^{i}_{LiCl}$= 2.0 M, critical {W12} concentration, $c$$i$ {W12}(red circles) for the onset of liquid− liquid separated PEG−{W12} coacervate formation (red shaded region) is plotted against PEG $M_w.$ At $c$$i$ {W12} < $c$$i$ {W12} the mixture of PEG−LiCl and {W12} solution exhibits a monophasic homogeneous solution (black squares).« less

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