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Complexation between Oppositely Charged Polyelectrolytes in Dilute Solution: Effects of Charge Asymmetry

Chen, Shensheng and Zhang, Pengfei and Wang, Zhen-Gang (2022) Complexation between Oppositely Charged Polyelectrolytes in Dilute Solution: Effects of Charge Asymmetry. Macromolecules, 55 (10). pp. 3898-3909. ISSN 0024-9297. doi:10.1021/acs.macromol.2c00339.

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We use dissipative particle dynamics to study polyelectrolyte complexation in dilute solutions under conditions of either chain-length or concentration asymmetry between the polycation and the polyanion, characterized by the macromolecular charge ratio of the minor component to the major component. Our results show that generally the systems form clusters carrying net macromolecular charges. The stoichiometry of these net-charged macromolecular clusters depends on the overall charge asymmetry, and clusters with certain stoichiometry can dominate the cluster population under a wide range of chain-length and concentration asymmetry. The morphology and stability of these net-charged clusters are closely related to their stoichiometry. When the charge ratio reaches a threshold value, the polyions condense into a single large coacervate cluster, signaling the onset of macroscopic coacervation. The threshold value is less for concentration asymmetry systems than for chain-length asymmetry systems at the same salt concentration. This threshold value decreases with added salt, as salt ions cause merging of small clusters into larger ones, eventually leading to the dominance of a single large cluster. This “salting-out” phenomenon is followed by a “salting-in” behavior, as further addition of salt dissolves the large cluster. The preferred size and composition of the net-charged clusters observed in the simulation highlight the significant role of length and concentration asymmetry on polyelectrolyte complex coacervation and hint at the possibility of a microstructured liquid.

Item Type:Article
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URLURL TypeDescription
Chen, Shensheng0000-0002-6427-935X
Zhang, Pengfei0000-0002-4226-1394
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2022 American Chemical Society. Received: February 15, 2022; Revised: April 23, 2022; Published: May 13, 2022. This research was supported by funding from Hong Kong Quantum AI Lab Ltd. This research used resources of the Center for Functional Nanomaterials (CFN), which is a U.S. Department of Energy Office of Science User Facility, at Brookhaven National Laboratory under Contract DE-SC0012704. P.Z. acknowledges the financial support provided by the National Natural Science Foundation of China (22073016 and 21803011) and the award of Shanghai Dongfang Scholar. The authors declare no competing financial interest.
Funding AgencyGrant Number
Hong Kong Quantum AI Lab Ltd.UNSPECIFIED
Department of Energy (DOE)DE-SC0012704
National Natural Science Foundation of China22073016
National Natural Science Foundation of China21803011
Shanghai Dongfang ScholarUNSPECIFIED
Subject Keywords:Chemical structure, Cluster chemistry, Counterions, Metal clusters, Salts
Issue or Number:10
Record Number:CaltechAUTHORS:20220520-388256000
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Official Citation:Complexation between Oppositely Charged Polyelectrolytes in Dilute Solution: Effects of Charge Asymmetry. Shensheng Chen, Pengfei Zhang, and Zhen-Gang Wang. Macromolecules 2022 55 (10), 3898-3909; DOI: 10.1021/acs.macromol.2c00339
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114842
Deposited By: George Porter
Deposited On:20 May 2022 22:30
Last Modified:08 Jun 2022 16:43

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