Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone–sulfone bonding

Fanfan Du; Baofu Qiao; Trung Dac Nguyen; Michael P. Vincent; Sharan Bobbala; Sijia Yi; Chamille Lescott; Vinayak P. Dravid; Monica Olvera de la Cruz; Evan Alexander Scott

doi:10.1038/s41467-020-18657-5

Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone–sulfone bonding

Fanfan Du, Baofu Qiao, Trung Dac Nguyen, Michael P. Vincent, Sharan Bobbala, Sijia Yi, Chamille Lescott, Vinayak P. Dravid, Monica Olvera de la Cruz, Evan Alexander Scott^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.

Original language	English (US)
Article number	4896
Journal	Nature communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-18657-5
State	Published - Dec 1 2020

Funding

The authors are grateful to Jonathan Remis for cryo-TEM observation. We thank the support from the Center for Computation & Theory of Soft Materials, the BioCryo facility of Northwestern University’s NUANCE Center, the Integrated Molecular Structure Education and Research Center, Structural Biology Facility, NU Atomic, the Nanoscale Characterization Experimental Center, Robert H. Lurie Comprehensive Cancer Center Flow Cytometry Core, and Biological Imaging Facility at Northwestern University. SAXS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was supported by the National Institutes of Health Director’s New Innovator Award (grant no. 1DP2HL132390-01), the National Institute of Allergy and Infectious Diseases (grant no. 5R21AI137932-02), the National Science Foundation CAREER Award (grant no. 1453576), the Louis A. Simpson & Kimberly K. Querrey Center for Regenerative Nano-medicine Regenerative Nanomedicine Catalyst Award, and the Department of Energy Award DE-FG02-08ER46539, and the Sherman Fairchild Foundation.

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1038/s41467-020-18657-5

Cite this

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title = "Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone–sulfone bonding",

abstract = "Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.",

author = "Fanfan Du and Baofu Qiao and Nguyen, {Trung Dac} and Vincent, {Michael P.} and Sharan Bobbala and Sijia Yi and Chamille Lescott and Dravid, {Vinayak P.} and {Olvera de la Cruz}, Monica and Scott, {Evan Alexander}",

note = "Funding Information: The authors are grateful to Jonathan Remis for cryo-TEM observation. We thank the support from the Center for Computation & Theory of Soft Materials, the BioCryo facility of Northwestern University{\textquoteright}s NUANCE Center, the Integrated Molecular Structure Education and Research Center, Structural Biology Facility, NU Atomic, the Nanoscale Characterization Experimental Center, Robert H. Lurie Comprehensive Cancer Center Flow Cytometry Core, and Biological Imaging Facility at Northwestern University. SAXS experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was supported by the National Institutes of Health Director{\textquoteright}s New Innovator Award (grant no. 1DP2HL132390-01), the National Institute of Allergy and Infectious Diseases (grant no. 5R21AI137932-02), the National Science Foundation CAREER Award (grant no. 1453576), the Louis A. Simpson & Kimberly K. Querrey Center for Regenerative Nano-medicine Regenerative Nanomedicine Catalyst Award, and the Department of Energy Award DE-FG02-08ER46539, and the Sherman Fairchild Foundation. Publisher Copyright: {\textcopyright} 2020, The Author(s).",

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AU - Du, Fanfan

AU - Qiao, Baofu

AU - Nguyen, Trung Dac

AU - Vincent, Michael P.

AU - Bobbala, Sharan

AU - Yi, Sijia

AU - Lescott, Chamille

AU - Dravid, Vinayak P.

AU - Olvera de la Cruz, Monica

AU - Scott, Evan Alexander

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N2 - Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.

AB - Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.

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Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone–sulfone bonding

Abstract

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ASJC Scopus subject areas

UN SDGs

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