Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels

Krogstad, Daniel V.; Lynd, Nathaniel A.; Choi, Soo-Hyung; Spruell, Jason M.; Hawker, Craig J.; Kramer, Edward J.; Tirrell, Matthew V.

doi:10.1021/ma302299r

Title: Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels

Full Record
Other Related Research

Abstract

Structure-property relationships were established for complex coacervate hydrogels formed from binary aqueous solutions of oppositely charged ABA triblock copolymers. The charged triblock copolymers were synthesized by functionalizing poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] with either guanidinium or sulfonate functional groups. When aqueous solutions (ca. 5-40 wt %) of these oppositely charged polymers were mixed, the electrostatic interactions of the functionalized blocks led to the association of the oppositely charged end-blocks into phase-separated complex coacervate domains bridged by the uncharged, hydrophilic PEO midblock. The resulting structures were studied by small-angle X-ray scattering (SAXS) and dynamic mechanical spectroscopy. The organization of the coacervate domains was shown to affect substantially the viscoelastic properties of the hydrogels, with the storage modulus increasing significantly as the mixtures transformed from a disordered array of domains to an ordered BCC structure with increasing block copolymer concentration. As the polymer concentration was further increased to 30 wt %, a hexagonal structure appeared, which coincided with a 25% drop in the modulus. Further structural changes, resulting in variations in the viscoelastic response, were also induced through changes in salt concentration. The viscoelastic properties and the physical nature of the cross-links have important implications for the applicability of these gelsmore » as injectable drug delivery systems.« less

Authors:: Krogstad, Daniel V.; Lynd, Nathaniel A.; Choi, Soo-Hyung; Spruell, Jason M.; Hawker, Craig J.; Kramer, Edward J.; Tirrell, Matthew V.

Publication Date:: 2013-02-26

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: University of Chicago - Institute for Molecular Engineering; USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division; National Science Foundation (NSF)

OSTI Identifier:: 1395152

DOE Contract Number:: AC02-06CH11357

Resource Type:: Journal Article

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 46; Journal Issue: 4; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Citation Formats


                    Krogstad, Daniel V., Lynd, Nathaniel A., Choi, Soo-Hyung, Spruell, Jason M., Hawker, Craig J., Kramer, Edward J., and Tirrell, Matthew V. Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels.  United States: N. p., 2013. 
        Web.  doi:10.1021/ma302299r.

Copy to clipboard


                    Krogstad, Daniel V., Lynd, Nathaniel A., Choi, Soo-Hyung, Spruell, Jason M., Hawker, Craig J., Kramer, Edward J., & Tirrell, Matthew V. Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels.  United States.  https://doi.org/10.1021/ma302299r

Copy to clipboard


                    Krogstad, Daniel V., Lynd, Nathaniel A., Choi, Soo-Hyung, Spruell, Jason M., Hawker, Craig J., Kramer, Edward J., and Tirrell, Matthew V. 2013.  
        "Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels".  United States.  https://doi.org/10.1021/ma302299r.

Copy to clipboard


                    
@article{osti_1395152,

  title        = {Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels},

  author       = {Krogstad, Daniel V. and Lynd, Nathaniel A. and Choi, Soo-Hyung and Spruell, Jason M. and Hawker, Craig J. and Kramer, Edward J. and Tirrell, Matthew V.},

  abstractNote = {Structure-property relationships were established for complex coacervate hydrogels formed from binary aqueous solutions of oppositely charged ABA triblock copolymers. The charged triblock copolymers were synthesized by functionalizing poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] with either guanidinium or sulfonate functional groups. When aqueous solutions (ca. 5-40 wt %) of these oppositely charged polymers were mixed, the electrostatic interactions of the functionalized blocks led to the association of the oppositely charged end-blocks into phase-separated complex coacervate domains bridged by the uncharged, hydrophilic PEO midblock. The resulting structures were studied by small-angle X-ray scattering (SAXS) and dynamic mechanical spectroscopy. The organization of the coacervate domains was shown to affect substantially the viscoelastic properties of the hydrogels, with the storage modulus increasing significantly as the mixtures transformed from a disordered array of domains to an ordered BCC structure with increasing block copolymer concentration. As the polymer concentration was further increased to 30 wt %, a hexagonal structure appeared, which coincided with a 25% drop in the modulus. Further structural changes, resulting in variations in the viscoelastic response, were also induced through changes in salt concentration. The viscoelastic properties and the physical nature of the cross-links have important implications for the applicability of these gels as injectable drug delivery systems.},

  doi          = {10.1021/ma302299r},

  url          = {https://www.osti.gov/biblio/1395152},
  journal      = {Macromolecules},

  issn         = {0024-9297},

  number       = 4,

  volume       = 46,

  place        = {United States},

  year         = {2013},

  month        = {2}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1021/ma302299r

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Small Angle Neutron Scattering Study of Complex Coacervate Micelles and Hydrogels Formed from Ionic Diblock and Triblock Copolymers

Journal Article Krogstad, Daniel; Choi, Soo-Hyung; Lynd, Nathaniel; ... - Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

A complex coacervate is a fluid phase that results from the electrostatic interactions between two oppositely charged macromolecules. The nature of the coacervate core structure of hydrogels and micelles formed from complexation between pairs of diblock or triblock copolymers containing oppositely charged end-blocks as a function of polymer and salt concentration was investigated. Both ABA triblock copolymers of poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] and analogous poly[(allyl glycidyl ether)-b-(ethylene oxide)] diblock copolymers, which were synthesized to be nearly one-half of the symmetrical triblock copolymers, were studied. The poly(allyl glycidyl ether) blocks were functionalized with either guanidinium or sulfonate groups viamore »« less
https://doi.org/10.1021/jp509175a
Magnetic hydrogels from alkyne/cobalt carbonyl-functionalized ABA triblock copolymers

Journal Article Jiang, Bingyin; Hom, Wendy; Chen, Xianyin; ... - Journal of the American Chemical Society

A series of alkyne-functionalized poly(4-(phenylethynyl)styrene)-block-poly(ethylene oxide)-block-poly(4-(phenylethynyl)styrene) (PPES-b-PEO-b-PPES) ABA triblock copolymers was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. PES_n[Co₂(CO)₆]_x-EO₈₀₀-PES_n[Co₂(CO)₆]_x ABA triblock copolymer/cobalt adducts (10–67 wt % PEO) were subsequently prepared by reaction of the alkyne-functionalized PPES block with Co₂(CO)₈ and their phase behavior was studied by TEM. Heating triblock copolymer/cobalt carbonyl adducts at 120 °C led to cross-linking of the PPES/Co domains and the formation of magnetic cobalt nanoparticles within the PPES/Co domains. Magnetic hydrogels could be prepared by swelling the PEO domains of the cross-linked materials with water. Furthermore, swelling tests, rheological studies and actuation tests demonstrated thatmore »« less
Cited by 11
https://doi.org/10.1021/jacs.6b01271

Full Text Available
Viscoelastic Properties, Ionic Conductivity, and Materials Design Considerations for Poly(styrene-b-ethylene oxide-b-styrene)-Based Ion Gel Electrolytes

Journal Article Zhang, Sipei; Lee, Keun; Sun, Jingru; ... - Macromolecules

The viscoelastic properties and ionic conductivity of ion gels based on the self-assembly of a poly(styrene-b-ethylene oxide-b-styrene) (SOS) triblock copolymer (M{sub n,S} = 3 kDa, M{sub n,O} = 35 kDa) in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMI][TFSA]) were investigated over the composition range of 10-50 wt % SOS and the temperature range of 25-160 C. The poly(styrene) (PS) end-blocks associate into micelles, whereas the poly(ethylene oxide) (PEO) midblocks are well-solvated by this ionic liquid. The ion gel with 10 wt % SOS melts at 54 C, with the longest relaxation time exhibiting a similar temperature dependence to that of themore »« less
https://doi.org/10.1021/ma201356j
Structure, Morphology, and Rheology of Polyelectrolyte Complex Hydrogels Formed by Self-Assembly of Oppositely Charged Triblock Polyelectrolytes

Journal Article Srivastava, Samanvaya; Levi, Adam; Goldfeld, David; ... - Macromolecules

We present scattering and rheology studies on model polyelectrolyte complex (PEC) hydrogels that form upon self-assembly of symmetric oppositely charged triblock polyelectrolytes in aqueous media. The hydrogel assembly is driven by associative phase separation of charged end-blocks to form PECs while the neutral mid-blocks restrict bulk phase separation of the PECs, leading to three-dimensional networks with PEC domains surrounded by neutral polymer coronae at sufficiently high polymer concentrations. Comprehensive characterization of the hydrogel structure (PEC domain size, morphology, spacing, and ordering) was enabled by a series of triblock polyelectrolytes with independently varying block lengths, facilitating the construction of morphology mapsmore »« less
https://doi.org/10.1021/acs.macromol.0c00847
Self-Assembly and Critical Aggregation Concentration Measurements of ABA Triblock Copolymers with Varying B Block Types: Model Development, Prediction, and Validation

Journal Article Aydin, Fikret; Chu, Xiaolei; Uppaladadium, Geetartha; ... - Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

The dissipative particle dynamics (DPD) simulation technique is a coarse-grained (CG) molecular dynamics-based approach that can effectively capture the hydrodynamics of complex systems while retaining essential information about the structural properties of the molecular species. An advantageous feature of DPD is that it utilizes soft repulsive interactions between the beads, which are CG representation of groups of atoms or molecules. In this study, we used the DPD simulation technique to study the aggregation characteristics of ABA triblock copolymers in aqueous medium. Pluronic polymers (PEG-PPO-PEG) were modeled as two segments of hydrophilic beads and one segment of hydrophobic beads. Tyrosine-derived PEG_5K-b-oligo(desaminotyrosylmore »« less
Cited by 16
https://doi.org/10.1021/acs.jpcb.5b12594

Full Text Available

Similar Records