Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials
SCIE
SCOPUS
- Title
- Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials
- Authors
- KIM, HYUNGBIN; Lee, Jinhoon; Hong, Yuri; Lim, Chanoong; Lee, Dong Woog; Oh, Dongyeop X.; Waite, J. Herbert; Hwang, Dong Soo
- Date Issued
- 2022-06
- Publisher
- American Chemical Society (ACS)
- Abstract
- The load-bearing proteins in mussel holdfasts rely on condensed tris-catecholato-Fe3+ coordination complexes for their toughness and shock-absorbing properties, and this feature has been successfully translated into synthetic materials with short-term high-performance properties. However, oxidation of catecholic DOPA (3,4-dihydroxyphenylalanine) remains a critical impediment to achieving materials with longer-lasting performance. Here, following the natural mussel pathway for protein processing, we explore how DOPA oxidation impacts coacervation of mussel foot protein-1 (mfp-1) and its capacity for phase-specific metal uptake in vitro. Without metal, DOPA oxidation changed the rheological properties (i.e., viscosity, loss, and storage moduli) of mfp-1 coacervate droplets. However, oxidation-dependent changes were recovered with dithiothreitol (DTT), completely restoring the behavior of mfp-1 coacervates prior to oxidation. With metal, mfp-1 coacervates exhibited gel-like behavior with high viscosity and cohesive forces by forming recognizable bis- and tris-catecholato-Fe complexes, linked to increased energy dissipation and toughness of byssus. These results indicate that Fe3+-mediated conversion of liquid-liquid phase-separated polymers into metal-coordinated networks is thorough and rapid, and DTT effectively maintains redox integrity. Our study provides much-needed improvements for processing catechol-functionalized polymers into high-performance materials.
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/112775
- DOI
- 10.1021/acs.chemmater.2c00406
- ISSN
- 0897-4756
- Article Type
- Article
- Citation
- Chemistry of Materials, vol. 34, no. 11, page. 5074 - 5083, 2022-06
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