Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials
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...
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Veröffentlicht in: | Chemistry of materials 2022-06, Vol.34 (11), p.5074-5083 |
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description | 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. |
doi_str_mv | 10.1021/acs.chemmater.2c00406 |
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Herbert ; Hwang, Dong Soo</creator><creatorcontrib>Kim, Hyungbin ; Lee, Jinhoon ; Hong, Yuri ; Lim, Chanoong ; Lee, Dong Woog ; Oh, Dongyeop X. ; Waite, J. Herbert ; Hwang, Dong Soo</creatorcontrib><description>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. 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Herbert</creatorcontrib><creatorcontrib>Hwang, Dong Soo</creatorcontrib><title>Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials</title><title>Chemistry of materials</title><addtitle>Chem. Mater</addtitle><description>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. 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Herbert</creator><creator>Hwang, Dong Soo</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-3665-405X</orcidid><orcidid>https://orcid.org/0000-0002-2487-2255</orcidid><orcidid>https://orcid.org/0000-0002-8608-027X</orcidid><orcidid>https://orcid.org/0000-0003-4683-7386</orcidid><orcidid>https://orcid.org/0000-0001-9250-8968</orcidid><orcidid>https://orcid.org/0000-0002-1572-9270</orcidid><orcidid>https://orcid.org/0000-0002-0312-7256</orcidid><orcidid>https://orcid.org/0000-0001-6903-0855</orcidid></search><sort><creationdate>20220614</creationdate><title>Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials</title><author>Kim, Hyungbin ; Lee, Jinhoon ; Hong, Yuri ; Lim, Chanoong ; Lee, Dong Woog ; Oh, Dongyeop X. ; Waite, J. Herbert ; Hwang, Dong Soo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a295t-aafbd555e65256399b95a75b1a8a10820c4fa09f706fe61ca3c27f736c421f193</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kim, Hyungbin</creatorcontrib><creatorcontrib>Lee, Jinhoon</creatorcontrib><creatorcontrib>Hong, Yuri</creatorcontrib><creatorcontrib>Lim, Chanoong</creatorcontrib><creatorcontrib>Lee, Dong Woog</creatorcontrib><creatorcontrib>Oh, Dongyeop X.</creatorcontrib><creatorcontrib>Waite, J. 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Mater</addtitle><date>2022-06-14</date><risdate>2022</risdate><volume>34</volume><issue>11</issue><spage>5074</spage><epage>5083</epage><pages>5074-5083</pages><issn>0897-4756</issn><eissn>1520-5002</eissn><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.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.chemmater.2c00406</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0003-3665-405X</orcidid><orcidid>https://orcid.org/0000-0002-2487-2255</orcidid><orcidid>https://orcid.org/0000-0002-8608-027X</orcidid><orcidid>https://orcid.org/0000-0003-4683-7386</orcidid><orcidid>https://orcid.org/0000-0001-9250-8968</orcidid><orcidid>https://orcid.org/0000-0002-1572-9270</orcidid><orcidid>https://orcid.org/0000-0002-0312-7256</orcidid><orcidid>https://orcid.org/0000-0001-6903-0855</orcidid></addata></record> |
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title | Essential Role of Thiols in Maintaining Stable Catecholato-Iron Complexes in Condensed Materials |
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