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Main Authors: VanArsdale, Eric, Atoyebi, Olufolasade, Nag, Okhil, Laskoski, Matthew, Glaser, Evan, Oh, Eunkeu, Vora, Gary J, Wang, Zheng
Format: Artículo científico
Language:en
Published: International journal of molecular sciences 2025
Subjects:
Online Access:https://pubmed.ncbi.nlm.nih.gov/40565001/
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author VanArsdale, Eric
Atoyebi, Olufolasade
Nag, Okhil
Laskoski, Matthew
Glaser, Evan
Oh, Eunkeu
Vora, Gary J
Wang, Zheng
author_facet VanArsdale, Eric
Atoyebi, Olufolasade
Nag, Okhil
Laskoski, Matthew
Glaser, Evan
Oh, Eunkeu
Vora, Gary J
Wang, Zheng
VanArsdale, Eric
Atoyebi, Olufolasade
Nag, Okhil
Laskoski, Matthew
Glaser, Evan
Oh, Eunkeu
Vora, Gary J
Wang, Zheng
collection PubMed - marine biology
contents The Orthovanadate-Catalyzed Formation of a Thermally Inert and Low-Redox-Potential Melanin. VanArsdale, Eric Atoyebi, Olufolasade Nag, Okhil Laskoski, Matthew Glaser, Evan Oh, Eunkeu Vora, Gary J Wang, Zheng Melanins Oxidation-Reduction Vanadates Catalysis Catechols Selenious Acid Dihydroxyphenylalanine Catechol-like compounds are found throughout biology in the form of both redox-active and metal-binding functional groups. Within the marine environment, catechol groups are known to coordinate strongly with vanadate and ferric ions, and this binding is regulated through redox mechanisms. While investigating marine melanin formation in vitro, we found that DOPA, a catechol-containing amino acid, reacts with both metals differently when provided with sulfite, a weak reductant, and selenite, a weak oxidant. Both compounds interacted with the DOPA-vanadium complex, but only selenite, the more redox-labile chalcogenide, led to the creation of melanin particulates. When DOPA, vanadate, and selenite are present together, a metal-binding spectra shift and a melanin variant are rapidly observed. This variant was found to form large, elongated filaments with a low carboxylic acid content and a unique electron paramagnetic resonance signature. When compared to enzymatically produced melanin, this chemically synthesized variant was more thermally and biologically inert, exhibiting a lower redox activity. The results demonstrate that the regulation of the redox environment from metal-catechol interactions can help to control both the chemical and physical properties of melanin aggregates, suggesting a scalable and cell- and enzyme-free synthesis pathway for applications that may require inert materials of strict composition.
format Artículo científico
id pubmed_40565001
institution PubMed
language en
publishDate 2025
publisher International journal of molecular sciences
record_format pubmed
spellingShingle The Orthovanadate-Catalyzed Formation of a Thermally Inert and Low-Redox-Potential Melanin.
VanArsdale, Eric
Atoyebi, Olufolasade
Nag, Okhil
Laskoski, Matthew
Glaser, Evan
Oh, Eunkeu
Vora, Gary J
Wang, Zheng
Melanins
Oxidation-Reduction
Vanadates
Catalysis
Catechols
Selenious Acid
Dihydroxyphenylalanine
The Orthovanadate-Catalyzed Formation of a Thermally Inert and Low-Redox-Potential Melanin. VanArsdale, Eric Atoyebi, Olufolasade Nag, Okhil Laskoski, Matthew Glaser, Evan Oh, Eunkeu Vora, Gary J Wang, Zheng Melanins Oxidation-Reduction Vanadates Catalysis Catechols Selenious Acid Dihydroxyphenylalanine Catechol-like compounds are found throughout biology in the form of both redox-active and metal-binding functional groups. Within the marine environment, catechol groups are known to coordinate strongly with vanadate and ferric ions, and this binding is regulated through redox mechanisms. While investigating marine melanin formation in vitro, we found that DOPA, a catechol-containing amino acid, reacts with both metals differently when provided with sulfite, a weak reductant, and selenite, a weak oxidant. Both compounds interacted with the DOPA-vanadium complex, but only selenite, the more redox-labile chalcogenide, led to the creation of melanin particulates. When DOPA, vanadate, and selenite are present together, a metal-binding spectra shift and a melanin variant are rapidly observed. This variant was found to form large, elongated filaments with a low carboxylic acid content and a unique electron paramagnetic resonance signature. When compared to enzymatically produced melanin, this chemically synthesized variant was more thermally and biologically inert, exhibiting a lower redox activity. The results demonstrate that the regulation of the redox environment from metal-catechol interactions can help to control both the chemical and physical properties of melanin aggregates, suggesting a scalable and cell- and enzyme-free synthesis pathway for applications that may require inert materials of strict composition.
title The Orthovanadate-Catalyzed Formation of a Thermally Inert and Low-Redox-Potential Melanin.
topic Melanins
Oxidation-Reduction
Vanadates
Catalysis
Catechols
Selenious Acid
Dihydroxyphenylalanine
url https://pubmed.ncbi.nlm.nih.gov/40565001/