Reexamination of the mechanisms of oxidative transformation of the insect cuticular sclerotizing precursor, 1,2-dehydro-N-acetyldopamine

Abebe, Adal; Zheng, Dong; Evans, John F.; Sugumaran, Manickam

doi:10.1016/j.ibmb.2010.06.005

Cited by 24 publications

(46 citation statements)

References 37 publications

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“…To observe the H 2 O 2 generation during the process of catechol crosslinking, we compared PEG-D4 that was cured for 5 min with PEG-D4 that was cured for 16 hrs. The 5 min-cured hydrogel appeared light yellowish in color (Figure S3), which transitioned into dark reddish brown with time as catechol polymerizes through a mechanism that resembles quinone methide tanning [35]. Our experimental design aimed at minimizing the compositional differences between samples and the only variable that we examined here was the different time points after the initiation of the oxidative catechol crosslinking (e.g., 5 min- vs. 16 hrs-cured PEG-D4).…”

Section: Resultsmentioning

confidence: 99%

“…NaIO 4 -mediated crosslinking of catechol involves the formation of α,β-dehydro intermediates (Scheme 1) [26, 35, 47]. Addition of IO 4 − oxidizes dopamine to dopamine quinone (reaction A), which tautomerizes to form α,β-dehydrodopamine (reaction B).α,β-dehydrodopamine recovers a reduced catechol side chain, which is further oxidized to its corresponding quinone (reaction C).…”

Section: Discussionmentioning

confidence: 99%

“…Addition of IO 4 − oxidizes dopamine to dopamine quinone (reaction A), which tautomerizes to form α,β-dehydrodopamine (reaction B).α,β-dehydrodopamine recovers a reduced catechol side chain, which is further oxidized to its corresponding quinone (reaction C). Crosslinking between α,β-dehydrodopamine and α,β-dehydrodopamine quinone resulted in the formation of dehydro dimer (reaction D), leading to subsequent polymerization (reaction E) [35, 47]. When catechol (i.e., dopamine and α,β-dehydrodopamine) was oxidized to its corresponding quinone (dopamine quinone and α,β-dehydrodopamine quinone, respectively) (reactions A and C, respectively), new oxidant species are generated during the process.…”

Section: Discussionmentioning

confidence: 99%

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Model polymer system for investigating the generation of hydrogen peroxide and its biological responses during the crosslinking of mussel adhesive moiety

2017

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Mussel adhesive moiety, catechol, has been utilized to design a wide variety of biomaterials. However, the biocompatibility and biological responses associated with the byproducts generated during the curing process of catechol has never been characterized. An in situ curable polymer model system, 4-armed polyethylene glycol polymer end-capped with dopamine (PEG-D4), was used to characterize the production of hydrogen peroxide (H2O2) during the oxidative crosslinking of catechol. Although PEG-D4 cured rapidly (under 30 seconds), catechol continues to polymerize over several hours to form a more densely crosslinked network over time. PEG-D4 hydrogels were examined at two different time points; 5 min and 16 hrs after initiation of crosslinking. Catechol in the 5 min-cured PEG-D4 retained the ability to continue to crosslink and generated an order of magnitude higher H2O2 (40 μM) over 6 hrs when compared to 16 hrs-cured samples that ceased to crosslink. H2O2 generated during catechol crosslinking exhibited localized cytotoxicity in culture and upregulated the expression of an antioxidant enzyme, peroxiredoxin 2, in primary dermal and tendon fibroblasts. Subcutaneous implantation study indicated that H2O2 released during oxidative crosslinking of PEG-D4 hydrogel promoted superoxide generation, macrophage recruitment, and M2 macrophage polarization in tissues surrounding the implant. Given the multitude of biological responses associated with H2O2, it is important to monitor and tailor the production of H2O2 generated from catechol-containing biomaterials for a given application.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Model polymer system for investigating the generation of hydrogen peroxide and its biological responses during the crosslinking of mussel adhesive moiety

2017

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“…Quinone methide isomerase acts on unstable NADA and NBAD quinone methides and converts them to 1,2-dehydro- N -acyldopamine derivatives [63,65,66]. Further oxidation of dehydro dopamine derivatives produces the reactive quinone methide imine amides that crosslink proteins and chitin or react with parent catechols forming dimers, trimers and other oligomers [67,68,69]. …”

Section: Insects Use Melanization and Sclerotization For Cuticulamentioning

confidence: 99%

“…These oxidations produce in both cases, oligomeric products before polymers are generated. In the case of dehydro NADA, we have demonstrated the production of not only dimers and trimers, but also oligomers up to hexamers by mass spectral studies [69]. Similarly, for both DHICA and DHI, oligomeric products have been characterized [70,71,72,73,74].…”

Section: Insects Use Melanization and Sclerotization For Cuticulamentioning

confidence: 99%

Critical Analysis of the Melanogenic Pathway in Insects and Higher Animals

Sugumaran

Barek

2016

IJMS

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160

184

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Animals synthesize melanin pigments for the coloration of their skin and use it for their protection from harmful solar radiation. Insects use melanins even more ingeniously than mammals and employ them for exoskeletal pigmentation, cuticular hardening, wound healing and innate immune responses. In this review, we discuss the biochemistry of melanogenesis process occurring in higher animals and insects. A special attention is given to number of aspects that are not previously brought to light: (1) the molecular mechanism of dopachrome conversion that leads to the production of two different dihydroxyindoles; (2) the role of catecholamine derivatives other than dopa in melanin production in animals; (3) the critical parts played by various biosynthetic enzymes associated with insect melanogenesis; and (4) the presence of a number of important gaps in both melanogenic and sclerotinogenic pathways. Additionally, importance of the melanogenic process in insect physiology especially in the sclerotization of their exoskeleton, wound healing reactions and innate immune responses is highlighted. The comparative biochemistry of melanization with sclerotization is also discussed.

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Effect of Substituents in Mussel‐inspired Surface Primers on their Oxidation and Priming Efficiency

et al. 2021

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Marine mussels contain an abundant catechol moiety, 3,4‐dihydroxyphenylalanine (DOPA), in their interfacial foot proteins. DOPA contributes to both surface adhesion and bridging between the surface and overhead proteins (surface priming) by taking advantage of the unique redox properties of catechol. Inspired by the mussel surface priming mechanism, herein we synthesized a series of DOPA‐mimetic analogs – a bifunctional group molecule, consisting of a catechol group and an acrylic group at the opposite ends. The surface primers with differently substituted (−COOH, −CH3) alkyl chains in the middle spacer were synthesized. Time‐dependent oxidation and redox potentials of the surface primers were studied in an oxidizing environment to gain a better understanding of the mussel‘s redox chemistry. The thickness and degree of priming of the surface primers on silicon‐based substrates were analyzed by ellipsometry and UV/Vis absorption spectroscopy. The post‐reactivity of the acrylic groups of the primed layer was first visualized through a reaction with an acrylic group‐reactive dye.

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Reexamination of the mechanisms of oxidative transformation of the insect cuticular sclerotizing precursor, 1,2-dehydro-N-acetyldopamine

Cited by 24 publications

References 37 publications

Model polymer system for investigating the generation of hydrogen peroxide and its biological responses during the crosslinking of mussel adhesive moiety

Model polymer system for investigating the generation of hydrogen peroxide and its biological responses during the crosslinking of mussel adhesive moiety

Critical Analysis of the Melanogenic Pathway in Insects and Higher Animals

Effect of Substituents in Mussel‐inspired Surface Primers on their Oxidation and Priming Efficiency

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