Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods

There is strong adsorption of metal ions and their complexes to chitin, which depends on both the oxidation and complexation states of many of the said elements (whereas others display chemical reactions detectable via electrochemical methods while being retained by chitin); thus, ad- and desorption...

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Main Authors: Stefan Fränzle, Felix Blind
Format: Article
Language:English
Published: MDPI AG 2022-07-01
Series:Polysaccharides
Subjects:
Online Access:https://www.mdpi.com/2673-4176/3/3/31
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author Stefan Fränzle
Felix Blind
author_facet Stefan Fränzle
Felix Blind
author_sort Stefan Fränzle
collection DOAJ
description There is strong adsorption of metal ions and their complexes to chitin, which depends on both the oxidation and complexation states of many of the said elements (whereas others display chemical reactions detectable via electrochemical methods while being retained by chitin); thus, ad- and desorption at ambient water concentrations (often in the nMol/L range) are controlled by the presence and photochemical properties (concerning Eu and probably U and Ag) of mainly biogenic organic matter (both DOC and POC, and DON). With chitin forming the outer hull of mobile organisms (animals), this biopolymer is expected to take part in metal distribution in aquatic (limnetic and riverine) ecosystems. Having studied the attachment of many different elements to both crayfish and grafted (marine shrimp) chitin, with the highest accumulations observed in Bi, V, Ni, and LREEs, one should consider secondary biochemical transformations which take place at different water and sediment levels. After chitin had been embedded into sediment, methanogenesis (which requires Ni), Bi, and Sb biomethylations and photodesorption in the illuminated water column will occur if there are appropriate organics, causing the vertical separation of Eu from other REEs, at least during the daytime. Eutrophication will enhance both the production and especially the photooxidation rates of organics in water because phosphorylated sugars and lipids are formed quantitatively within min P, which enter water and undergo Eu-mediated photooxidation much more readily. Another biopolymer, gelatin, acts as an inert matrix-enhancing organic photooxidation product via Eu, producing chemical waves, indicating autocatalysis upon light impact. From the redox-related photodesorption of metal analytes from chitin, both sensors and devices for (light-assisted) electrochemical energy conversion are being developed by our workgroup. The electrochemical determination of adsorption thermodynamics on chitin is thus directly linked to its applications in environmental monitoring and technology.
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spelling doaj.art-ee62396550364d168e6406c9f810066c2023-11-23T18:32:18ZengMDPI AGPolysaccharides2673-41762022-07-013351554310.3390/polysaccharides3030031Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic ArthropodsStefan Fränzle0Felix Blind1IHI (International Institute) Zittau, TU Dresden, Markt 23, D-02763 Zittau, GermanyIHI (International Institute) Zittau, TU Dresden, Markt 23, D-02763 Zittau, GermanyThere is strong adsorption of metal ions and their complexes to chitin, which depends on both the oxidation and complexation states of many of the said elements (whereas others display chemical reactions detectable via electrochemical methods while being retained by chitin); thus, ad- and desorption at ambient water concentrations (often in the nMol/L range) are controlled by the presence and photochemical properties (concerning Eu and probably U and Ag) of mainly biogenic organic matter (both DOC and POC, and DON). With chitin forming the outer hull of mobile organisms (animals), this biopolymer is expected to take part in metal distribution in aquatic (limnetic and riverine) ecosystems. Having studied the attachment of many different elements to both crayfish and grafted (marine shrimp) chitin, with the highest accumulations observed in Bi, V, Ni, and LREEs, one should consider secondary biochemical transformations which take place at different water and sediment levels. After chitin had been embedded into sediment, methanogenesis (which requires Ni), Bi, and Sb biomethylations and photodesorption in the illuminated water column will occur if there are appropriate organics, causing the vertical separation of Eu from other REEs, at least during the daytime. Eutrophication will enhance both the production and especially the photooxidation rates of organics in water because phosphorylated sugars and lipids are formed quantitatively within min P, which enter water and undergo Eu-mediated photooxidation much more readily. Another biopolymer, gelatin, acts as an inert matrix-enhancing organic photooxidation product via Eu, producing chemical waves, indicating autocatalysis upon light impact. From the redox-related photodesorption of metal analytes from chitin, both sensors and devices for (light-assisted) electrochemical energy conversion are being developed by our workgroup. The electrochemical determination of adsorption thermodynamics on chitin is thus directly linked to its applications in environmental monitoring and technology.https://www.mdpi.com/2673-4176/3/3/31chitin–metal ion interactionsredoxphotoredox desorption of Mdaily vertical migration of aquatic arthropodsmineral (catalyst) formation from decaying chitinEu photochemistry
spellingShingle Stefan Fränzle
Felix Blind
Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
Polysaccharides
chitin–metal ion interactions
redox
photoredox desorption of M
daily vertical migration of aquatic arthropods
mineral (catalyst) formation from decaying chitin
Eu photochemistry
title Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
title_full Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
title_fullStr Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
title_full_unstemmed Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
title_short Reversible Metal Ion/Complex Binding to Chitin Controlled by Ligand, Redox, and Photochemical Reactions and Active Movement of Chitin on Aquatic Arthropods
title_sort reversible metal ion complex binding to chitin controlled by ligand redox and photochemical reactions and active movement of chitin on aquatic arthropods
topic chitin–metal ion interactions
redox
photoredox desorption of M
daily vertical migration of aquatic arthropods
mineral (catalyst) formation from decaying chitin
Eu photochemistry
url https://www.mdpi.com/2673-4176/3/3/31
work_keys_str_mv AT stefanfranzle reversiblemetalioncomplexbindingtochitincontrolledbyligandredoxandphotochemicalreactionsandactivemovementofchitinonaquaticarthropods
AT felixblind reversiblemetalioncomplexbindingtochitincontrolledbyligandredoxandphotochemicalreactionsandactivemovementofchitinonaquaticarthropods