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1.
J Inorg Biochem ; 238: 112063, 2023 01.
Article in English | MEDLINE | ID: mdl-36370505

ABSTRACT

The popular genetic model organism Caenorhabditis elegans (C. elegans) encodes 34 globins, whereby the few that are well-characterized show divergent properties besides the typical oxygen carrier function. Here, we present a biophysical characterization and expression analysis of C. elegans globin-3 (GLB-3). GLB-3 is predicted to exist in two isoforms and is expressed in the reproductive and nervous system. Knockout of this globin causes a 99% reduction in fertility and reduced motility. Spectroscopic analysis reveals that GLB-3 exists as a bis-histidyl-ligated low-spin form in both the ferrous and ferric heme form. A function in binding of diatomic gases is excluded on the basis of the slow CO-binding kinetics. Unlike other globins, GLB-3 is also not capable of reacting with H2O2, H2S, and nitrite. Intriguingly, not only does GLB-3 contain a high number of cysteine residues, it is also highly stable under harsh conditions (pH = 2 and high concentrations of H2O2). The resilience diminishes when the N- and C-terminal extensions are removed. Redox potentiometric measurements reveal a slightly positive redox potential (+8 ± 19 mV vs. SHE), suggesting that the heme iron may be able to oxidize cysteines. Electron paramagnetic resonance shows that formation of an intramolecular disulphide bridge, involving Cys70, affects the heme-pocket region. The results suggest an involvement of the globin in (cysteine) redox chemistry.


Subject(s)
Caenorhabditis elegans Proteins , Caenorhabditis elegans , Animals , Caenorhabditis elegans/genetics , Caenorhabditis elegans/metabolism , Globins/chemistry , Caenorhabditis elegans Proteins/genetics , Caenorhabditis elegans Proteins/metabolism , Cysteine/metabolism , Hydrogen Peroxide/metabolism , Heme/chemistry , Nervous System/metabolism
2.
Chem Commun (Camb) ; 53(67): 9340-9343, 2017 Aug 17.
Article in English | MEDLINE | ID: mdl-28783198

ABSTRACT

Beside activity, electrocatalyst stability is gaining in importance. The most common degradation mechanism is the loss of the active surface area due to nanoparticle growth via coalescence/agglomeration. We propose a particle confinement strategy via vertically oriented graphene deposition to overcome degradation of the nanoparticles.

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