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Macrocyclic complexes as models for copper(II) bonding in cupredoxins: Proof of concept
Ulrichová, Tereza ; Hermann, Petr (advisor) ; Hudeček, Jiří (referee)
Currently, modified electron transport metaloproteins with presence ion Cu(II) in their active site are most commonly used to study kinetics of electron transfer. One of the most studied model protein is cupredoxin azurin from P. aeruginosa with standard redox potential approximately 310-360 nm (depends on experimental conditions and techniques). Ion Cu(II) in azurin is coordinated by the side chain atoms of His46 , His117 , Cys112 , Met121 and carbonyl of Gly45 . The aim of this work was to prepare macrocyclic ligand, 1-[1H-imidazol-2- yl)methyl]-1,4,7-triazacycklononanu (LIM ), which would be able to form stable complexes with both of copper ions Cu(II) and Cu(I). Such as macrocyclic complexes could be utilized as low molecular models of active sites in proteins. The ligand was prepared using five-step synthesis employing protection of macrocycle, reduction and subsequent bromation of 1H- imidazol-2-karbaldehyd, and following alkylation reaction. Deprotection of macrocycle revealed final product of ligand. All reaction intermediates and prepared ligand were characterized by NMR and MS. Potentiometric titrations determined ligand protonation constant (log K1 = 10,62, log K2 = 6,65, log K3 = 4,91), which describe acid-base properties of a ligand in an aqueous solution. Similarly, the coordination...
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Macrocyclic complexes as models for copper(II) bonding in cupredoxins: Proof of concept
Ulrichová, Tereza ; Hermann, Petr (advisor) ; Hudeček, Jiří (referee)
Currently, modified electron transport metaloproteins with presence ion Cu(II) in their active site are most commonly used to study kinetics of electron transfer. One of the most studied model protein is cupredoxin azurin from P. aeruginosa with standard redox potential approximately 310-360 nm (depends on experimental conditions and techniques). Ion Cu(II) in azurin is coordinated by the side chain atoms of His46 , His117 , Cys112 , Met121 and carbonyl of Gly45 . The aim of this work was to prepare macrocyclic ligand, 1-[1H-imidazol-2- yl)methyl]-1,4,7-triazacycklononanu (LIM ), which would be able to form stable complexes with both of copper ions Cu(II) and Cu(I). Such as macrocyclic complexes could be utilized as low molecular models of active sites in proteins. The ligand was prepared using five-step synthesis employing protection of macrocycle, reduction and subsequent bromation of 1H- imidazol-2-karbaldehyd, and following alkylation reaction. Deprotection of macrocycle revealed final product of ligand. All reaction intermediates and prepared ligand were characterized by NMR and MS. Potentiometric titrations determined ligand protonation constant (log K1 = 10,62, log K2 = 6,65, log K3 = 4,91), which describe acid-base properties of a ligand in an aqueous solution. Similarly, the coordination...
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