Carbonic anhydrase activity of dinuclear CuII complexes with patellamide model ligands

Comba, Peter, Gahan, Lawrence R., Hanson, Graeme R, Maeder, Marcel and Westphal, Michael (2014) Carbonic anhydrase activity of dinuclear CuII complexes with patellamide model ligands. Dalton Transactions, 43 8: 3144-3152. doi:10.1039/c3dt53135j

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Author Comba, Peter
Gahan, Lawrence R.
Hanson, Graeme R
Maeder, Marcel
Westphal, Michael
Title Carbonic anhydrase activity of dinuclear CuII complexes with patellamide model ligands
Formatted title
Carbonic anhydrase activity of dinuclear CuII complexes with patellamide model ligands
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
1477-9234
Publication date 2014-02-28
Year available 2013
Sub-type Article (original research)
DOI 10.1039/c3dt53135j
Open Access Status File (Publisher version)
Volume 43
Issue 8
Start page 3144
End page 3152
Total pages 9
Place of publication Cambridge, United Kingdom
Publisher R S C Publications
Language eng
Formatted abstract
The dicopper(II) complexes of six pseudo-octapeptides, synthetic analogues of ascidiacyclamide and the patellamides, found in ascidians of the Pacific and Indian Oceans, are shown to be efficient carbonic anhydrase model complexes with kcat up to 7.3 × 103 s−1 (uncatalyzed: 3.7 × 10−2 s−1; enzyme-catalyzed: 2 × 105–1.4 × 106 s−1) and a turnover number (TON) of at least 1700, limited only by the experimental conditions used. So far, no copper-based natural carbonic anhydrases are known, no faster model systems have been described and the biological role of the patellamide macrocycles is so far unknown. The observed CO2 hydration rates depend on the configuration of the isopropyl side chains of the pseudo-octapeptide scaffold, and the naturally observed R*,S*,R*,S* geometry is shown to lead to more efficient catalysts than the S*,S*,S*,S* isomers. The catalytic efficiency also depends on the heterocyclic donor groups of the pseudo-octapeptides. Interestingly, the dicopper(II) complex of the ligand with four imidazole groups is a more efficient catalyst than that of the close analogue of ascidiacyclamide with two thiazole and two oxazoline rings. The experimental observations indicate that the nucleophilic attack of a CuII-coordinated hydroxide at the CO2 carbon center is rate determining, i.e. formation of the catalyst-CO2 adduct and release of carbonate/bicarbonate are relatively fast processes.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published online 2 December 2013

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
Centre for Advanced Imaging Publications
 
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Created: Sat, 08 Feb 2014, 00:28:31 EST by Sandrine Ducrot on behalf of Centre for Advanced Imaging