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- W786764358 abstract "The alkylsulfatase AtsK is one of several proteins expressed by Pseudomonas putida under sulfate starvation, which enable the organism to use various organic sulfonates and sulfate esters as a sulfur source. AtsK liberates sulfate and the corresponding aldehyde from aliphatic sulfate esters. The enzyme requires iron(II) and alpha-ketoglutaric acid for catalysis. This co-substrate is transformed into succinate and carbon dioxide, thus the enzyme belongs to the family of non-heme-Fe(II)-alpha-ketoglutarate dependent dioxygenases. The thesis describes the crystal structures of various AtsK-ligand complexes and the characterization of the iron centre in the Fe(II)-alpha-ketoglutarate-AtsK complex via X-ray absorption spectroscopy. Combination of these results with structural and spectroscopical data available for other Fe(II)-alpha-ketoglutarate dependent dioxygenases allows to formulate a catalytic mechanism for AtsK, which is discussed by means of characteristics common for the whole enzyme family. Some Fe(II)-alpha-ketoglutarate dependent dioxygenases are known to oxidize the co-substrate in the absence of the substrate. Concomitant with this uncoupled co-substrate oxidation, reactive radical species are formed. Tyrosine side chains could be shown to act as scavengers for these species and protect the organism from severe damage. The structure of AtsK in complex with Fe(II) and succinate gives evidence that AtsK possesses the same type of mechanism for self protection. Furthermore, the crystal structure of AtsK in complex with different organic sulfur compounds shows the binding mode for aliphatic sulfonates in the active site to be identical to the one for sulfate esters. The conclusion that the latter are substrates of AtsK as well could be confirmed by activity assays." @default.
- W786764358 created "2016-06-24" @default.
- W786764358 creator A5041887118 @default.
- W786764358 date "2022-02-20" @default.
- W786764358 modified "2023-10-18" @default.
- W786764358 title "Strukturuntersuchungen zum Reaktionsmechanismus an der Alkylsulfatase AtsK aus Pseudomonas putida S-313" @default.
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