The eukaryotic enzyme Bds1 is an alkyl but not an aryl sulfohydrolase.

The eukaryotic enzyme Bds1 is an alkyl but not an aryl sulfohydrolase.
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DOI:
10.1016/j.bbrc.2017.07.092
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发表时间:
2017-09-16
影响因子:
3.1
通讯作者:
Fox JL
Fox JL
中科院分区:
生物学4区
文献类型:
--
作者:
Waddell GL;Gilmer CR;Taylor NG;Reveral JRS;Forconi M;Fox JL

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酿酒酵母中的真核酶Bds 1是一种金属β-内酰胺酶相关酶,其进化起源于细菌水平基因转移,具有未知的生物学作用。以前,Bds 1被报道为烷基和芳基硫酸酯酶。然而,我们在这里证明,Bds 1作用于伯烷基硫酸盐(6-12个碳原子),但不是芳基硫酸盐对硝基苯基硫酸盐和对硝基儿茶酚硫酸盐。Bds 1水解底物1-己基硫酸酯的表观催化速率常数比其细菌同系物SdsA 1催化的反应低100倍以上。我们发现,Bds 1共享一个催化机制与SdsA 1,其中的硫酸酯的碳原子是亲核攻击的主题,而不是硫原子,导致在C-O键裂解。与SdsA 1和另一种对仲烷基硫酸盐具有选择性的细菌同系物Pisa 1相反,Bds 1对仲烷基硫酸盐没有显示出任何实质性的活性。Bds 1和SdsA 1对支链伯烷基硫酸盐、伯和仲类固醇硫酸盐或磷酸二酯都没有任何显著的活性。因此,迄今为止已经鉴定和表征的与SdsA 1同源的酶在它们对伯和仲烷基硫酸盐的选择性方面不同,但不表现出芳基硫酸酯酶活性。
The eukaryotic enzyme Bds1 in Saccharomyces cerevisiae is a metallo-β-lactamase-related enzyme evolutionarily originating from bacterial horizontal gene transfer that serves an unknown biological role. Previously, Bds1 was reported to be an alkyl and aryl sulfatase. However, we demonstrate here that Bds1 acts on primary alkyl sulfates (of 6–12 carbon atoms) but not the aryl sulfates p-nitrophenyl sulfate and p-nitrocatechol sulfate. The apparent catalytic rate constant for hydrolysis of the substrate 1-hexyl sulfate by Bds1 is over 100 times lower than that of the reaction catalyzed by its bacterial homolog SdsA1. We show that Bds1 shares a catalytic mechanism with SdsA1 in which the carbon atom of the sulfate ester is the subject of nucleophilic attack, rather than the sulfur atom, resulting in C–O bond lysis. In contrast to SdsA1 and another bacterial homolog with selectivity for secondary alkyl sulfates named Pisa1, Bds1 does not show any substantial activity towards secondary alkyl sulfates. Neither Bds1 nor SdsA1 have any significant activity towards a branched primary alkyl sulfate, primary and secondary steroid sulfates, or phosphate diesters. Therefore, the enzymes homologous to SdsA1 that have been identified and characterized thus far vary in their selectivity towards primary and secondary alkyl sulfates but do not exhibit aryl sulfatase activity.
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