Nunes Catarina I P, Brás Joana L A, Najmudin Shabir, Moura José J G, Moura Isabel, Carepo Marta S P
REQUIMTE-CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Campus de Caparica, 2829-516, Caparica, Portugal.
J Biol Inorg Chem. 2014 Dec;19(8):1277-85. doi: 10.1007/s00775-014-1184-8. Epub 2014 Aug 20.
Desulfovibrio alaskensis G20, a sulfate-reducing bacterium, contains an arsRBC2C3 operon that encodes two putative arsenate reductases, DaG20_ArsC2 and DaG20_ArsC3. In this study, resistance assays in E. coli transformed with plasmids containing either of the two recombinant arsenate reductases, showed that only DaG20_ArsC3 is functional and able to confer arsenate resistance. Kinetic studies revealed that this enzyme uses thioredoxin as electron donor and therefore belongs to Staphylococcus aureus plasmid pI258 and Bacillus subtilis thioredoxin-coupled arsenate reductases family. Both enzymes from this family contain a potassium-binding site, but only in Sa_ArsC does potassium actually binds resulting in a lower K m. Important differences between the S. aureus and B. subtilis enzymes and DaG20_ArsC3 are observed. DaG20_ArsC3 contains only two (Asn10, Ser33) of the four (Asn10, Ser33, Thr63, Asp65) conserved amino acid residues that form the potassium-binding site and the kinetics is not significantly affected by the presence of either potassium or sulfate ions. Isothermal titration calorimetry measurements confirmed nonspecific binding of K(+) and Na(+), corroborating the non-relevance of these cations for catalysis. Furthermore, the low K m and high k cat values determined for DaG20_ArsC3 revealed that this enzyme is the most catalytically efficient potassium-independent arsenate reductase described so far and, for the first time indicates that potassium binding is not essential to have low K m, for Trx-arsenate reductases.
阿拉斯加脱硫弧菌G20是一种硫酸盐还原菌,含有一个arsRBC2C3操纵子,该操纵子编码两种假定的砷酸盐还原酶,即DaG20_ArsC2和DaG20_ArsC3。在本研究中,对用含有这两种重组砷酸盐还原酶之一的质粒转化的大肠杆菌进行的抗性测定表明,只有DaG20_ArsC3具有功能并能够赋予砷酸盐抗性。动力学研究表明,该酶使用硫氧还蛋白作为电子供体,因此属于金黄色葡萄球菌质粒pI258和枯草芽孢杆菌硫氧还蛋白偶联砷酸盐还原酶家族。该家族的两种酶都含有一个钾结合位点,但实际上只有金黄色葡萄球菌的ArsC能结合钾,从而导致较低的米氏常数。观察到金黄色葡萄球菌和枯草芽孢杆菌的酶与DaG20_ArsC3之间存在重要差异。DaG20_ArsC3仅含有形成钾结合位点的四个保守氨基酸残基(天冬酰胺10、丝氨酸33、苏氨酸63、天冬氨酸65)中的两个(天冬酰胺10、丝氨酸33),并且动力学不受钾离子或硫酸根离子存在的显著影响。等温滴定量热法测量证实了K(+)和Na(+)的非特异性结合,证实了这些阳离子与催化作用无关。此外,为DaG20_ArsC3测定的低米氏常数和高催化常数表明,该酶是迄今为止描述的催化效率最高的非依赖钾的砷酸盐还原酶,并且首次表明钾结合对于硫氧还蛋白-砷酸盐还原酶具有低米氏常数并非必不可少。