Centre for Human Immunology, Department of Microbiology and Immunology, University of Western Ontario, London, Ontario N6A 5C1, Canada.
Protein Sci. 2012 Sep;21(9):1366-75. doi: 10.1002/pro.2123. Epub 2012 Aug 10.
Polyisoprenyl-phosphate N-acetylaminosugar-1-phosphate transferases (PNPTs) constitute a family of eukaryotic and prokaryotic membrane proteins that catalyze the transfer of a sugar-1-phosphate to a phosphoisoprenyl lipid carrier. All PNPT members share a highly conserved 213-Valine-Phenylalanine-Methionine-Glycine-Aspartic acid-217 (VFMGD) motif. Previous studies using the MraY protein suggested that the aspartic acid residue in this motif, D267, is a nucleophile for a proposed double-displacement mechanism involving the cleavage of the phosphoanhydride bond of the nucleoside. Here, we demonstrate that the corresponding residue in the E. coli WecA, D217, is not directly involved in catalysis, as its replacement by asparagine results in a more active enzyme. Kinetic data indicate that the D217N replacement leads to more than twofold increase in V(max) without significant change in the K(m) for the nucleoside sugar substrate. Furthermore, no differences in the binding of the reaction intermediate analog tunicamycin were found in D217N as well as in other replacement mutants at the same position. We also found that alanine substitutions in various residues of the VFMGD motif affect to various degrees the enzymatic activity of WecA in vivo and in vitro. Together, our data suggest that the highly conserved VFMGD motif defines a common region in PNPT proteins that contributes to the active site and is likely involved in the release of the reaction product.
多异戊烯基磷酸 N-乙酰氨基葡萄糖-1-磷酸转移酶(PNPTs)构成了一个真核生物和原核生物膜蛋白家族,其催化将糖-1-磷酸转移到磷酸异戊烯脂质载体上。所有 PNPT 成员都具有高度保守的 213-Valine-Phenylalanine-Methionine-Glycine-Aspartic acid-217(VFMGD)基序。以前使用 MraY 蛋白的研究表明,该基序中的天冬氨酸残基 D267 是提议的双置换机制中的亲核试剂,该机制涉及核苷磷酸酐键的裂解。在这里,我们证明大肠杆菌 WecA 中的相应残基 D217 不直接参与催化,因为其被天冬酰胺取代会导致酶更活跃。动力学数据表明,D217N 取代导致 V(max)增加两倍以上,而核苷糖底物的 K(m)没有明显变化。此外,在 D217N 以及同一位置的其他替换突变体中,均未发现反应中间类似物衣霉素结合的差异。我们还发现,VFMGD 基序中各种残基的丙氨酸取代在体内和体外均不同程度地影响 WecA 的酶活性。总之,我们的数据表明,高度保守的 VFMGD 基序定义了 PNPT 蛋白中的一个共同区域,该区域有助于活性位点,并且可能参与了反应产物的释放。