Henriksen A, Aghajari N, Jensen K F, Gajhede M
Center for Crystallographic Studies, University of Copenhagen, København, Denmark.
Biochemistry. 1996 Mar 26;35(12):3803-9. doi: 10.1021/bi952226y.
Orotate phosphoribosyltransferase (OPRTase) is involved in the biosynthesis of pyrimidine nucleotides. Alpha-D-ribosyldiphosphate 5-phosphate (PRPP) and orotate are utilized to form pyrophosphate and orotidine 5'-monophosphate (OMP) in the presence of divalent cations, preferably Mg2+. OMP is thereafter converted to uridine 5'-monophosphate by OMP decarboxylase. We have determined the 2.4 angstrom structure of Escherichia coli OPRTase, ligated with sulfate, by molecular replacement and refined the structure to an R-factor of 18.3% for all data. In the structure of the E. coli enzyme we have determined the fold of a flexible loop region with a highly conserved amino acid sequence among OPRTases, a region known to take part in catalysis. The structure of this region was not determined in the model used for molecular replacement, and it involves interactions at the dimer interface through a bound sulfate ion. Crystalline E. coli OPRTase is a homodimer, with sulfate ions inhibiting enzyme activity bound in the dimer interface close to the flexible loop region. Although this loop is very close in space to the sulfate binding site, and sulfate is found in both interfaces of the homodimer, the loop structure is only traceable in one monomer. We expect that the mobility of this loop is important for catalysis, and, on the basis of the reported structure and the structure of Salmonella typhimurium OPRTase.OMP, we propose that the movement of this loop in association with the movement of OMP is vital to catalysis. Apart from the flexible loop region and a solvent-exposed loop (residues 158-164), the most significant differences in structure between S. typhimurium OPRTase.OMP and E. coli OPRTase are found in the substrate binding regions: the 5'-phosphate binding region (residues 120-131), the binding region for the orotate part of OMP (residues 25-27), and the pyrophosphate binding region (residues 71-73).
乳清酸磷酸核糖转移酶(OPRTase)参与嘧啶核苷酸的生物合成。在二价阳离子(最好是Mg2+)存在的情况下,α-D-核糖二磷酸5-磷酸(PRPP)和乳清酸被用于形成焦磷酸和乳清苷5'-单磷酸(OMP)。此后,OMP通过OMP脱羧酶转化为尿苷5'-单磷酸。我们通过分子置换确定了与硫酸盐结合的大肠杆菌OPRTase的2.4埃结构,并将该结构精修至所有数据的R因子为18.3%。在大肠杆菌酶的结构中,我们确定了OPRTases中具有高度保守氨基酸序列的柔性环区域的折叠,该区域已知参与催化作用。在用于分子置换的模型中未确定该区域的结构,它通过结合的硫酸根离子在二聚体界面处发生相互作用。结晶的大肠杆菌OPRTase是一种同型二聚体,二聚体界面靠近柔性环区域处结合的硫酸根离子会抑制酶活性。尽管该环在空间上与硫酸根结合位点非常接近,并且在同型二聚体的两个界面中都发现了硫酸根,但环结构仅在一个单体中可追踪到。我们预计该环的流动性对催化作用很重要,并且基于已报道的结构和鼠伤寒沙门氏菌OPRTase.OMP的结构,我们提出该环与OMP的移动相关联的运动对催化作用至关重要。除了柔性环区域和溶剂暴露环(残基158 - 164)外,鼠伤寒沙门氏菌OPRTase.OMP和大肠杆菌OPRTase在结构上最显著的差异存在于底物结合区域:5'-磷酸结合区域(残基120 - 131)、OMP的乳清酸部分结合区域(残基25 - 27)和焦磷酸结合区域(残基71 - 73)。