D'Avino Rossana, Camardella Laura, Christensen Tove M I E, Giovane Alfonso, Servillo Luigi
Institute of Protein Biochemistry, CNR, Napoli, Italy.
Proteins. 2003 Dec 1;53(4):830-9. doi: 10.1002/prot.10487.
The molecular model of Lycopersicon esculentum (tomato) pectin methylesterase (PME) was built by using the X-ray crystal structure of PME from the phytopathogenic bacterium Erwinia chrysanthemi as a template. The overall structure and the position of catalytically important residues (Asp132, Asp 153, and Arg 221, located at the bottom of the active site cleft) are conserved. Instead, loop regions forming the walls of the catalytic site are much shorter and form a less deep cleft, as already revealed by the carrot PME crystal structure. The protein inhibitor of pectin methylesterase (PMEI) isolated from kiwi fruit binds tomato PME with high affinity. Conversely, no complex formation between the inhibitor and PME from E. chrysanthemi is observed, and the activity of this enzyme is unaffected by the presence of the inhibitor. Fluorescence quenching experiments on tomato PME and on PME-PMEI complex suggest that tryptophanyl residues present in the active site region are involved in the interaction and that the inhibitor interacts with plant PME at the level of the active site. We also suggest that the more open active site cleft of tomato PME allows the interaction with the inhibitor. Conversely, the narrow and deep cleft of the active site of E. chrysanthemi PME hinders this interaction. The pH-dependent changes in fluorescence emission intensity observed in tomato PME could arise as the result of protonation of an Asp residue with unusually high pKa, thus supporting the hypothesis that Asp132 acts as acid/base in the catalytic cycle.
以植物致病细菌菊欧文氏菌果胶甲酯酶(PME)的X射线晶体结构为模板,构建了番茄果胶甲酯酶(PME)的分子模型。其整体结构以及催化关键残基(位于活性位点裂隙底部的Asp132、Asp153和Arg221)的位置是保守的。相反,正如胡萝卜PME晶体结构所揭示的那样,构成催化位点壁的环区域要短得多,形成的裂隙也较浅。从猕猴桃中分离得到的果胶甲酯酶蛋白抑制剂(PMEI)能与番茄PME高亲和力结合。相反,未观察到该抑制剂与菊欧文氏菌PME之间形成复合物,且该酶的活性不受抑制剂存在的影响。对番茄PME和PME - PMEI复合物进行的荧光猝灭实验表明,活性位点区域存在的色氨酸残基参与了相互作用,且抑制剂在活性位点水平与植物PME相互作用。我们还认为,番茄PME活性位点裂隙更开放,有利于与抑制剂相互作用。相反,菊欧文氏菌PME活性位点狭窄且深的裂隙阻碍了这种相互作用。在番茄PME中观察到的荧光发射强度随pH的变化可能是由于具有异常高pKa的Asp残基质子化所致,从而支持了Asp132在催化循环中作为酸/碱的假设。