Jackman M P, Hajnal A, Lerch K
Biochemisches Institut, Universität Zürich, Switzerland.
Biochem J. 1991 Mar 15;274 ( Pt 3)(Pt 3):707-13. doi: 10.1042/bj2740707.
Site-directed mutagenesis was used to determine the functional role of several residues of Streptomyces glaucescens tyrosinase. Replacement of His-37, -53, -193 or -215 by glutamine yields albino phenotypes, as determined by expression on melanin-indicator plates. The purified mutant proteins display no detectable oxy-enzyme and increased Cu lability at the binuclear active site. The carbonyl derivatives of H189Q and H193Q luminesce, with lambda max. displaced more than 25 nm to a longer wavelength compared with native tyrosinase. The remaining histidine mutants display no detectable luminescence. The results are consistent with these histidine residues (together with His-62 and His-189 reported earlier) acting as Cu ligands in the Streptomyces glaucescens enzyme. Conservative substitution of the invariant Asn-190 by glutamine also gives an albino phenotype, no detectable oxy-enzyme and labilization of active-site Cu. The luminescence spectrum of carbonyl-N190Q, however, closely resembles that of the native enzyme under conditions promoting double Cu occupancy of the catalytic site. A critical role for Asn-190 in active-site hydrogen-bonding interactions is proposed.
定点诱变用于确定浅绿链霉菌酪氨酸酶几个残基的功能作用。通过在黑色素指示平板上表达确定,用谷氨酰胺取代His-37、-53、-193或-215会产生白化表型。纯化的突变蛋白在双核活性位点未显示可检测到的氧合酶,且铜的稳定性增加。H189Q和H193Q的羰基衍生物发出荧光,与天然酪氨酸酶相比,其最大发射波长(λmax)向更长波长位移超过25 nm。其余组氨酸突变体未显示可检测到的荧光。结果表明,这些组氨酸残基(连同之前报道的His-62和His-189)在浅绿链霉菌酶中作为铜配体发挥作用。将不变的Asn-190保守地替换为谷氨酰胺也会产生白化表型,未检测到氧合酶且活性位点的铜不稳定。然而,在促进催化位点双铜占据的条件下,羰基-N190Q的荧光光谱与天然酶的荧光光谱非常相似。有人提出Asn-190在活性位点氢键相互作用中起关键作用。