Persaud K C, Pain R H, Virden R
Biochem J. 1986 Aug 1;237(3):723-30. doi: 10.1042/bj2370723.
Conditions have been established where the deactivation of the beta-lactamase from Staphylococcus aureus PC1 by the penicillin substrate, quinacillin, is close to complete but fully reversible. The temperature-dependence of the rate of re-activation indicated a half-life of about 170 min for the deactivated state at 0 degrees C. Measurement of the relative viscosity of mixtures of enzyme and quinacillin at 8.4 degrees C ruled out any significant difference in shape or solvation between the deactivated and the normal enzyme. C.d. measurements of the deactivated protein, separated from excess quinacillin, showed that the quinacillin side-chain chromophore was bound in an asymmetric environment. The ellipticity associated with the bound quinacillin chromophore decreased with the same first-order rate constant as that for reappearance of enzyme activity. These findings support the accumulation of a deactivated state that contains bound quinacillin or a derivative. Quinacillin caused a 3-fold increase in the rate of 3H exchange-out (at a rate that was low compared with that for the substantially unfolded or expanded protein). However, there was rapid exchange-out of about 50 3H atoms on addition of 1 M-urea to the deactivated enzyme, whereas the same concentration had no effect on the exchange-out of 3H from native enzyme. The interpretation that quinacillin increases the susceptibility of the native state to unfolding in the presence of urea is supported by the demonstration that SO4(2)- ions decreased the rate and extent of deactivation but had no effect on the rate of re-activation, as predicted from the observation that SO4(2)- ions, in competition with urea, stabilize the native state relative to the partially unfolded state H [Mitchinson & Pain (1985) J. Mol. Biol. 184, 331-342].
已建立了相关条件,在这些条件下,青霉素底物喹那西林使金黄色葡萄球菌PC1的β-内酰胺酶失活接近完全,但完全可逆。再活化速率的温度依赖性表明,在0℃时失活状态的半衰期约为170分钟。在8.4℃下对酶和喹那西林混合物的相对粘度进行测量,排除了失活酶和正常酶在形状或溶剂化方面的任何显著差异。对从过量喹那西林中分离出的失活蛋白进行圆二色性测量表明,喹那西林侧链发色团在不对称环境中结合。与结合的喹那西林发色团相关的椭圆率以与酶活性重新出现相同的一级速率常数下降。这些发现支持了含有结合的喹那西林或其衍生物的失活状态的积累。喹那西林使3H交换出的速率增加了3倍(与基本上未折叠或伸展的蛋白质相比,该速率较低)。然而,向失活酶中加入1 M尿素后,约50个3H原子迅速交换出,而相同浓度对天然酶中3H的交换出没有影响。SO4(2)-离子降低了失活速率和程度,但对再活化速率没有影响,这一结果支持了喹那西林在尿素存在下增加天然状态对去折叠敏感性的解释,正如从观察到SO4(2)-离子与尿素竞争时相对于部分未折叠状态H稳定天然状态所预测的那样[米奇森和佩恩(1985年)《分子生物学杂志》184卷,331 - 342页]。