Chemistry and Biochemistry of Energy Transferring Reactions in Biological Systems

肌浆网钙转运ATPase通过去除催化金属离子的解偶联作用将被进一步表征。将确定金属离子的特异性和解偶联的发展和消失的速率和平衡常数。涉及钙在低亲和力部位的结合和释放的步骤将被直接测量，以确定这些步骤的机制和热力学。亲核试剂与磷酸化吡啶的结构-反应性关联将被用来确定催化中是否存在偏磷酸盐中间体。尽管关于产生碳正离子的化学反应已经开展了大量的工作，但通过捕获反应来间接探测这些工作的数量有限。我们会做到这一点的。碳上的取代反应以及硫胺素的电离也将被研究。通过这项工作，正在建立对生物学中的矢量过程的机械论理解。了解生命系统中催化过程的基础和效率对于基础工作和应用都是非常重要的。基因工程最合理的方法需要这项工作提供的机械细节层面的信息。

Uncoupling of the calcium transporting ATPase of sarcoplasmic reticulum by removal of the catalytic metal ion will be characterized further. The metal ion specificity and rate and equilibrium constants for development and disappearance of the uncoupling will be determined. The steps involving the binding and release of calcuim at the low affinity site will be measured directly to determine the mechanism and thermodynamics of these steps. Structure- reactivity correlations for nucleophilic reagents with phosphorylated pyridines will be done in order to determine if there is a metaphosphate intermediate in catalysis. Although an enormous amount of work has been carried out on chemical reactions that generate carbocations a limited amount of work has probed these indirectly by trapping reactions. This will be done. The substitution reactions at carbon will be investigated as will the ionization of thiamine. A mechanistic understanding of vectorial processes in biology is being established with this work. Knowledge of the basis the efficiency of catalytic processes in living systems is of great importance for fundamental work and for applications. The most rational approach to genetic engineering requires information at the level of mechanistic detail that this work provides