Femtosecond dynamics coupled to chemical barrier crossing in a Born-Oppenheimer enzyme

Contributions of fast (femtosecond) dynamic motion to barrier crossing at enzyme catalytic sites is in dispute. Human purine nucleoside phosphorylase (PNP) forms a ribocation-like transition state in the phosphorolysis of purine nucleosides and fast protein motions have been proposed to participate in barrier crossing. In the present study, 13 C-, 15 N-, 2 H-labeled human PNP (heavy PNP) was expressed, purified to homogeneity, and shown to...