Static and Dynamic Heterogeneity

Single molecule experiments have been useful in detecting new properties of enzymes such as static heterogeneity (differences between individual molecules in the native state) and dynamic heterogeneity (slow conformational transitions that regulate catalysis).

Individual molecules of PHBH show a wide variation in rates of transition between the in and out conformation even after the enzyme has been purified to homogeneity by FPLC. The out to in transition (light to dark) in particular is very heterogeneous with some molecules rapidly going back and forth from out to in and some slowly or not at all.



The cause of the heterogeneity is unknown at this point. An interesting possibility is that differences in the reaction rates reflect the position of the loop around the conserved residues Proline 292 and Proline 293. The negative charge on the 4 position of the p-hydroxybenzoate substrate repels the dipole on Proline 293 and the resulting force is transmitted through the rigid di-proline segment to the rest of the backbone of the protein. This force is eventually responsible for the movement of the flavin to the out position. Mutating Serine 293 is known to drastically increase the flexibility of the enzyme. A dynamic heterogeneity may arise by differences in the position of the loop either altering the rate of entry of water into the active site or by altering the speed in which the negative charge of hydroxide is transmitted into movement of the flavin.




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