Infrared Spectroscopy During Electrocatalytic Turnover Reveals the Ni‐L Active Site State During H2 Oxidation by a NiFe Hydrogenase

A novel in situ IR spectroscopic approach is demonstrated for the characterization of hydrogenase during catalytic turnover. E. coli hydrogenase 1 (Hyd‐1) is adsorbed on a high surface‐area carbon electrode and subjected to the same electrochemical control and efficient supply of substrate as in protein film electrochemistry during spectral acquisition. The spectra reveal that the active site state known as Ni‐L, observed in other NiFe hydrogenases only under illumination or at cryogenic temperatures, can be generated reversibly in the dark at ambient temperature under both turnover and non‐turnover conditions. The observation that Ni‐L is present at all potentials during turnover under H₂ suggests that the final steps in the catalytic cycle of H₂ oxidation by Hyd‐1 involve sequential proton and electron transfer via Ni‐L. A broadly applicable IR spectroscopic technique is presented for addressing electrode‐adsorbed redox enzymes under fast catalytic turnover.     

The emergence of kinship behavior in structured populations of unrelated individuals

The paper provides an explanation for altruistic behavior based on the matching and learning technology in the population. In a infinite structured population, in which individuals meet and interact with their neighbors, individuals learn by imitating their more successful neighbors. We ask which strategies are robust against invasion of mutants: A strategy is unbeatable if when all play it and a finite group of identical mutants enters then the learning process eliminates the mutants with probability 1. We find that such an unbeatable strategy is necessarily one in which each individual behaves as if he is related to his neighbors and takes into account their welfare as well as his. The degree to which he cares depends on the radii of his neighborhoods. Received June 1996/Revised version October 1998     

Synthesis of oxirnes. IV. 2-pyridinealdoxime methiodides from 2-picoline methiodides

The Ortoleva-King-Krohnke sequence was used to prepare substituted 2-pyridinealdoxime methiodides. The methodology was extended to prepare three analogs in which two molecules of 5-hydroxy-2-pyridinealdoxime methiodide were coupled through the 5-position with dihalides.