Preparation and characterization of an intramolecular electron transfer in a pentaammineruthenium derivative of Candida krisei cytochrome c

A semisynthetic binuclear metalloprotein has been prepared by appending the pentaammineruthenium moiety to histidine 39 of the cytochrome c from the yeast Candida krusei. The site of ruthenium binding was identified by peptide mapping. Spectroscopic and electrochemical properties of the derivative indicate the protein conformation is unperturbed by the modification. A preliminary (minimum) rate constant of 170s^(-1) has been determined for the intramolecular electron transfer from ruthenium(II) to iron(III), which occurs over a distance of at least 13Å (barring major conformational changes). Electrochemical studies indicate that this reaction should proceed with a driving force of ~170mV. The rate constant is an order of magnitude faster than that observed in horse heart cytochrome c for intramolecular electron transfer from pentaammineruthenium(II)(histidine 33) to iron(III) (over a similar distance, and with a similar driving force), suggesting a medium or orientation effect makes the Candida intramolecular electron transfer more favorable.

Logarithmic Potential Theory on Riemann Surfaces

We develop a logarithmic potential theory on Riemann surfaces which generalizes logarithmic potential theory on the complex plane. We show the existence of an equilibrium measure and examine its structure. This leads to a formula for the structure of the equilibrium measure which is new even in the plane. We then use our results to study quadrature domains, Laplacian growth, and Coulomb gas ensembles on Riemann surfaces. We prove that the complement of the support of the equilibrium measure satisfies a quadrature identity. Furthermore, our setup allows us to naturally realize weak solutions of Laplacian growth (for a general time-dependent source) as an evolution of the support of equilibrium measures. When applied to the Riemann sphere this approach unifies the known methods for generating interior and exterior Laplacian growth. We later narrow our focus to a special class of quadrature domains which we call Algebraic Quadrature Domains. We show that many of the properties of quadrature domains generalize to this setting. In particular, the boundary of an Algebraic Quadrature Domain is the inverse image of a planar algebraic curve under a meromorphic function. This makes the study of the topology of Algebraic Quadrature Domains an interesting problem. We briefly investigate this problem and then narrow our focus to the study of the topology of classical quadrature domains. We extend the results of Lee and Makarov and prove (for n ≥ 3) c ≤ 5n-5, where c and n denote the connectivity and degree of a (classical) quadrature domain. At the same time we obtain a new upper bound on the number of isolated points of the algebraic curve corresponding to the boundary and thus a new upper bound on the number of special points. In the final chapter we study Coulomb gas ensembles on Riemann surfaces.