University of Illinois Urbana-Champaign

Covalent Attachment of Coordinatively-Saturated Metal Complexes to Horse Cytochrome-C Lysines

Wallin, Sten Andreas

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Description

Title
Covalent Attachment of Coordinatively-Saturated Metal Complexes to Horse Cytochrome-C Lysines
Author(s)
Wallin, Sten Andreas
Issue Date
1988
Doctoral Committee Chair(s)
Scott, R.A.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
  • Chemistry, Biochemistry
  • Chemistry, Inorganic
Abstract
  • The coordinatively saturated complexes $\rm Ru\sp{II}(NH\sb3)\sb5INH\sp{2+}$ (INH = isonicotinic acid) and $\rm Ru\sp{II}bp\sb2cmbpH\sp{2+}$ (bp = 2,2$\sp\prime$-bipyridine, cmbp = 4$\sp\prime$-methyl-2,2$\sp\prime$-bipyridine-4-carboxylic acid) have been covalently attached to horse cytochrome c via a carbodiimide-promoted condensation of the pendant carboxylate of the complexes with the $\varepsilon$-amine of lysine to form an amide-bond linkage.
  • The reaction of the O-acylisourea (Ru$\sp{II}$(NH$\sb3)\sb5$IN/EDC) $\sp{3+}$, formed by the reaction of $\rm Ru\sp{II}(NH\sb3)\sb5IN\sp{+} (pK\sb{a}$ = 2.75 $\pm$ 0.10) with EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) at pH $\sim$ 2.7, with cytochrome c at 6.0 $$ 1 s$\sp{-1}$ for the intramolecular conversion of ${\rm Ru\sp{III}}$-${\rm Fe\sp{II}}$ to ${\rm Ru\sp{III}}$-${\rm Fe\sp{III}}$.
  • Singly-modified Rubp$\sb2$cmbp/cyt c was prepared from (Rubp$\sb2$-cmbp/EDC) $\sp{3+}$ and cytochrome c by the same procedure used for Ru(NH$\sb3)\sb5$IN/cyt c. Preliminary peptide mapping results identify the site of modification of some of the components in the mixture of Rubp$\sb2$cmpb/cyts c. It appears that the product distribution is governed more by hydrophobic interactions between (Rubp$\sb2$cmbp/-EDC) $\sp{3+}$ and cytochrome c than by simple electrostatic considerations.
Graduation Semester
1988
Type of Resource
text
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