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Type of Document	Dissertation
Author	Yamane, Tetsuo
URN	etd-07202006-091354
Persistent URL	http://resolver.caltech.edu/CaltechETD:etd-07202006-091354
Title	I. Complexes of mercury (I) with polyphosphate and dicarboxylate anions and mercury (II) pyrophosphate complexes. II. The interaction of mercuric chloride with deoxyribonucleic acid
Degree	PhD
Option	Chemistry
Advisory Committee	Advisor Name Title Norman R. Davidson Committee Chair
Keywords	none
Date of Defense	1960-01-01
Availability	unrestricted
Abstract NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. Part I: It has been discovered that mercurous mercury forms complexes with pyrophosphate, tripolyphosphate, oxalate, [...]-dimethylmalonate, and succinate. These complexes are stable towards disproportionation to mercury (II) complexes and mercury. If L(-q) is the anion, the principal complexes are Hg2L2(-2q+2) and Hg2(OH)L(-q+1). The formation constants were determined from the potential of a mercury-mercurous electrode in ligand solutions. Theory and experiment agree that mercurous complexes of ligands (such as NH3 and CN-) which form strong covalent bonds to mercury are unstable towards disproportionation to give mercuric complexes but "ionic" chelating ligands can form stable mercurous complexes. The mercury (II) pyrophosphate complex was studied from the potential of a Pt electrode in Hg2(I), Hg(II), pyrophosphate solutions at pH 7-10. The principal species is Hg(OH)(P2O7)(-3), with a formation constant of (2.8±0.6)10(17)M-2. Part II: The interaction of mercury (II) with DNA was studied. The formation of the DNA-Hg(II) complex is reversible according to spectrophotometric, viscometric, and biological criteria. Based on the ultraviolet absorption spectra and on the number of protons liberated from DNA during complexation, the binding sites of Hg(II) to DNA are discussed.
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