Platinum(II) complexes as spectroscopic probes for biomolecules

• Main Author: Ratilla, Eva
• Other Authors: United States. Department of Energy. Office of Energy Research.
• Format: Thesis
• Language: English
• Published: Ames Laboratory 1990
• Subjects: Thiols; Imidazoles; Chemical Reactions; Platinum Chlorides; 75 Condensed Matter Physics; Superconductivity And Superfluidity; Nucleic Acids; Arginine; Platinum Isotopes; Platinum 195; Proteins; Magnetic Resonance; Ligands; Platinum Complexes; Transition Element Compounds 400201* > Chemical & Physicochemical Properties; Transition Element Complexes; Ph Value; Azoles; Labelled Compounds; Histidine; Isotopes; Spectra; Chlorides; Crystal Structure; Even-Odd Nuclei; Chemical Shift; 59 Basic Biological Sciences; Heterocyclic Acids; 550200 > Biochemistry; Isomeric Transition Isotopes; Cysteine; Organic Acids; Internal Conversion Radioisotopes; Nuclei; Carboxylic Acids; Organic Compounds; Amino Acids; Platinum Compounds; 656002 > Condensed Matter Physics > General Techniques In Condensed Matter > (1987-); Guanidines; Halogen Compounds; Structural Chemical Analysis; Heterocyclic Compounds; Chlorine Compounds; Resonance; Cytochromes; Pigments; Dna; Halides; Radioisotopes; Carbonic Acid Derivatives; Days Living Radioisotopes; 37 Inorganic; Organic; Physical And Analytical Chemistry; Complexes; Organic Nitrogen Compounds; Organic Sulfur Compounds; Nuclear Magnetic Resonance; Chemical Bonds; Stable Isotopes; Heavy Nuclei; Carbonic acid
• Online Access: https://doi.org/10.2172/6491206; https://digital.library.unt.edu/ark:/67531/metadc1204881/

The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.