Synthesis and Characterization of Hybrid Drugs Based on Ruthenium Complex Moiety and Biologically Active Organic Compounds
Synthesis and Characterization of Hybrid Drugs Based on Ruthenium Complex Moiety and Biologically Active Organic Compounds

Author: Michał Pawel Łomzik

Publisher:

Published: 2016

Total Pages: 0

ISBN-13:

DOWNLOAD EBOOK

The main goal of this thesis was synthesis and preliminary characterization of novel ruthenium(II) polypyridyl complexes bearing biologically active molecules as potential theranostic agents. Luminescence for the diagnostic applications, and cytotoxicity for the anticancer, therapeutic applications are considered as the theranostic properties. Four new ligands containing biologically active moieties - 5-(4-4'-methyl-[2,2'-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4'-methyl-[2,2'-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) were synthesized and characterized. The ligands were used to obtain nine novel ruthenium(II) polypyridyl complexes. Six complexes were synthesized with ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) and three with ligands L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2'-bipyridine, Mebpy = 4,4'-dimethyl-2,2-bipyridine, tBubpy = 4,4'-tert-butyl-2,2'-bipyridine, Phbpy = 4,4'-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). The spectroscopic and photophysical properties of those complexes were determined. The presence of ligands L1-L4 in the structure of the complex decreased luminescence quantum yield and luminescence lifetime in comparison with unmodified [Ru(bpy)3]2+ complex. The theoretical calculations have shown that ligands L1-L4 do not have influence on ruthenium core geometry. However, they increased the energy of the HOMO that resulted in a shorter band gap. The simulated electronic absorption spectra were in a good agreement with the experimental data. The interactions between the studied ruthenium complexes and human serum albumin (HSA) were investigated. All studied Ru(II) complexes exhibited strong affinity to HSA with the association constant 105 M-1s-1, which suggests formation of Ru complex-HSA adducts. It was also determined that ruthenium complexes most likely bind to the hydrophobic pocket of protein, located in Sudlow's site I in the subdomain II A. Preliminary cytotoxicity evaluation for the studied ruthenium complexes showed their cytotoxic activity towards cancer cell lines. Those results, together with good luminescence properties of the studied ruthenium complexes (luminescence lifetimes and luminescence quantum yield) make them interesting candidates for potential theranostic applications.

Design, Synthesis and Characterization of Ruthenium(ii) and Rhenium(i) Complexes with Functionalized Ligands for Photo-And Electrochemi- Luminescence, Solvatochromism, Molecular Recognition and HPLC Separation Studies
Design, Synthesis and Characterization of Ruthenium(ii) and Rhenium(i) Complexes with Functionalized Ligands for Photo-And Electrochemi- Luminescence, Solvatochromism, Molecular Recognition and HPLC Separation Studies

Author: Meijin Li

Publisher: Open Dissertation Press

Published: 2017-01-27

Total Pages:

ISBN-13: 9781361428276

DOWNLOAD EBOOK

This dissertation, "Design, Synthesis and Characterization of Ruthenium(II) and Rhenium(I) Complexes With Functionalized Ligands for Photo-and Electrochemi- Luminescence, Solvatochromism, Molecular Recognition and HPLC Separation Studies" by Meijin, Li, 李梅金, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN, SYNTHESIS AND CHARACTERIZATION OF RUTHENIUM(II) AND RHENIUM(I) COMPLEXES WITH FUNCTIONALIZED LIGANDS FOR PHOTO- AND ELECTROCHEMI- LUMINESCENCE, SOLVATOCHROMISM, MOLECULAR RECOGNITION AND HPLC SEPARATION STUDIES Submitted by LI MEIJIN for the degree of Doctor of Philosophy at The University of Hong Kong in July 2006 A series of ruthenium(II) and rhenium(I) diimine complexes containing thia-, selena- and aza-crowns derived from 1,10-phenanthroline, [Ru(bpy) (phen-3S)](ClO ) 2 4 2 (phen-3S = 1,13-dioxa-4,7,10-trithiacyclopentadecano[2,3-f][1,10]phenanthroline), [Ru(bpy) (phen-2S)](ClO ) (phen-2S = 1,7,10,16-tetraoxa-4,13-dithiacyclohexa- 2 4 2 dodecano[2,3-f][1,10]phenanthroline), [Ru(bpy) (phen-S)](ClO ) (phen-S = 1,4,10,13- 2 4 2 tetraoxa-7-thiacyclopentadecano[2,3-f][1,10]phenanthroline), [Ru(bpy) (phen-Se)](ClO ) 2 4 2 (phen-Se = 1,4,10,13-tetraoxa-7-selenacyclopentadecano[2,3-f][1,10]phenanthroline), [Ru(bpy) (phen-OEt](ClO ) (phen-OEt = 5,6-diethoxy-[1,10]phenanthroline), 2 4 2 [Ru(bpy) (phen-2NH)](ClO ) (phen-2NH = 1,13-diaxa-4,7,10-trioxacyclopenta- 2 4 2 decano[2,3-f][1,10]phenanthroline), [Re(CO) (py)(phen-3S)]PF, [Re(CO) (py)(phen-S)]OTf 3 6 3 and [Re(CO) (py)(phen-Se)]OTf have been synthesized and characterized, and their photophysics, electrogenerated chemiluminescence (ECL) and electrochemistry were studied. Their interaction with metal ions was investigated by UV-vis, luminescence, NMR spectroscopy and ECL. [Ru(bpy) (phen-3S)](ClO ) and [Re(CO) (py)(phen-3S)]