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4.11 Mengyu Wang thesis 4.11 final format approved LW 04-14-16.pdf (3.14 MB)
ETD Abstract Container
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Synthesis, Characterization, DNA Binding and DNA Photocleavage of Two New Dipyrromethenes and Their Ruthenium (II) and N-Methylated Analogs
Author Info
Wang, Mengyu
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=dayton1460657926
Abstract Details
Year and Degree
2016, Master of Science (M.S.), University of Dayton, Chemistry.
Abstract
Two new bridging ligands have been synthesized by solvent-free reactions of substituted benzaldehydes, 3-methoxy-4-hydroxy benzaldehyde and flurobenzaldehyde, with isoquino[5,6-c]pyrrole resulting in two new organic chromophores with two peripheral nitrogen coordination sites capable of metal interaction. The ligands have been characterized by
1
HNMR, mass spectroscopy, elemental analysis, UV/Vis spectroscopy, and cyclic voltammetry. Both ligands display low energy
π
-
π
* transitions above 500 nm with modest molar absorptivities. To make chromophores water soluble, N-methylated dipyrromethenes were synthesized and show bathochromic shifts compared to the neutral dipyrromethenes, which suggests that localized positive charge on the peripheral nitrogen of N-methylated compounds stabilize the
π
* orbitals. When coordinated to two ruthenium (II) bis(bipyridyl) groups, the new bimetallic complexes generated give an overall 2
+
charge. The electronic transition of the bimetallic ruthenium (II) complexes display typical bipyridyl intraligand
π
-
π
* transitions at 295 nm and metal-to-ligand charge-transfer transitions above 500 nm with molar absorptivities greater than 40000 M
-1
cm
-1
. Oxidation of the ruthenium (II) metal centers to ruthenium (III) occurs at potentials above 0.80 V versus the Ag/ AgCl reference electrode. Binding studies with calf thymus DNA (ctDNA) show intrinsic binding constants as high as 10
5
M
-1
(10
6
M
-1
for Ru
2
-IsoQvan, complex III) indicating very strong interactions of N-methylated and ruthenium compounds with DNA. In this study, the N-methylated and ruthenium compounds are water-soluble and show the ability to photonick plasmid DNA when irradiated with low-energy light above 550 nm for brief periods of time. In addition, one of the complexes, Ru
2
-IsoQvan (complex III), shows the ability to initiate double-strand breaks of plasmid DNA by gel electrophoresis. Studies indicate that the photoinduced mechanism of Ru
2
-IsoQvan (complex III) is quite complex and both type I and type II pathways are involved resulting in both the formation of singlet oxygen and radicals. In addition, singlet oxygen is responsible for DNA double-strand breaking.
Committee
Shawn Swavey (Advisor)
Matt Lopper (Committee Member)
Kevin Church (Committee Member)
Pages
71 p.
Subject Headings
Chemistry
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RIS
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Citations
Wang, M. (2016).
Synthesis, Characterization, DNA Binding and DNA Photocleavage of Two New Dipyrromethenes and Their Ruthenium (II) and N-Methylated Analogs
[Master's thesis, University of Dayton]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1460657926
APA Style (7th edition)
Wang, Mengyu.
Synthesis, Characterization, DNA Binding and DNA Photocleavage of Two New Dipyrromethenes and Their Ruthenium (II) and N-Methylated Analogs.
2016. University of Dayton, Master's thesis.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=dayton1460657926.
MLA Style (8th edition)
Wang, Mengyu. "Synthesis, Characterization, DNA Binding and DNA Photocleavage of Two New Dipyrromethenes and Their Ruthenium (II) and N-Methylated Analogs." Master's thesis, University of Dayton, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1460657926
Chicago Manual of Style (17th edition)
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Document number:
dayton1460657926
Download Count:
381
Copyright Info
© 2016, all rights reserved.
This open access ETD is published by University of Dayton and OhioLINK.