Synthesis and spectroscopy of ruthenium-modified nucleic acids
<p>Redox-active probes are designed and prepared for use in DNA-mediated electron transfer studies. These probes consist of ruthenium(II) complexes bound to nucleosides that possess metal-binding ligands. Low- and high-potential oxidants are synthesized from these modified nucleosides and d...
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Online Access: | https://thesis.library.caltech.edu/8151/1/Krider_es_2001.pdf Krider, Elizabeth Stratford (2001) Synthesis and spectroscopy of ruthenium-modified nucleic acids. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/s0za-ec86. https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161 <https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161> |
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ndltd-CALTECH-oai-thesis.library.caltech.edu-81512021-04-20T05:01:40Z https://thesis.library.caltech.edu/8151/ Synthesis and spectroscopy of ruthenium-modified nucleic acids Krider, Elizabeth Stratford <p>Redox-active probes are designed and prepared for use in DNA-mediated electron transfer studies. These probes consist of ruthenium(II) complexes bound to nucleosides that possess metal-binding ligands. Low- and high-potential oxidants are synthesized from these modified nucleosides and display reversible one-electron electrochemical behavior. The ruthenium-modified nucleosides exhibit distinct charge-transfer transitions in the visible region that resemble those of appropriate model complexes. Resonance Raman and time-resolved emission spectroscopy are used to characterize the nature of these transitions.</p> <p>The site-specific incorporation of these redox-active probes into oligonucleotides is explored using post-synthetic modification and solid-phase synthetic methods. The preparation of the metal-binding nucleosides, their incorporation into oligonucleotides, and characterization of the resulting oligonucleotides is described. Because the insertion of these probes into modified oligonucleotides using post-synthetic modification is unsuccessful, solid-phase synthetic methods are explored. These efforts lead to the first report of 3'-metallated oligonucleotides prepared completely by automated solid-phase synthesis. Preliminary efforts to prepare a bis-metallated oligonucleotide by automated synthesis are described.</p> <p>The electrochemical, absorption, and emissive features of the ruthenium-modified oligonucleotides are unchanged from those of the precursor metallonucleoside. The absence of any change in these properties upon incorporation into oligonucleotides and subsequent hybridization suggests that the incorporated ruthenium(II) complex is a valuable probe for DNA-mediated electron transfer studies.</p> 2001 Thesis NonPeerReviewed application/pdf en other https://thesis.library.caltech.edu/8151/1/Krider_es_2001.pdf Krider, Elizabeth Stratford (2001) Synthesis and spectroscopy of ruthenium-modified nucleic acids. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/s0za-ec86. https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161 <https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161> https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161 CaltechTHESIS:03202014-093625161 10.7907/s0za-ec86 |
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<p>Redox-active probes are designed and prepared for use in DNA-mediated electron
transfer studies. These probes consist of ruthenium(II) complexes bound to nucleosides
that possess metal-binding ligands. Low- and high-potential oxidants are synthesized
from these modified nucleosides and display reversible one-electron electrochemical
behavior. The ruthenium-modified nucleosides exhibit distinct charge-transfer transitions
in the visible region that resemble those of appropriate model complexes. Resonance
Raman and time-resolved emission spectroscopy are used to characterize the nature of
these transitions.</p>
<p>The site-specific incorporation of these redox-active probes into oligonucleotides
is explored using post-synthetic modification and solid-phase synthetic methods. The
preparation of the metal-binding nucleosides, their incorporation into oligonucleotides,
and characterization of the resulting oligonucleotides is described. Because the insertion
of these probes into modified oligonucleotides using post-synthetic modification is
unsuccessful, solid-phase synthetic methods are explored. These efforts lead to the first
report of 3'-metallated oligonucleotides prepared completely by automated solid-phase
synthesis. Preliminary efforts to prepare a bis-metallated oligonucleotide by automated
synthesis are described.</p>
<p>The electrochemical, absorption, and emissive features of the ruthenium-modified
oligonucleotides are unchanged from those of the precursor metallonucleoside. The
absence of any change in these properties upon incorporation into oligonucleotides and
subsequent hybridization suggests that the incorporated ruthenium(II) complex is a
valuable probe for DNA-mediated electron transfer studies.</p> |
author |
Krider, Elizabeth Stratford |
spellingShingle |
Krider, Elizabeth Stratford Synthesis and spectroscopy of ruthenium-modified nucleic acids |
author_facet |
Krider, Elizabeth Stratford |
author_sort |
Krider, Elizabeth Stratford |
title |
Synthesis and spectroscopy of ruthenium-modified nucleic acids |
title_short |
Synthesis and spectroscopy of ruthenium-modified nucleic acids |
title_full |
Synthesis and spectroscopy of ruthenium-modified nucleic acids |
title_fullStr |
Synthesis and spectroscopy of ruthenium-modified nucleic acids |
title_full_unstemmed |
Synthesis and spectroscopy of ruthenium-modified nucleic acids |
title_sort |
synthesis and spectroscopy of ruthenium-modified nucleic acids |
publishDate |
2001 |
url |
https://thesis.library.caltech.edu/8151/1/Krider_es_2001.pdf Krider, Elizabeth Stratford (2001) Synthesis and spectroscopy of ruthenium-modified nucleic acids. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/s0za-ec86. https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161 <https://resolver.caltech.edu/CaltechTHESIS:03202014-093625161> |
work_keys_str_mv |
AT kriderelizabethstratford synthesisandspectroscopyofrutheniummodifiednucleicacids |
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