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Lim, Mi Hee
MetalloNeuroChemistry Lab (MNCL)
Research Interests
  • Neurodegenerative disease, small molecule design, network between metal, proteins, and ROS

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Sensitivity of Ru(bpy)(2)dppz(2+) Luminescence to DNA Defects

Cited 49 times inthomson ciCited 44 times inthomson ci
Title
Sensitivity of Ru(bpy)(2)dppz(2+) Luminescence to DNA Defects
Author
Lim, Mi HeeSong, HangOlmon, Eric D.Dervan, Elizabeth E.Barton, Jacqueline K.
Keywords
BASE MISMATCHES; ABASIC SITES; RHODIUM INTERCALATOR; LINEAR DICHROISM; NUCLEIC-ACIDS; LIGHT-SWITCH; BINDING; RECOGNITION; COMPLEXES; OLIGONUCLEOTIDES
Issue Date
2009-06
Publisher
AMER CHEMICAL SOC
Citation
INORGANIC CHEMISTRY, v.48, no.12, pp.5392 - 5397
Abstract
The luminescent characteristics of Ru(bpy) 2dppz 2+ (dppz = dipyrido[3,2-a:2′,3′-e]phenazine), a DNA light switch, were investigated in the presence of oligonucleotides containing single base mismatches or an abasic site. In water, the ruthenium luminescence is quenched, but, bound to well matched duplex DNA, the Ru complex luminesces. Here we show that with DNAs containing a defect, rac-, Δ-, and λ-Ru(bpy) 2dppz 2+ exhibit significant luminescent enhancements above that with well matched DNA. In the presence of a single base mismatch, large luminescent enhancements are evident for the Δ-Ru isomer; the λ-isomer shows particularly high luminescence bound to an oligonucleotide containing an abasic site. Similar increases are not evident with two common DNA-binding organic fluorophores, ethidium bromide and TO-PRO-3. Titrations with hairpin oligonucleotides containing a variable mismatch site show correlation between the level of luminescent enhancement and the thermodynamic destabilization associated with the mismatch. This correlation is reminiscent of that found earlier for a bulky rhodium complex that binds mismatched DNA sites through metalloinsertion, where the complex binds the DNA from the minor groove side, ejecting the mismatched bases into the major groove. Differential quenching studies with minor and major groove quenchers and time-resolved emission studies support this metalloinsertion mode for the dppz complex at the defect site. Certainly these data underscore the utility of Ru(bpy) 2dppz 2+ as a sensitive luminescent reporter of DNA and its defects.
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DOI
10.1021/ic900407n
ISSN
0020-1669
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PHY_Journal Papers
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