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Interactions of Binuclear Ruthenium(II) Complexes with Oligonucleotides in Hydrogel Matrix: Enantioselective Threading Intercalation into GC Context
journal contribution
posted on 2013-03-14, 00:00 authored by Piotr Hanczyc, Per Lincoln, Bengt NordenA stretched poly(vinyl alcohol) (PVA)
film provides a unique matrix
that enables also short DNA oligonucleotide duplex to be oriented
and studied by linear dichroism (LD). This matrix further allows controlling
DNA secondary structure by proper hydration (A or B form), and such
humid films could potentially also mimic the molecular crowding in
cellular contexts. However, early attempts to study intercalators
and groove binders for probing DNA in PVA failed due to competitive
matrix binding. Here we report the successful orientation in PVA of
DNA oligonucleotide duplex hairpins with thread-intercalated binuclear
complex [μ-(11,11′-bidppz)(phen)4Ru2]4+, and how LD depends on oligonucleotide sequence and
metal center chirality. Opposite enantiomers of the ruthenium complex,
ΔΔ and ΛΛ, were investigated with respect
to enantioselectivity toward GC stretches as long as 22 bp. LD, supported
by emission kinetics, reveals that threading intercalation occurs
only with ΔΔ whereas ΛΛ remains externally
bound, probably in either or both of the grooves of the GC-DNA. Enantioselective
binding properties of sterically rigid DNA probes such as the ruthenium
complexes could find applications for targeting nucleic acids, e.g.,
to inhibit transcription in therapeutic context such as treatment
of malaria or cancer.
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Keywords
oligonucleotide sequenceEnantioselective Threading IntercalationΔΔGC stretchesemission kineticsDNA oligonucleotide duplex hairpinsstudy intercalatorsgroove bindersEnantioselective binding propertiescontextHydrogel Matrixmatrix bindingPVA22 bpruthenium complexesmetal center chiralityΛΛfilmDNA oligonucleotide duplexLDGC ContextADNA probes
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