Abstract

Photophysical studies have been undertaken to characterize the binding interactions of enantiomers of Ru(phen)3(2+), Ru(DIP)3(2+), and racemic Ru(bpy)2dppz2+ (where phen = 1,10-phenanthroline, DIP = 4,7-diphenylphenanthroline, and dppz = dipyridophenazine) with Z-form poly d(GC). Parallel enhancements in steady state luminescent intensity and a lengthening of luminescent lifetimes are seen for ruthenium enantiomers with Z-DNA as for B-DNA but with enantio-selectivities reversed. Greater enhancements are seen for DELTA-isomers with the right-handed helix but for LAMBDA-isomers with the left-handed helix. Ru(bpy)2dppz2+, an avid intercalator in B-DNA, displays no luminescence free in aqueous solution, but luminesces brightly bound to either B- or Z-poly d(GC). Stern-Volmer quenching studies also support the enantio-selective preference in binding to B-DNA by DELTA-isomers and a reversal with binding to Z-DNA preferentially by the LAMBDA-isomers. Steady state polarization studies indicate a rigid association of the complexes with both B-and Z-DNA on the time-scale of their emission and again with symmetrical enantioselectivities for the left and right-handed helices. Given the well characterized intercalative association of the complexes with B-DNA, the parallel results seen here with Z-DNA point strongly to a comparable intercalative association with the Z-form helix. That molecules may interact with Z-DNA through intercalation has not been demonstrated previously and now requires consideration in describing the range of interactions of small molecules and proteins with Z-DNA.

Publication Date

5-25-1991

Comments

Article may be found at: http://nar.oxfordjournals.org/content/vol19/issue10/index.dtl ISSN:1362-4962 Note: imported from RIT’s Digital Media Library running on DSpace to RIT Scholar Works in February 2014.

Document Type

Article

Department, Program, or Center

Thomas H. Gosnell School of Life Sciences (COS)

Campus

RIT – Main Campus

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