Use of Selective Deuteration and 1H NMR in Demonstrating Major Groove Binding of .DELTA.-[Ru(phen)2dppz]2+ to d(GTCGAC)2

Dupureur, Cynthia M.; Barton, Jacqueline K.

doi:10.1021/ja00101a053

Cited by 188 publications

(166 citation statements)

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“…Significantly, insertion differs from the previously well characterized intercalation [22][23][24][25][34][35][36][37] in that the DNA does not unwind to enable a ligand to enter the base stack, but rather the incoming ligand simply ejects both bases of the destabilized or weakly bonded pair. The present NMR study confirms that minimal perturbation of the DNA is required for insertion of the bulky ligand and base ejection.…”

Section: Comparison With the Crystal Structurementioning

confidence: 83%

Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

2007

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The bulky octahedral complex, Rh(bpy) 2 chrysi 3+ (chrysi = 5, 6-chrysenequinone diimine), binds single base mismatches in a DNA duplex with micromolar binding affinities and high selectivity. Here we present an NMR solution study to characterize the binding mode of this bulky metal complex with its target CC mismatch in the oligonucleotide duplex (5′-CGGACTCCG-3′) 2 . Both NOESY and COSY studies indicate that Rh(bpy) 2 chrysi 3+ inserts deeply in the DNA at the mismatch site via the minor groove and with ejection of both destabilized cytosines into the opposite major groove. The insertion only minimally distorts the conformation of the oligonucleotide local to the binding site. Both flanking, well-matched base pairs remain tightly hydrogen-bonded to each other, and 2D DQF-COSY experiments indicate that all sugars maintain their original C2′ endo conformation. Remarkably, 31 P NMR reveals that opening of the phosphate angles from a B I to a B II conformation is sufficient for insertion of the bulky metal complex. These results corroborate those obtained crystallographically and, importantly, provide structural evidence for this specific insertion mode in solution.

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Section: Comparison With the Crystal Structurementioning

confidence: 83%

Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

2007

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“…It is noteworthy that we have seen previously for Ru(bpy) 2 dppz 2+ fluorescence and NMR results that are consistent with a mixture of straight-on and side-on orientations in matched duplex DNA. 23 Here, at the matched site, the eilatin complex can easily rotate within the intercalation site and maintain significant overlap with the bases above and below. Indeed, the stacking area appears comparable to that of the phi complex, just as their binding affinities for matched sites are similar.…”

Section: Implications For the Design Of Bulky Metalloinsertorsmentioning

confidence: 99%

Binding of Ru(bpy)₂(eilatin)²⁺ to Matched and Mismatched DNA

Zeglis

Barton

2008

Inorg. Chem.

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The DNA-binding properties of Ru(bpy) 2 (eilatin) 2+ have been investigated to determine if the sterically expansive eilatin ligand confers specificity for destabilized single-base mismatches in DNA. Competitive DNA photocleavage experiments employing a sequence-neutral metallointercalator, Rh(bpy) 2 (phi) 3+ (phi = 9,10-phenanthrenequinonediimine), and a mismatchspecific metalloinsertor, Rh(bpy) 2 (chrysi) 3+ (chrysi = chrysene-5,6-quinonediimine), reveal that the eilatin complex binds to a CC mismatched site with an apparent binding constant of 2.2(2) × 10 6 M −1 . Nonetheless, the selectivity in binding mismatched DNA is not high: competitive titrations with Rh(bpy) 2 (phi) 3+ show that the complex binds also to well-matched B-form sites. Thus, Ru (bpy) 2 (eilatin) 2+ , despite containing the extremely expansive eilatin ligand, displays lower selectivity for the mismatch than does Rh(bpy) 2 (chrysi) 3+ , a metalloinsertor containing the smaller, though still bulky, chrysene-5,6-quinonediimine ligand. In summary, the size and shape of the eilatin ligand allow stacking with both well-matched and mismatched DNA.

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“…Despite this limitation this route has proven to be particularly useful in the synthesis of deuteriated ligands containing aliphatic moieties, such as polydentate macrocylic ligands [19(b),28-30] and in the partial deuteriation of polyaromatic hydrocarbons via Diels-Alder reactions [31]. Incorporation of deuteriated precursors has also been used in the preparation of partially deuteriated dppz (d 6 -dipyridophenazine) where oxidation of d 8 -1,10-phenanthroline to the 5,6-diphenone was followed by condensation with o-phenylenediamine to form the target ligand [32]. [35], RuCl 3 and IrCl 3 [36] (deuteriation of mono-substituted aromatics and α,β-unsaturated acids) have been used successfully towards deuterium exchange.…”

Section: Hydrogen Isotope Exchange Reactions Involving O-h N-h and mentioning

confidence: 99%

The effect of deuteriation on the emission lifetime of inorganic compounds

Browne

Vos

2001

Coordination Chemistry Reviews

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Abstract.The application of deuteriation of both ligands and solvents on the photophysical properties of transition metal complexes in solution and glassy matrices is reviewed. The reduction in amplitude and frequency of vibrational modes due to deuterium's increased mass, relative to hydrogen, has a significant effect on non-radiative deactivation processes, which can occur through both intra-and inter-molecular vibrational coupling. The effect of deuteriation on excited state lifetimes has allowed for its application in probing the nature of excited state decay processes. The effects of isotopic exchange on vibrational spectroscopies such as resonance Raman and low temperature high-resolution emission spectroscopies are also addressed briefly.

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Use of Selective Deuteration and 1H NMR in Demonstrating Major Groove Binding of .DELTA.-[Ru(phen)2dppz]2+ to d(GTCGAC)2

Cited by 188 publications

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Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

Binding of Ru(bpy)₂(eilatin)²⁺ to Matched and Mismatched DNA

The effect of deuteriation on the emission lifetime of inorganic compounds

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Use of Selective Deuteration and 1H NMR in Demonstrating Major Groove Binding of .DELTA.-[Ru(phen)2dppz]2+ to d(GTCGAC)2

Cited by 188 publications

References 0 publications

Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

Binding of Ru(bpy)2(eilatin)2+ to Matched and Mismatched DNA

The effect of deuteriation on the emission lifetime of inorganic compounds

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Product

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Binding of Ru(bpy)₂(eilatin)²⁺ to Matched and Mismatched DNA