Solution structure and behaviour of Δ-m-α-[Ru(R,R- picchxnMe2)(phi)]2+ by NMR spectroscopy and molecular modelling

Emma M. Proudfoot, Joel P. Mackay, Peter Karuso

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The self-association of the DNA metalloprobe Δ-cis-α-[Ru(R,R- picchxnMe2)(phi)]2+ (α-phi) in aqueous solution has been investigated using 1H NMR spectroscopy and molecular modelling. The concentration dependence of proton chemical shifts of the complex gave initial indications of a self-associated species, while its structural isomer Δ-cis-β-[Ru(R,R-picchxnMe2)(phi)]2+ (β-phi) showed no such dependence. 2D-COSY and 2D-ROESY experiments were used for the complete assignment of the proton resonances of both isomers and allowed a qualitative determination of the self-association of the a isomer through the detection of intermolecular ROEs. NMR spectroscopy can also be effectively used to differentiate Δ- and Λ-diastereomers. In addition, we show, by pulsed field gradient longitudinal eddy-current delay (PFGLED) NMR spectroscopy, that α-phi self-associates at higher concentrations with an effective molecular weight at 25 mM three times that at 2.5 mM. This apparent oligomerisation was not observed for the β-isomer.

LanguageEnglish
Pages165-170
Number of pages6
JournalDalton Transactions
Issue number2
DOIs
Publication statusPublished - 21 Jan 2003

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Molecular modeling
Isomers
Nuclear magnetic resonance spectroscopy
Protons
Association reactions
Oligomerization
Chemical shift
Eddy currents
Molecular weight
DNA
Experiments

Cite this

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title = "Solution structure and behaviour of Δ-m-α-[Ru(R,R- picchxnMe2)(phi)]2+ by NMR spectroscopy and molecular modelling",
abstract = "The self-association of the DNA metalloprobe Δ-cis-α-[Ru(R,R- picchxnMe2)(phi)]2+ (α-phi) in aqueous solution has been investigated using 1H NMR spectroscopy and molecular modelling. The concentration dependence of proton chemical shifts of the complex gave initial indications of a self-associated species, while its structural isomer Δ-cis-β-[Ru(R,R-picchxnMe2)(phi)]2+ (β-phi) showed no such dependence. 2D-COSY and 2D-ROESY experiments were used for the complete assignment of the proton resonances of both isomers and allowed a qualitative determination of the self-association of the a isomer through the detection of intermolecular ROEs. NMR spectroscopy can also be effectively used to differentiate Δ- and Λ-diastereomers. In addition, we show, by pulsed field gradient longitudinal eddy-current delay (PFGLED) NMR spectroscopy, that α-phi self-associates at higher concentrations with an effective molecular weight at 25 mM three times that at 2.5 mM. This apparent oligomerisation was not observed for the β-isomer.",
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Solution structure and behaviour of Δ-m-α-[Ru(R,R- picchxnMe2)(phi)]2+ by NMR spectroscopy and molecular modelling. / Proudfoot, Emma M.; Mackay, Joel P.; Karuso, Peter.

In: Dalton Transactions, No. 2, 21.01.2003, p. 165-170.

Research output: Contribution to journalArticleResearchpeer-review

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