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

doi:10.1039/b208846k

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

Department of Molecular Sciences

Research output: Contribution to journal › Article

10 Citations (Scopus)

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.

Original language	English
Pages (from-to)	165-170
Number of pages	6
Journal	Dalton Transactions
Issue number	2
DOIs	https://doi.org/10.1039/b208846k
Publication status	Published - 21 Jan 2003

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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.",

author = "Proudfoot, {Emma M.} and Mackay, {Joel P.} and Peter Karuso",

year = "2003",

month = "1",

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doi = "10.1039/b208846k",

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publisher = "Royal Society of Chemistry",

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T1 - Solution structure and behaviour of Δ-m-α-[Ru(R,R- picchxnMe2)(phi)]2+ by NMR spectroscopy and molecular modelling

AU - Proudfoot, Emma M.

AU - Mackay, Joel P.

AU - Karuso, Peter

PY - 2003/1/21

Y1 - 2003/1/21

N2 - 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.

AB - 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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DO - 10.1039/b208846k

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JO - Dalton Transactions

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