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.
| Language | English |
|---|---|
| Pages | 165-170 |
| Number of pages | 6 |
| Journal | Dalton Transactions |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 21 Jan 2003 |
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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 journal › Article › Research › peer-review
TY - JOUR
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.
UR - http://www.scopus.com/inward/record.url?scp=2942642705&partnerID=8YFLogxK
U2 - 10.1039/b208846k
DO - 10.1039/b208846k
M3 - Article
SP - 165
EP - 170
JO - Journal of the Chemical Society - Dalton Transactions
T2 - Journal of the Chemical Society - Dalton Transactions
JF - Journal of the Chemical Society - Dalton Transactions
SN - 1477-9226
IS - 2
ER -