Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides

Gabriella Bobba; Rachel. S. Dickins; S. D. Kean; Céline E. Mathieu; David Parker; Robert D. Peacock; Giuliano Siligardi; Martin J. Smith; J. A. Gareth Williams; Carlos F.G.C. Geraldes

doi:10.1039/B104796P

Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides

Gabriella Bobba, Rachel. S. Dickins, S. D. Kean, Céline E. Mathieu, David Parker, Robert D. Peacock, Giuliano Siligardi, Martin J. Smith , J. A. Gareth Williams, Carlos F.G.C. Geraldes

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

The interaction of Δ- and Δ-Eu and Yb cationic complexes bearing an N-methylphenanthridinium chromophore with [(CG)₆]₂, [(AT)₆]₂ and [CGCGAATTCGCG]₂ has been interrogated by ESMS, ¹H NMR, absorption, difference circular dichroism, fluorescence quenching and Ln luminescence emission spectroscopy. Stepwise complexation occurs with up to 3 : 1 limiting stoichiometry for [(CG)₆]₂ and 2 : 1 for [CGCGAATTCGCG]₂, as indicated by absorption measurements and direct ESMS observation of the non-covalent duplex adducts. Binding to [(CG)₆]₂ occurred with an affinity of 8.7 × 10⁶ M^-1 duplex^-1 for the Δ-Eu isomer which was 50 times greater than to [(AT)₆]₂. A primary component of the free energy of binding has been linked to an intercalative interaction, supported by absorption, ICD and fluorescence quenching characteristics. The lanthanide coordination environment and local helicity remain unchanged but the oligonucleotide underwent distinctive changes in local helicity and pitch which were sensitive to the handedness of the Ln complex and in certain cases to the nature of the Ln ion (Yb vs. Eu). With [CGCGAATTCGCG]₂ ¹H NMR TOCSY and NOESY analysis in the presence of increasing concentrations of the Gd analogues revealed that the most avid complex binding site was located in the centre of the oligonucleotide, with the Δ-isomer binding more strongly.

Original language	English
Pages (from-to)	1729-1737
Number of pages	9
Journal	Journal of the Chemical Society, Perkin Transactions 2
Issue number	9
DOIs	https://doi.org/10.1039/B104796P
Publication status	Published - 1 Oct 2001
Externally published	Yes

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Bobba, G., Dickins, R. S., Kean, S. D., Mathieu, C. E., Parker, D., Peacock, R. D., Siligardi, G., Smith , M. J., Gareth Williams, J. A., & Geraldes, C. F. G. C. (2001). Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides. Journal of the Chemical Society, Perkin Transactions 2, (9), 1729-1737. https://doi.org/10.1039/B104796P

@article{9ff157ec1d77419b9f5e2b98cd3a08d9,

title = "Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides",

abstract = "The interaction of Δ- and Δ-Eu and Yb cationic complexes bearing an N-methylphenanthridinium chromophore with [(CG)6]2, [(AT)6]2 and [CGCGAATTCGCG]2 has been interrogated by ESMS, 1H NMR, absorption, difference circular dichroism, fluorescence quenching and Ln luminescence emission spectroscopy. Stepwise complexation occurs with up to 3 : 1 limiting stoichiometry for [(CG)6]2 and 2 : 1 for [CGCGAATTCGCG]2, as indicated by absorption measurements and direct ESMS observation of the non-covalent duplex adducts. Binding to [(CG)6]2 occurred with an affinity of 8.7 × 106 M-1 duplex-1 for the Δ-Eu isomer which was 50 times greater than to [(AT)6]2. A primary component of the free energy of binding has been linked to an intercalative interaction, supported by absorption, ICD and fluorescence quenching characteristics. The lanthanide coordination environment and local helicity remain unchanged but the oligonucleotide underwent distinctive changes in local helicity and pitch which were sensitive to the handedness of the Ln complex and in certain cases to the nature of the Ln ion (Yb vs. Eu). With [CGCGAATTCGCG]2 1H NMR TOCSY and NOESY analysis in the presence of increasing concentrations of the Gd analogues revealed that the most avid complex binding site was located in the centre of the oligonucleotide, with the Δ-isomer binding more strongly.",

author = "Gabriella Bobba and Dickins, {Rachel. S.} and Kean, {S. D.} and Mathieu, {C{\'e}line E.} and David Parker and Peacock, {Robert D.} and Giuliano Siligardi and Smith, {Martin J.} and {Gareth Williams}, {J. A.} and Geraldes, {Carlos F.G.C.}",

year = "2001",

month = oct,

day = "1",

doi = "10.1039/B104796P",

language = "English",

pages = "1729--1737",

journal = "Journal of the Chemical Society, Perkin Transactions 2",

issn = "1470-1820",

publisher = "Royal Society of Chemistry",

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}

Bobba, G, Dickins, RS, Kean, SD, Mathieu, CE, Parker, D, Peacock, RD, Siligardi, G, Smith , MJ, Gareth Williams, JA & Geraldes, CFGC 2001, 'Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides', Journal of the Chemical Society, Perkin Transactions 2, no. 9, pp. 1729-1737. https://doi.org/10.1039/B104796P

Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides. / Bobba, Gabriella; Dickins, Rachel. S.; Kean, S. D. et al.
In: Journal of the Chemical Society, Perkin Transactions 2, No. 9, 01.10.2001, p. 1729-1737.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides

AU - Bobba, Gabriella

AU - Dickins, Rachel. S.

AU - Kean, S. D.

AU - Mathieu, Céline E.

AU - Parker, David

AU - Peacock, Robert D.

AU - Siligardi, Giuliano

AU - Smith , Martin J.

AU - Gareth Williams, J. A.

AU - Geraldes, Carlos F.G.C.

PY - 2001/10/1

Y1 - 2001/10/1

N2 - The interaction of Δ- and Δ-Eu and Yb cationic complexes bearing an N-methylphenanthridinium chromophore with [(CG)6]2, [(AT)6]2 and [CGCGAATTCGCG]2 has been interrogated by ESMS, 1H NMR, absorption, difference circular dichroism, fluorescence quenching and Ln luminescence emission spectroscopy. Stepwise complexation occurs with up to 3 : 1 limiting stoichiometry for [(CG)6]2 and 2 : 1 for [CGCGAATTCGCG]2, as indicated by absorption measurements and direct ESMS observation of the non-covalent duplex adducts. Binding to [(CG)6]2 occurred with an affinity of 8.7 × 106 M-1 duplex-1 for the Δ-Eu isomer which was 50 times greater than to [(AT)6]2. A primary component of the free energy of binding has been linked to an intercalative interaction, supported by absorption, ICD and fluorescence quenching characteristics. The lanthanide coordination environment and local helicity remain unchanged but the oligonucleotide underwent distinctive changes in local helicity and pitch which were sensitive to the handedness of the Ln complex and in certain cases to the nature of the Ln ion (Yb vs. Eu). With [CGCGAATTCGCG]2 1H NMR TOCSY and NOESY analysis in the presence of increasing concentrations of the Gd analogues revealed that the most avid complex binding site was located in the centre of the oligonucleotide, with the Δ-isomer binding more strongly.

AB - The interaction of Δ- and Δ-Eu and Yb cationic complexes bearing an N-methylphenanthridinium chromophore with [(CG)6]2, [(AT)6]2 and [CGCGAATTCGCG]2 has been interrogated by ESMS, 1H NMR, absorption, difference circular dichroism, fluorescence quenching and Ln luminescence emission spectroscopy. Stepwise complexation occurs with up to 3 : 1 limiting stoichiometry for [(CG)6]2 and 2 : 1 for [CGCGAATTCGCG]2, as indicated by absorption measurements and direct ESMS observation of the non-covalent duplex adducts. Binding to [(CG)6]2 occurred with an affinity of 8.7 × 106 M-1 duplex-1 for the Δ-Eu isomer which was 50 times greater than to [(AT)6]2. A primary component of the free energy of binding has been linked to an intercalative interaction, supported by absorption, ICD and fluorescence quenching characteristics. The lanthanide coordination environment and local helicity remain unchanged but the oligonucleotide underwent distinctive changes in local helicity and pitch which were sensitive to the handedness of the Ln complex and in certain cases to the nature of the Ln ion (Yb vs. Eu). With [CGCGAATTCGCG]2 1H NMR TOCSY and NOESY analysis in the presence of increasing concentrations of the Gd analogues revealed that the most avid complex binding site was located in the centre of the oligonucleotide, with the Δ-isomer binding more strongly.

U2 - 10.1039/B104796P

DO - 10.1039/B104796P

M3 - Article

AN - SCOPUS:0034741423

SN - 1470-1820

SP - 1729

EP - 1737

JO - Journal of the Chemical Society, Perkin Transactions 2

JF - Journal of the Chemical Society, Perkin Transactions 2

IS - 9

ER -

Chiroptical, ESMS and NMR spectroscopic study of the interaction of enantiopure lanthanide complexes with selected self-complementary dodecamer oligonucleotides

Abstract

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