Complexation of [2.2]paracyclophane with β- and γ-cyclodextrins studied by HPLC and NMR

• Authors: Helena Dodziuk , Anna Bielejewska , Wojciech Schilf , Haruhisa Ueda
• Languages of publication: EN

Abstracts

EN

The NMR spectra of [2.2]paracyclophane with β- or γ-cyclodextrin in DMF-d7 at room temperature do not show significant complexation, while HPLC of the complexes in mixed H2O:alcohol solvents demonstrate complexation with different stoichiometries. At 243 K in DMF solution the H3 and H5 NMR signals of γ-cyclodextrin (but not β) exhibit complexation-induced chemical shifts denoting complex formation. According to HPLC, at room temperature the [2.2]paracyclophane complex with β-cyclodextrin in 20% H2O:EtOH exhibits 1:2 stoichiometry with K 1 = 1×102 ± 2, K 2 = 9.0×104 ± 2×103 (K = 9×106) while that with γ-cyclodextrin in 50% H2O:MeOH exhibits 1:1 stoichiometry with K 1 = 4×103 ± 150 M−1. Thermodynamic parameters for both complexes have been estimated from the retention time temperature dependence. For the β-cyclodextrin complexation at 25°C ΔG 0CD is −39.7 kJ mol−1 while ΔH 0CD and ΔS 0CD are −88.2 kJ mol−1 and −0.16 kJ mol−1 K−1. For γ-cyclodextrin, the corresponding values are ΔG 0CD = −20.5 kJ mol−1, ΔH 0CD = −33.5 kJ mol−1 and ΔS 0CD = −0.04 kJ mol−1 K−1. [...]

Keywords

EN

Cyclodextrin cyclophane complexes; HPLC; NMR; Thermodynamic parameters

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2011
• Volume: 9
• Issue: 6
• Pages: 1056-1061

Dates

published

1 - 12 - 2011

online

27 - 9 - 2011

Contributors

author

Helena Dodziuk

• Institute of Physical Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Poland

author

Anna Bielejewska

• Institute of Physical Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Poland

author

Wojciech Schilf

• Institute of Organic Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Poland

author

Haruhisa Ueda

• Department of Physical Chemistry, Hoshi University, 4-41Ebara 2-chome, Shinagawa-ku, 142-8501, Tokyo, Japan

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Identifiers

DOI

10.2478/s11532-011-0095-6