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Inclusion Complex Formation of Thiacalix[4]arene and Xe in Aqueous Solution Studied by Hyperpolarized 129Xe NMR

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Abstract

The inclusion complex formation of 4-sulfothiacalix[4]arene sodium salt (STCAS) and Xe has been investigated by using hyperpolarized 129Xe NMR spectroscopy. Our new continuous-flow type hyperpolarizing system has advantageous capabilities that can supply hyperpolarized gases continuously and directly to a sample solution in a NMR tube. Consequently saturated Xe concentration in the aqueous solution of STCAS is maintained during the NMR experiment, and 129Xe NMR spectra can be obtained in remarkably short time. STCAS concentration dependence of 129Xe chemical shift has been analyzed in an elaborated way by a computer method as well as a simple graphic method that we have proposed. The association constant K:13.6±0.8 M−1 at 25 °C was obtained, and further analysis of the temperature dependence has successfully given thermodynamic parameters of enthalpy (ΔH) and entropy (ΔS) for the inclusion complex formation: ΔH = −11.9±1.9 kJ mol−1 and ΔS = −17.4±5.8 JK−1 mol−1. The energetic aspects of complex formation are discussed from the size effect and from the molecular theory of standard entropy, and a release of definite number of water molecules from STCAS cavity is suggested in the inclusion complex formation with Xe.

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Abbreviations

FID:

Free Induction Decay

HP:

Hyperpolarized

NMR:

Nuclear Magnetic Resonance

PSAS:

p-phenolsulfonic acid sodium salt

RF:

Radio-Frequency

SPINOE:

Spin Polarization-Induced Nuclear Overhauser Effect

STCAS:

4-Sulfothiacalix[4]arene sodium salt.

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Authors and Affiliations

  1. Division of Health Sciences, Graduate School of Medicine, Osaka University, 1-7 Yamadaoka, Suita, Osaka, 565-0871, Japan

    Junko Fukutomi, Yuko Adachi, Akari Kaneko, Atsuomi Kimura & Hideaki Fujiwara

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  1. Junko Fukutomi
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  2. Yuko Adachi
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  3. Akari Kaneko
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  4. Atsuomi Kimura
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  5. Hideaki Fujiwara
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Correspondence to Junko Fukutomi.

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Fukutomi, J., Adachi, Y., Kaneko, A. et al. Inclusion Complex Formation of Thiacalix[4]arene and Xe in Aqueous Solution Studied by Hyperpolarized 129Xe NMR. J Incl Phenom Macrocycl Chem 58, 115–122 (2007). https://doi.org/10.1007/s10847-006-9130-1

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