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Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores

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Six kinds of tetra alkylester type calix[4]arene derivatives, (R1=R2=CH31, C2H52, C3H73,n-C4H94,t-C4H95,n-C10H216), a diethyl-didecyl mixed ester type (R1=C2H5, R2 =C10H217), and three kinds of lower rim bridged types (R1=C2H5, R2−R2=―(CH2)10―∶8, ―(CH2)12―∶9, ―(CH2)2(OCH2CH2)3―∶10) were characterized by electrochemical measurement to elucidate the effect of the length of the alkyl group of alkoxycarbonyl substituents on Na+ selectivity. To obtain excellent Na+ selective ionophores, introduction of short chain alkyl groups rather than long chain ones, such as a decyl group, and maintenance of sufficient solubility of the calix[4]arene derivatives in the membrane solvent are required concurrently. Among the calix[4]arenes tested, 25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-p-tert-butylcalix[4]arene2, and the diethyl-didecyl mixed ester type derivative7 are the best ionophores for a Na+ selective electrode. On the other hand, sodium selectivity of the bridged type derivative9 is comparable or even superior to that of the known bis(12-crown-4).

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Correspondence to Y. Shibutani.

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This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.

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Shibutani, Y., Yoshinaga, H., Yakabe, K. et al. Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores. J Incl Phenom Macrocycl Chem 19, 333–342 (1994). https://doi.org/10.1007/BF00708991

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Key words

  • Calix[4]arene
  • Na+ selective ionophore
  • lower rim bridged calix[4]arene