Springer Online Journal Archives 1860-2000
Chemistry and Pharmacology
Summary The macrocyclic polyethers 4′-methylbenzo-15-crown-5 (15C5) and 4′-methylbenzo-18-crown-6 (18C6) as well as the corresponding crown polymers and crown-styrene copolymers were used as carriers for the transport of sodium and potassium picrate or the corresponding chlorides across a stirred, chloroform membrane. The observation of pronounced bathochromic shifts in the optical spectra of picrate salts on increasing the interionic ion pair distance could be utilized in determining the nature and structure of the migrating species. These species were found to be ion pair crown complexes of at least two kinds, viz., crown-complexed tight ion pairs and crown-separated ion pairs. The feasibility to thus identify the detailed structure of the migrating ionic entity is important as solvents of low polarity such as chloroform or hexane have been used as liquid membranes to represent the interior of biomembranes. The structure of the ion pair is expected to be an important consideration in correlating properties such as membrane potentials or cation selectivities with ionic distribution equilibria. Ion pair extraction equilibrium constants were determined in the H2O−CHCl3 system for the various crown species. The values for 18C6 with sodium and potassium picrate are nearly the same as those for the corresponding polymers. The same was found with 15C5 and sodium picrate; but the potassium forms, in addition to a 1∶1 complex, a 1∶2 complex with 15C5, making the corresponding polymer a more effective extracting agent. The ionic distribution data were interpreted in terms of the salt partition coefficients and the complex formation constants of the ion pair crown complexes in chloroform. The salt migration across the liquid membrane was found to be controlled by the diffusion of the ion pair complex in the chloroform, the extraction equilibrium across the interphase being rapidly established. The thickness of the diffusion layer adjacent to the water-chloroform interphase was estimated to be 50 μ. The ratios of the salt fluxes under otherwise identical conditions were found to be governed by the extraction equilibrium constants, the selectivity ratio for the potassium-to-sodium picrate with 18C6 being 118. This ratio, which was also determined for other crown species, was found to be anion dependent.
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