Selectivity alkali metal cations

In mimicking this type of function, noncyclic artificial carboxylic ionophores having two terminal groups of hydroxyl and carboxylic acid moieties were synthesized and the selective transport of alkali metal cations were examined by Yamazaki et al. 9 10). Noncyclic polyethers take on a pseudo-cyclic structure when coordinating cations and so it is possible to achieve the desired selectivity for specific cations by adjusting the length of the polyether chain 2). However, they were not able to observe any relationship between the selectivity and the structure of the host molecules in an active transport system using ionophores 1-3 10). (Table 1)... 

By considering the stability constant and the lipophilicity of host molecules, Fyles et al. synthesized a series of carboxylic ionophores having a crown ether moiety and energetically developed the active transport of alkali metal cations 27-32). Ionophores 19-21 possess appropriate stability constants for K+ and show effective K+-selective transports (Fig. 5). Although all of the corresponding [15]crown-5 derivatives (22-24) selectively transport Na+, their transport rates are rather slow compared with... 

There are two general classes of naturally-occurring antibiotics which influence the transport of alkali metal cations through natural and artificial membranes. The first category contains neutral macrocyclic species which usually bind potassium selectively over sodium. The second (non-cyclic) group contains monobasic acid functions which help render the alkaline metal complexes insoluble in water but soluble in non-polar solvents (Lauger, 1972 Painter Pressman, 1982). The present discussion will be restricted to (cyclic) examples from the first class. 

Polymeric pseudocrown ether networks have been generated in situ by the photopolymerization of poly(ethylene glycol) diacrylate transition metal complexes <00CM633>, and the effect of metal ion templation was evaluated. The 1,6,13,18-tetraoxa[6.6]paracyclophane-3,15-diyne (termed pyxophanes) was prepared from hydroquinone and l,4-dichlorobut-2-yne it forms size-selective 7i-complexes with alkali metal cations <00CC2377>. Dibenzo[ ]crown-m have been used in numerous elegant studies in which they were the needles that were threaded by diverse reagents the resultant... 

Electrodes based on solutions of cyclic polyethers in hydrocarbons show a selective response to alkali metal cations. The cyclic structure and physical dimensions of these compounds enable them to surround and replace the hydration shell of the cations and carry them into the membrane phase. Conduction occurs by diffusion of these charged complexes, which constitute a space charge within the membrane. Electrodes with a high selectivity for potassium over sodium (> 1000 1) have been produced. 

They form relatively stable complexes with monovalent cations, especially with alkali metal cations, where the complex stability has ion-selective character [88, 100, 193, 202, 213]. 

The 2-(AuC1)4 and 2-(PtCl2SMe2)4 complexes (see above), show extractability properties vs. alkali metal ions, with a greater affinity for than for other alkali metal ions [48]. No structural data were available and the nature of the binding in the formation of these complexes was not investigated. Similarly, the anionic complexes [2-Cu4(/t-Cl)4(/t3-Cl)] and [2-Ag4(/t-Cl)4(/t4-Cl)] have been shown to act as host for the selective binding of alkali metal cations and divalent metal ions like or Pb. Both complexes... 

Lariat ethers of structure 8 were found to be selective toward Li ion and the lariat crown ether-Li+ complexes are more stable than the corresponding complexes with Na or K+, in methanol. Nevertheless, experiments conducted in aqueous solution showed that Na+ had a better complexation ability than the other two alkali metal cations. Hence, selective complexation of lariat crown ethers with cations changes with the solvent system this may be due in part to the difference in solvation between solvent and cation (Figure 9 f. ... 

Development of lithium selective electrodes (LiSE) and their application in clinical chemistry have been amply reviewed Several models of lithium ion specific electrodes are commercially available. The central problems in developing such sensing devices are their dynamic range, the accuracy and precision by which the signals are correlated to the concentration of the analyte and the selectivity towards that species, especially in relation to other alkali metal cations. Additional problems of practical importance are the times of response and recovery and the durability of the electrode in the intended service. 

Impetus was given to work in the field of selective cation complex-ation by the observation of Moore and Pressman (5) in 1964 that the macrocyclic antibiotic valinomycin is capable of actively transporting K+ across mitochondrial membranes. This observation has been confirmed and extended to numerous macrocyclic compounds. There is now an extensive literature on the selective complexation and transport of alkali metal ions by various macrocyclic compounds (e.g., valinomycin, mo-nactin, etc.) (2). From solution spectral (6) and crystal X-ray (7) studies we know that in these complexes the alkali metal cation is situated in the center of the inwardly oriented oxygen donor atoms. Similar results are found from X-ray studies of cyclic polyether complexes of alkali metal ions (8) and barium ion (9). These metal macrocyclic compound systems are especially noteworthy since they involve some of the few cases where alkali metal ions participate in complex ion formation in aqueous solution. 

Figure 15. Selectivity of transport rate of alkali metal cations relative to Na by active transporters (C8TrgP)4mTet ( ), (C8TrgP)6Hex(A), (G82P)2Di (o), (A82P)4Tet ( ), (G8Trg)4Tet...

Pedersen used reactions of nucleophilic substitution to synthesize most of the crown ethers he has obtained. On the other hand, Lehn and his coworkers [17] (Fig. 7.1.4) carried out cyclization reactions involving amide formation under high dilution conditions in their quest for cryptands such as 54. Pedersen analysis of the selective inclusion of alkali metal cations into the crown ethers cavity... 

NaCl from water.27 Moore and Pressman s discovery that the antibiotic valinomydn exhibits alkali metal cation selectivity in rat liver mitochondria then provided a starting point for studies in the area of M"+ selectivity by biological and model systems.28... 

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