Transport of alkali cations through thin lipid membranes by (222)C10-Cryptand, an ionizable mobile carrier

Abstract

The kinetics of K+ and Na+ transport across the membrane of large unilamellar vesicles (L.U.V.) were compared at two pH's, with two carriers: (222)C10-cryptand (diaza-1,10-decyl-5-hexaoxa-4,7,13,16,21,24-bicyclo[8.8.8.]+ ++hexacosane) and valinomcyin, i.e. an ionizable macrobicyclic amino polyether and a neutral macrocyclic antibiotic. The rate of cation transport by (222)C10 saturated as cation and carrier concentrations rose. The apparent affinity of (222)C10 for K+ was higher and less pH dependent than that for Na+ but resembled the affinity of valinomycin for K+. The efficiency of (222)C10 transport of K+ decreased as the pH fell and the carrier concentration rose, and was about ten times lower than that of valinomycin. Noncompetitive K+/Na+ transport selectivity of (222)C10 decreased as pH, and cation and carrier concentrations rose, and was lower than that of valinomycin. Transport of alkali cations by (222)C10 and valinomycin was noncooperative. Reaction orders in cation n(S) and carrier m(M) varied with the type of cation and carrier and were almost independent of pH; n(S) and m(M) were not respectively dependent on carrier or cation concentrations. The apparent estimated constants for cation translocation by (222)C10 were higher in the presence of Na+ than of K+ due to higher carrier saturation by K+, and decreased as pH and carrier concentration increased. Equilibrium potential was independent of the nature of carrier and transported cation. Results are discussed in terms of the structural, physiocochemical and electrical characteristics of carriers and complexes.

Efficiency, Na+/K+ selectivity and temperature dependence of ion transport through lipid membranes by (221)C10-Cryptand, an ionizable mobile carrier

“…]tricosane (Clement et al, 1976), is an amphiphilic molecule composed of a hydrophilic intramolecular binding cavity and a ten-carbon aliphatic side chain allow- . This c o m p o u n d is similar in size and shape to (222)C10-cryptand, w h i c h was r e c e n t l y s h o w n to b e h a v e like a m o b i l e c a r r i e r (Castaing et al, 1986). In (221)C~0-cryptand, one o f the chains of the mac r o b i c y c l i c m o l e c u l e is s h o r t e n e d by a -CHz-CH2-Ounit.…”

“…T h e p r e s e n t s t u d y quantifies the kinetic p a r a meters of N a + and K + t r a n s p o r t by (221)C10-cryptand at two p H ' s , as was p r e v i o u s l y d o n e at 25~ in the c a s e o f (222)Cj0-cryptand (Castaing et al, 1986), and f o c u s s e s on their t e m p e r a t u r e -i n d u c e d variations. The i o n o p h o r i c p r o p e r t i e s o f the m a c r o c y c l i c antibiotic n o n a c t i n w e r e also investigated, as u n d e r the p r e s e n t e x p e r i m e n t a l c o n d i t i o n s , this neutral m o b i l e c a r r i e r ( H l a d k y , 1975a,b) was e x p e c t e d to t r a n s p o r t b o t h K + and N a + ions (Zt~st et al, 1973).…”

“…Nonactin was dissolved in absolute ethanol, and (221)Ct0 in benzene. The other solutions were identical to those used previously (Castaing et al, 1986).…”

“…Proton outfluxes measurements were performed according to Castaing et al (1986) except that, in the present work, the pH variations were recorded continuously as a function of time. At steady-state transport, the buffering power of the sample was measured by adding 5 x 10 .4 M H2804 which allowed the magnitude of the proton efflux to be determined at any time during transport.…”

“…Large unilamellar vesicles (LUV) were prepared according to Szoka and Papahadjopoulos (1978) as previously reported (Castaing et al, 1986).…”