Membrane transport ionophores

Hosts such as crown ethers and cryptands are useful as phase transfer agents and mimics of biological membrane transporting ionophores. 

Painter, G. R., Pressman, B. C. Dynamic Aspects of Ionophore Mediated Membrane Transport, ibid., p. 83M10... 

Dynamic aspects of ionophore mediated membrane transport. G. R. Painter and B. C. Pressman, Top. Curr. Chem., 1982,101, 83-110 (105). 

Lee, S. S. Yoon, I. Park, K.-M. Jung, J. H. Lindoy, L. F. Nezhadali, A. Rounaghi, G. Competitive bulk membrane transport and solvent extraction of transition and post transition metal ions using mixed-donor acyclic ligands as ionophores. J. Chem. Soc.-Dalton Trans. 2002, 2180-2184. 

There appear to be two major ways by which ionophores aid ions to cross membrane barriers. Ionophores such as valinomycin and nonactin enclose the cation such that the outside of the complex is quite hydro-phobic (and thus lipid-soluble). The transport behaviour thus involves binding of the cation at the membrane surface by the antibiotic, followed by diffusion of the complexed cation across the membrane to the opposite surface where it is released. Such carrier type ionophores can be very efficient, with one molecule facilitating the passage of thousands of ions per second. A prerequisite for efficient transport by this type of ionophore is that both the kinetics of complex formation and dissociation be fast. 

Mixed donor macrocycles have been employed in a number of applications involving the separation or analysis of manganesetll). These include examples of use of such a ligand as the extractant in solvent extraction processes " and as the ionophore in membrane transport studies. 

Polar Cell Systems for Membrane Transport Studies Direct current electrical measurement in epithelia steady-state and transient analysis, 171, 607 impedance analysis in tight epithelia, 171, 628 electrical impedance analysis of leaky epithelia theory, techniques, and leak artifact problems, 171, 642 patch-clamp experiments in epithelia activation by hormones or neurotransmitters, 171, 663 ionic permeation mechanisms in epithelia biionic potentials, dilution potentials, conductances, and streaming potentials, 171, 678 use of ionophores in epithelia characterizing membrane properties, 171, 715 cultures as epithelial models porous-bottom culture dishes for studying transport and differentiation, 171, 736 volume regulation in epithelia experimental approaches, 171, 744 scanning electrode localization of transport pathways in epithelial tissues, 171, 792. 

Casnati, A., Pochini, A., Ungaro, R. et al. 1995. Synthesis, complexation and membrane transport studies of 1,3-altemate calyx[4]arene crown-6 conformers A new class of cesium selective ionophores. J. Am. Chem. Soc. 117 2767-2777. 

Competitive (seven-metal) solvent extraction experiments (water/chloroform) and related bulk membrane transport (water/chloroform/water) experiments have been performed in which each of the four tri-branched ligands as well as their single ring analogues were employed as the extractant/ionophore in the respective chloroform phases [37], In both sets of experiments the aqueous source phases contained an equimolar mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Ag(I) and Pb(II) nitrates and were buffered at pH 4.9. For membrane transport the aqueous receiving phase was buffered at pH 3 under these conditions any transport will be driven by the back transfer of protons. Under the conditions employed, the results from the solvent extraction and the bulk membrane transport experiments clearly paralleled each other -for each ligand system high extraction/transport selectivity for Ag(I) was observed over the other six metal ions present in the respective source phases. 

The sapphyrin unit connected to natural ionophore lasalocid [78] has been used for the design of ligand 48. Membrane transport was measured for this ligand using a traditional U-tube arrangement. It was found that the ligand is able to transport amino acids in their zwitterionic form with a preference for the L-enantiomer of Phe. 

Ionophores are classified as either channel or carrier ionophores. Channel ionophores form channels across the membrane through which ions can diffuse down a concentration gradient. The nature of the channel depends on the ionophore, for example, gramicidin A channels are formed by two gramicidin molecules, N-terminus to N-terminus, each molecule forming a left-handed helix (Figure 7.1(a)). Carrier ionophores pick up an ion on one side of the membrane, transport it across, and release it into the fluid on the other side of the membrane. They usually transport specific ions. For example, valinomycin transports K+ but not Na+ Li+ ions (Figure 7.1(b)). 

Be familiar with the composition and structure of biologic membranes. Be able to place the various phospholipids in the membrane bilayer. Know the function and position of membrane proteins and their possible movements. Know how membrane fluidity is controlled. Know the nature of various mechanisms to transport substances across membranes, receptor-mediated endocytosis, active and facilitated transport, ionophores, and the various types of channels. Be able to solve simple mathematical problems by creating solute gradients across membranes. Know the names of substances that inhibit the various modes of transport across membranes. 

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