Transmembrane Transport by Artificial Systems

Ions and small molecules may be transported across cell membranes or lipid bilayers by artificial methods that employ either a carrier or channel mechanism. The former mechanism is worthy of brief investigation as it has several ramifications in the design of selectivity filters in artificial transmembrane channels. To date there are few examples where transmembrane studies have been carried out on artificial transporters. The channel mechanism is much more amenable to analysis by traditional biological techniques, such as planar bilayer and patch clamp methods, so perhaps it is not surprising that more work has been done to model transmembrane channels. 

Aside from opening a pore, the easiest method to transport material from one side of a phospholipid bilayer to the other is to design small molecules that mimic naturally occurring siderophores or ionophores. 

Many artificial complexants, in particular the crown ethers, are proposed to work by ionophore-facilitated ion transport. Crown ethers, such as those in Fig. 5.12, have 

Artificial analogues of the chloride transporter prodigiosin are effective symport HC1 carriers as exemplified in the model systems developed by the groups of Gale [39] and Davis [40], Biological inspiration is also behind another Cl- carrier. Cholic acid is a naturally occurring bile acid that functions as a surfactant in the intestine. Derivatives with three binding sites known as cholapods are able to transport isolated anions across lipid bilayers [41], 

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In the photosynthetic and mitochondrial membranes the components of the transmembrane electron transport chain are not linked with covalent bonds, but fixed in a protein matrix. An example of such an arrangement of the electron transport chain in an artificial system can be found in papers by Tabushi et al. [244, 245], which deal with the dark electron transfer across the lipid membranes containing the dimers of cytochrome c3 from Desulfovibrio vulgaris. The dimer size is about 60 A, i.e. it somewhat exceeds the membrane thickness. This enables electron to move across the membrane via the cytochrome along the chain of hem fragments embedded in the protein. However, the characteristic time of the transmembrane electron transfer by this method is rather long (about 10 s). 

Functional artificial ion channels have been reported which illustrate the general criteria. The most obvious course is to prepare oligopeptides with hi helical content (S). Other reported systems are bas on cyclo xtrin (6), polymeric crown ethers (7), and "bouquet" shaped crown ether and cyclodextrin motifs (8). One of the most active systems is a simple tris-crown ether derivative repented by Gokel for the transport of sodium ions(9). All of these systems envisage a uni- or bi-molecular transmembrane structure, similar to the gramicidin structurd paradigm. 

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