Photocaged zinc (II) cationophores for inter-vesicle signal transduction Shaun Gartland, Toby G. Johnson, Euan Walkley, Matthew J. Langton University of Oxford, UK Generating and maintaining an electrochemical gradient over cell membranes is vital for life. Nature controls membrane potentials with ion selective, membrane spanning protein channels which can facilitate the transport of hydrophilic charge carriers over the hydrophobic interior of a phospholipid bilayer, in some cases upon application of an external stimulus. If the ion transport process is mis-regulated, channelopathies occur which can lead to disease in the nervous, cardiovascular or immune systems. Synthetic species capable of transporting across the membrane have recently emerged as potential therapeutics for channelopathies. [1] Of the transporters demonstrated in the literature, those whose activity can be modulated by the application of external stimuli are particularly attractive. In this context, light shows immense promise as a non-invasive stimulus with high spaciotemporal control. Indeed, photo-switchable and photocaged transporters have been demonstrated in the literature. [2] Whilst there are many examples of anion transport across artificial lipid bilayers, there remain few examples of the transport of biologically relevant cations into artificial cells. In addition, the vast majority of transmembrane transport research carried out thus far has been conducted by considering only one family of vesicles. This is despite intercellular communication being vital in facilitating the survival of complex organisms. The few examples of inter-vesicular communication in the literature require biological components to achieve signal transduction. In this poster, I will present my recent work to develop the first artificial inter-vesicle communication network by anchoring a Zn(II) mobile ionophore to the membrane with a hydrophobic, photolabile group which inhibits the Lewis acidity of the chelating quinoline. [3]
Figure 1 (a) The light triggered intervesicle communication process demonstrated (b) The structure of clioquinol (1), photocaged clioquinol (2a) and magnesium green (MgG). References
1. Yang, G. Yu, J. L. Sessler, I. Shin, P. A. Gale and F. Huang, Chem , 2021, 7 , 3256-3291 2. Ahmad, S. A. Gartland, M. J. Langton, Angew. Chem. Int. Ed. , 22023, e202308842 3. A. Gartland, T. G. Johnson, E. Walkley, M. J. Langton, Angew. Chem. Int. Ed. , 2023, e20230980
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