Light-triggered modulation of cellular electrical activity by ruthenium diimine nanoswitches.

作者: Joyce G. Rohan , Y. Rose Citron , Alec C. Durrell , Lionel E. Cheruzel , Harry B. Gray

DOI: 10.1021/CN300213F

关键词:

摘要: Ruthenium diimine complexes have previously been used to facilitate light-activated electron transfer in the study of redox metalloproteins. Excitation at 488 nm leads a photoexcited state, which complex can either accept or donate an electron, respectively, presence soluble sacrificial reductant oxidant. Here, we describe novel application these mediating light-induced changes cellular electrical activity. We demonstrate that RubpyC17 ([Ru(bpy)_(2)(bpy-C17)]^(2+), where bpy is 2,2′-bipyridine and bpy-C17 2,2′-4-heptadecyl-4′-methyl-bipyridine), readily incorporates into plasma membrane cells, as evidenced by membrane-confined luminescence. Excitable cells incubated then illuminated ascorbate undergo depolarization leading firing action potentials. In contrast, same experiment performed with oxidant ferricyanide, instead ascorbate, hyperpolarization. These experiments suggest illumination membrane-associated alters cell potential increasing negative charge on outer face capacitor, effectively depolarizing membrane. rule out two alternative explanations for changes, using patch clamp experiments: (1) direct interaction ion channels (2) perforation. show incorporation neuroendocrine enables secretion monitored amperometry. While present work focused ruthenium complexes, findings point more generally broader other transition metal mediate biological changes.

参考文章(39)
Karl Kandler, Lawrence C. Katz, Julie A. Kauer, Focal photolysis of caged glutamate produces long-term depression of hippocampal glutamate receptors Nature Neuroscience. ,vol. 1, pp. 119- 123 ,(1998) , 10.1038/368
Harry B. Gray, Jay R. Winkler, Daniel G. Nocera, Kathryn M. Yocom, Emilio Bordignon, Electron-transfer kinetics of pentaammineruthenium(III)(histidine-33)-ferricytochrome c. Measurement of the rate of intramolecular electron transfer between redox centers separated by 15.ANG. in a protein Journal of the American Chemical Society. ,vol. 104, pp. 5798- 5800 ,(1982) , 10.1021/JA00385A047
Jonathan J. Wilker, Ivan J. Dmochowski, John H. Dawson, Jay R. Winkler, Harry B. Gray, Substrates for Rapid Delivery of Electrons and Holes to Buried Active Sites in Proteins Angewandte Chemie International Edition. ,vol. 38, pp. 89- 92 ,(1999) , 10.1002/(SICI)1521-3773(19990115)38:1/2<89::AID-ANIE89>3.0.CO;2-R
Horst. Elias, Mei H. Chou, Jay R. Winkler, Electron-transfer kinetics of zinc-substituted cytochrome c and its Ru(NH3)5(histidine-33) derivative Journal of the American Chemical Society. ,vol. 110, pp. 429- 434 ,(1988) , 10.1021/JA00210A019
Edward M Callaway, Rafael Yuste, Stimulating neurons with light Current Opinion in Neurobiology. ,vol. 12, pp. 587- 592 ,(2002) , 10.1016/S0959-4388(02)00364-1
I Jy Chang, Harry B. Gray, Jay R. Winkler, High-driving-force electron transfer in metalloproteins : intramolecular oxidation of ferrocytochrome c by Ru(2,2'-bpy)2(im)(His-33)3+ Journal of the American Chemical Society. ,vol. 113, pp. 7056- 7057 ,(1991) , 10.1021/JA00018A064
Anding Bi, Jinjuan Cui, Yu-Ping Ma, Elena Olshevskaya, Mingliang Pu, Alexander M. Dizhoor, Zhuo-Hua Pan, Ectopic Expression of a Microbial-Type Rhodopsin Restores Visual Responses in Mice with Photoreceptor Degeneration Neuron. ,vol. 50, pp. 23- 33 ,(2006) , 10.1016/J.NEURON.2006.02.026
Tomohiro Numata, Tatsuya Murakami, Fumiaki Kawashima, Nobuhiro Morone, John E. Heuser, Yuta Takano, Kei Ohkubo, Shunichi Fukuzumi, Yasuo Mori, Hiroshi Imahori, Utilization of Photoinduced Charge-Separated State of Donor–Acceptor-Linked Molecules for Regulation of Cell Membrane Potential and Ion Transport Journal of the American Chemical Society. ,vol. 134, pp. 6092- 6095 ,(2012) , 10.1021/JA3007275