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Organoplatinum Compounds as Anion‐Tuneable Uphill Hydroxide Transporters

Active transport of ions uphill, creating a concentration gradient across a cell membrane, is essential for life. It remains a significant challenge to develop synthetic systems that allow active uphill transport. Here, a transport process fuelled by organometallic compounds is reported that creates...

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Detalles Bibliográficos
Autores principales: Chen, Li‐Jun, Wu, Xin, Gilchrist, Alexander M., Gale, Philip A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9310596/
https://www.ncbi.nlm.nih.gov/pubmed/35192743
http://dx.doi.org/10.1002/anie.202116355
Descripción
Sumario:Active transport of ions uphill, creating a concentration gradient across a cell membrane, is essential for life. It remains a significant challenge to develop synthetic systems that allow active uphill transport. Here, a transport process fuelled by organometallic compounds is reported that creates a pH gradient. The hydrolysis reaction of Pt(II) complexes results in the formation of aqua complexes that established rapid transmembrane movement (“flip‐flop”) of neutral Pt−OH species, leading to protonation of the OH group in the inner leaflet, generating OH(−) ions, and so increasing the pH in the intravesicular solution. The organoplatinum complex effectively transports bound hydroxide ions across the membrane in a neutral complex. The initial net flow of the Pt(II) complex into the vesicles generates a positive electric potential that can further drive uphill transport because the electric potential is opposed to the chemical potential of OH(−). The OH(−) ions equilibrate with this transmembrane electric potential but cannot remove it due to the relatively low permeability of the charged species. As a result, effective hydroxide transport against its concentration gradient can be achieved, and multiple additions can continuously drive the generation of OH(−) against its concentration gradient up to ΔpH>2. Moreover, the external addition of different anions can control the generation of OH(−) depending on their anion binding affinity. When anions displayed very high binding affinities towards Pt(II) compounds, such as halides, the external anions could dissipate the pH gradient. In contrast, a further pH increase was observed for weak binding anions, such as sulfate, due to the increase of positive electric potential.