4.8 Article

Organoplatinum Compounds as Anion-Tuneable Uphill Hydroxide Transporters

期刊

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202116355

关键词

Anions; Ion Transport; Organoplatinum Compounds; Uphill Transport

资金

  1. University of Sydney
  2. Australian Research Council [DP180100612, DP200100453]
  3. Australian Government

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This article reports a transport process driven by organometallic compounds that creates a pH gradient and enables the uphill transport of hydroxide ions. The study shows that the addition of different anions can control the generation of OH- ions, which is important for regulating the transport process.
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 Delta pH>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.

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