Cellular Phosphate Sensing and Anion Binding by an Azacrown-Calixpyrrole Hybrid.

Autor: Ray D; Chemical Separations Group, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA., Sartori AR; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA., Radujević A; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA., George SM; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA., Postema R; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA., Tan X; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA., Bryantsev VS; Chemical Separations Group, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA., Anzenbacher P Jr; Chemistry Department, Bowling Green State University, Bowling Green, Ohio, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Nov 04; Vol. 30 (61), pp. e202401872. Date of Electronic Publication: 2024 Oct 16.
DOI: 10.1002/chem.202401872
Abstrakt: A hybrid receptor-sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor-sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (K assoc H 2 PO 4 - >H 2 P 2 O 7 2- >AMP - ≫ADP 2- or ATP 3- over halides, nitrate, or hydrogen sulfate; all Na + salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real-time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence-based microscale method compares favorably with the state-of-the-art techniques but can easily be practiced in a high-throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation.
(© 2024 Oak Ridge National Laboratory and The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH on behalf of Chemistry Europe.)
Databáze: MEDLINE
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