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Enhanced selectivity for Mg2+ with a phosphinate-based chelate : APDAP versus APTRA.

Walter, Edward R. H. and Fox, Mark A. and Parker, David and Williams, J. A. Gareth (2018) 'Enhanced selectivity for Mg2+ with a phosphinate-based chelate : APDAP versus APTRA.', Dalton transactions., 47 (6). pp. 1755-1763.


o-Aminophenol-N,N,O-triacetate, known as APTRA, is one of the most well-established ligands for targeting magnesium ions but, like other aminocarboxylate ligands, it binds Ca2+ much more strongly than Mg2+. The synthesis of an O-phosphinate analogue of APTRA is reported here, namely o-aminophenol-N,N-diacetate-O-methylene-methylphosphinate, referred to as APDAP. Metal binding studies monitored using UV-visible spectroscopy show that the affinity of APDAP for Ca2+ is reduced by over two orders of magnitude compared to APTRA, and for Zn2+ by over three orders of magnitude, whereas the affinity for Mg2+ is attenuated to a much lesser extent, by a factor of only about 7. The selectivity towards Mg2+ is thus substantially improved. DFT calculations support the notion that longer P–O and P–C bonds in APDAP (compared to corresponding C–O and C–C bonds in APTRA) favour a larger angle at the metal, an effect that is less unfavourable for smaller ions like Mg2+ than for larger ions such as Ca2+. Derivatives of APDAP can be anticipated that will offer improved sensing of Mg2+ in the presence of Ca2+, in the physiologically important millimolar concentration range.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Date accepted:05 January 2018
Date deposited:18 January 2018
Date of first online publication:16 January 2018
Date first made open access:05 January 2019

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