Achieving Selectivity for Phosphate over Pyrophosphate in Ethanol with Iron(III)-Based Fluorescent Probes.

Achieving Selectivity for Phosphate over Pyrophosphate in Ethanol with Iron(III)-Based Fluorescent Probes.
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DOI:
10.1021/jacsau.2c00200
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发表时间:
2022-07-25
期刊:
影响因子:
8
通讯作者:
Pierre, Valerie C
Pierre, Valerie C
中科院分区:
其他
文献类型:
--
作者:
Huang, Sheng-Yin;Pierre, Valerie C

文献摘要

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通过指示剂置换分析(IDA),合成了两种以1,2-羟基吡啶酮为配体的铁(III)分子受体,用于磷酸盐识别和荧光传感。四齿和五齿配体通过剩余的一个或两个开放配位中心使铁(III)中心能够识别阴离子。荧光素在这些部位的弱保护性配位阻止了曝气溶液中μ-oxo二聚体的形成。它被无机磷酸盐快速和选择性地置换,导致指示剂的荧光增加了20倍。这两种受体都表现出对无机磷的高亲和力和对常见竞争阴离子的高选择性,包括卤化物、醋酸盐、碳酸盐,以及值得注意的焦磷酸盐和砷酸盐。ATR-IR和31P核磁共振谱证实了磷酸盐与Fe(III)中心的配位。
Two iron(III)-based molecular receptors employing 1,2-hydroxypyridinone ligands were developed for phosphate recognition and fluorescence sensing via indicator displacement assay (IDA). The tetra- and pentadentate ligands enable anion recognition by the iron(III) center via its remaining one or two open coordination sites. Weak protective coordination of fluorescein at those sites prevents the formation of μ-oxo dimers in aerated solutions. Its rapid and selective displacement by inorganic phosphate results in a 20-fold increase in the fluorescence of the indicator. Both receptors exhibit high affinity for inorganic phosphate and high selectivity over common competing anions, including halides, acetate, carbonate, and, remarkably, pyrophosphate as well as arsenate. Coordination of phosphate to the iron(III) center was confirmed by ATR-IR and 31P NMR spectroscopy.