Function‐Targeted Lanthanide‐Anchored Polyoxometalate–Cyclodextrin Assembly: Discriminative Sensing of Inorganic Phosphate and Organophosphate

Abstract

Polyoxometalate (POM) clusters containing lanthanide ion (LnPOM) possess excellent luminescence features, but the envisaged applications are hindered by the challenges in integration into functional architectures. Herein, a novel cross-linked cyclodextrin (CL-CD) and LnPOM composite is developed and applied for discriminative detection of inorganic and organic phosphate phases. For inorganic phosphates, a ratiometric fluorescence response is demonstrated with excellent selectivity, and anti-interference ability in complex analyte mixtures. The outstanding performance is attributed to the high affinity of POM and distinct interactions between La 3+ and Eu 3+ with the phosphate. For organophosphates, a "signal-off" fluorescence response for p-nitrophenyl-substituted organophosphates is discovered due to the encapsulation of nitrophenyl group into the hydrophobic cavity of CD that enhances the interactions between POM and p-nitrophenyl phosphate. The discriminative responses of CL-CD-LnPOM to inorganic phosphates and organophosphates bring new insights into POM-based fluorescence probes for the detection of inorganic and organic phases based on the intrinsic structural difference between the phosphate analogs.

Multicharged cyclodextrin supramolecular assemblies

“…Mao and co-workers reported a sensing platform consisting of crosslinked cyclodextrin (CL-CD) and lanthanide-ion-containing polyoxometalate clusters (LnPOM) for the selective detection of inorganic and organic phosphates. 406 In this system, b-CD was first partially oxidized to obtain the aldehyde-containing b-CD, which afforded improved water solubility and higher reactivity with crosslinkers. Then, the Mo 7 O 24 6À [Mo 7 ] anion was locked in the CD molecular torus with the molar ratio of 2 : 1 (Mo 7 @CD) owing to the size-fitness.…”

Photothermal-healing, and record thermal stability and fire safety black phosphorus–boron hybrid nanocomposites: mechanism of phosphorus fixation effects and charring inspired by cell walls

“…4,7 PFRs inhibit combustion by capturing active free radicals in the gas phase, 8 signicantly increasing smoke and toxic gases, which are the main causes of casualties. More importantly, some PFRs have potential health hazards and long-lasting ecological risks, [9][10][11] and re is the fastest path to release and complex the products. On the other hand, PFRs bond with the matrix via the high-valence PO x to promote the formation of char in the condensed phase.…”

Graphene Nanobeacons with High‐Affinity Pockets for Combined, Selective, and Effective Decontamination and Reagentless Detection of Heavy Metals

“…[23] Although extremely sensitive, the use of noble metals and required methodology suggest the use of the sensor in dedicated high-end applications, where detection far below the drinking water allowance limits is required. Other sensing schemes rely on specialized (bio)molecules (DNA/aptamers, [22,28,[35][36][37][38][39] proteins, [40] organic molecules, [41] metal ion-imprinted polymers [25] ) to achieve selectivity and high binding affinity. Carbon/graphene dots may offer low limits of detection (LoDs; Table S1, Supporting Information) via simple fluorometric or electrochemical sensing, owing to their particularly small size, high surface area, and chemically rich shell, allowing for coordination with metal ions or further derivatization.…”