Functionalized lanthanide coordination polymer nanoparticles for selective sensing of hydrogen peroxide in biological fluids

Abstract

Lanthanide coordination polymers have recently emerged as very fascinating sensing materials due to their tunable structures and unique optical properties. However, a major problem concerning the applications of lanthanide coordination polymers for fluorescent sensing is their unselective recognition to analytes. In this work, a direct post-modification strategy was employed to prepare functionalized lanthanide coordination polymer nanoparticles (Phe/Tb-CPBA CPNPs) with specific response ability to hydrogen peroxide (H2O2) by using phenylalanine (Phe) as bridging ligands, terbium ions (Tb(3+)) as metal nodes and carboxyphenylboronic acids (CPBAs) as guest ligands. Phe/Tb-CPBA CPNPs emit a strong green fluorescence due to the removal of coordinated water molecules and the sensitization effect of CPBA. Upon the addition of H2O2, however, the quenched fluorescence of Phe/Tb-CPBA CPNPs can be observed owing to an intramolecular charge transfer effect. This finding led to a method for the quantitation of H2O2 in the 6 μM to 1 mM concentration range and with a detection limit at 2 μM. Because of the chemoselective H2O2-mediated oxidative deboronation, Phe/Tb-CPBA CPNPs as fluorescent sensors exhibit excellent selectivity to H2O2. Furthermore, Phe/Tb-CPBA CPNPs were successfully used to measure the level of H2O2 in urine samples and showed satisfactory results. We envision that the presented strategy could be extended to design other functionalized coordination polymers with desired functions for various biomedical applications.

Facile Synthesis of a Nickel Sulfide (NiS) Hierarchical Flower for the Electrochemical Oxidation of H2O2and the Methanol Oxidation Reaction (MOR)

“…24,25 Due to its key role, the determination of H 2 O 2 have arisen a great interest, hence many approaches have been developed, such as optical, titration-based, and electrochemical methods. [26][27][28] Among these methods, electrochemical analysis is particularly promising due to its many advantages such as low cost, easy to manipulate and fast analysis. 29 Although many nanostructures-based electrocatalysts such as prussianblue-grafted carbon nanotube/poly (4-vinylpyridine) 35 have been employed for this purpose, the preparation of the hierarchical nanostructure with high surface area is still a challenge for fabricating an efficient sensing platform for H 2 O 2 .…”

Surfactant-mediated morphology and fluorescent properties of amino acids-based lanthanide coordination polymers

“…3 To date, some biomolecule based-LnCPs have been synthesized and they showed great promise in chemical sensing 4,5 imaging 6 and drug delivery applications. Currently, amino acids, including aspartic acid, 9 cysteine, 10 phenylalanine, 11 and asparagines, 12 have been used as bridging ligands to prepare CPs. Amino acids are exible biomolecules and are attractive candidates as bridging ligands for the design and fabrication of CPs because of their low cost, diverse structures and functions.…”

New Nanomaterials and Luminescent Optical Sensors for Detection of Hydrogen Peroxide

“…A similar scheme could work for [14] and [22] where repetitive addition of TMB would be required for regeneration. For [21] a complete ligand exchange at the Tb 3+ -ions would be required to substitute the carboxyphenyl-4-oxo anions with carboxyphenyl-4-boronic acid groups. The introduction of reversibility is seen to be less easy for other probes [13,16,17] because it would be critical to achieve a reproducible regeneration step i.e., to restore the original particle size and regain the initial luminescence intensity.…”

“…After a further mixing loop, the resulting product stream would be measured via fluorescence spectroscopy. FIA-sensors could also be designed for the nanomaterials presented in [12,14,15,[20][21][22]24] if their synthesis can be easily performed and is not too expensive. The continuous feeding of the nanomaterial as required by a FIA instrument would rise the costs for continuous operation, otherwise.…”

“…In [21] functionalized lanthanide coordination polymer nanoparticles (CPNPs) were grown by a direct post-modification strategy to receive selectivity with respect to H2O2. The CPNPs contain terbium ions (Tb The use of upconversion photoluminescence (UCPL; an anti-Stokes emission) of nanoparticles avoids many disadvantages associated with fluorescence measurements in biological media like scattered light, autofluorescence and photobleaching.…”