pyrophosphate and dipicolinic-acid

We report a series of Cu(II) and Zn(II) complexes with different ligands containing a dipicolyl unit functionalized with urea groups that may contain or not a phenylboronic acid function. These complexes were designed for the recognition of phosphorylated anions through coordination to the metal ion reinforced by hydrogen bonds involving the anion and NH groups of urea. The complexes were isolated and several adducts with pyrophosphate were characterized using Xray diffraction measurements. Coordination of one of the urea nitrogen atoms to the metal ion promoted the hydrolysis of the ligands containing 1,3-diphenylurea units, while ligands bearing 1-ethyl-3-phenylurea groups did not hydrolyze significantly at room temperature. Spectrophotometric titrations, combined with ¹H and

Topics: Adenosine Diphosphate; Adenosine Monophosphate; Adenosine Triphosphate; Anions; Boronic Acids; Coordination Complexes; Copper; Diphosphates; Ligands; Magnetic Resonance Spectroscopy; Molecular Structure; Phosphates; Picolinic Acids; Urea; Water; Zinc

As a ubiquitous hydrolysis enzyme in phosphate metabolism, alkaline phosphatase (ALP) is a significant biomarker in laboratory research and clinic diagnosis. Herein, we report a highly water-soluble Eu(DPA)3@Lap nanohybrid material for the rapid and selective assay of PPi and ALP through a luminescence off-on recognition process. Eu(DPA)3@Lap was successfully prepared in an aqueous solution, and it exhibited strong luminescence emission, high photostability, and long lifetime. More interestingly, the strong luminescence of Eu(DPA)3@Lap can be remarkably quenched by Cu2+ due to the high impetus of coordination between the DPA ligand and Cu2+ ion. Using Cu2+ as a signal transducer, the luminescence could be recovered upon the addition of PPi ion owing to the formation of a Cu2+-PPi complex; thus, a luminescence turn-on assay for PPi ions was realized. Utilizing the ability of Cu2+ to differentiate between PPi and Pi, a convenient and straightforward luminescence assay for ALP activity was accomplished based on the specific dephosphorylation of PPi to Pi. To the best of our knowledge, this elaborate luminescence sensing system constitutes the first luminescent nanohybrid material based on a europium organic complex for ALP activity assay. Furthermore, the recognition process of PPi and ALP was completed in a convenient and facile mix-and-readout manner, and it revealed significant potential in point of care testing.

Topics: Alkaline Phosphatase; Diphosphates; Europium; Luminescence; Nanostructures; Picolinic Acids

A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III)-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III)-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP) and pyrophosphate, as well as dipicolinic acid (DPA) which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with μM and nM detection sensitivity for ATP and DPA, respectively.

Topics: Adenosine Triphosphate; Anions; Bacillus anthracis; beta-Cyclodextrins; Biomarkers; Diphosphates; Luminescence; Microchip Analytical Procedures; Microfluidic Analytical Techniques; Phosphates; Picolinic Acids