Lanthanide Coordination Polymer Nanoparticles as an Excellent Artificial Peroxidase for Hydrogen Peroxide Detection.

Lanthanide coordination polymer nanoparticles (Ln-CPNs) have been recently demonstrated as excellent platforms for biomolecule detection. In this work, we synthesized novel cerium coordination polymer nanoparticles ATP-Ce-Tris CPNs in a simple and quick way using ATP molecules as the biocompatible ligands to Ce(3+) ions in tris(hydroxymethyl)aminomethane hydrochloric (Tris-HCl) solution. In view of the excellent free radical scavenging property of cerium compounds, which is ascribed to the mixed valence state (Ce(3+), Ce(4+)) and the reversible switch from Ce(3+) to Ce(4+), the synthesized ATP-Ce-Tris CPNs was used as artificial peroxidase to selectively and sensitively detect H2O2. The sensing mechanism depends on the oxidation of the fluorescent ATP-Ce(III)-Tris CPNs to nonfluorescent ATP-Ce(IV)-Tris CPNs by H2O2. Compared with those inorganic cerium oxide sensors, this kind of fluoresence ATP-Ce-Tris CPNs sensor needs no additional organic redox dye, such as ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), TMB (3,3,5,5-tetramethylbenzidine), or fluorescein as signal molecules. Moreover, such ATP-Ce-Tris CPNs sensor exhibited a more sensitive response to H2O2 with a detection limit down to 0.6 nM, which is 2 orders of magnitude lower than those of cerium oxide sensors. This sensing platform was further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) for the oxidation of glucose and formation of H2O2.

Ratiometric fluorescence detection of sulfide ions based on lanthanide coordination polymer using guanosine diphosphate as ligand.

The efficiency of energy transfer from guanine nucleotide to terbium ion (Tb3+) is affected by the phosphate group significantly. Compared with the biomolecules 5'-GMP (guanosine monophosphate), guanosine diphosphate (GDP) exhibits better sensitize ability to Tb3+ ions luminescence. Assisted with the carboxycoumarin ligand, we synthesized a more stable optical Coumarin@GDP-Tb polymer with the characteristic emission peaks located on 440 nm and 545 nm in this work. The Coumarin@GDP-Tb polymer is not only rich in metal binding sites, but also maintains a moderate ionic binding force, which helps metal ions to bind or leave it easily. Experiment result shows that Coumarin@GDP-Tb polymer has the appropriate binding force for Fe2+ ions, which can be destroyed by sulfur ions (S2-) as the formation of FeS precipitation. Based on this, Coumarin@GDP-Tb was designed as the ratio fluorescence probe for sulfur ions detection, where the fluorescence at 545 nm can be selectively quenched by Fe2+ ions, while that at 440 nm was unaffected, in the presence of S2- ions, the quenched fluorescence can be recovered remarkably. With the increasing S2- ions from 0.1-45 µM, the ratio of fluorescence intensity at 545 nm to 440 nm (F545/F440) is linear to S2- concentration, and the detection limit of S2- was calculated to be 0.073 µM. Contrast to those fluorescence probes with single wavelength emission, Coumarin@GDP-Tb displays a comparable sensitivity, the introduced self-adjust wavelength improved the detection accuracy efficiently. The above 98.1 % recovery rates of S2- ions in the actual water sample demonstrated the practicability of Coumarin@GDP-Tb fluorescence probe.

Imaging hydroxyapatite in sub-retinal pigment epithelial deposits by fluorescence lifetime imaging microscopy with tetracycline staining.

SIGNIFICANCE: Recent evidence suggests that hydroxyapatite (HAP) in sub-retinal pigment epithelial (sub-RPE) deposits in aged human eyes may act to nucleate and contribute to their growth to clinically detectable size. Sub-RPE deposits such as drusen are clinical hallmarks of age-related macular degeneration (AMD), therefore enhanced and earlier detection is a clinical need. We found that tetracycline-family antibiotics, long known to stain HAP in teeth and bones, can also label the HAP in sub-RPE deposits. However, HAP-bound tetracycline fluorescence excitation and emission spectra overlap with the well-known autofluorescence of outer retinal tissues, making them difficult to resolve. AIM: In this initial study, we sought to determine if the HAP-bound tetracyclines also exhibit enhanced fluorescence lifetimes, providing a useful difference in lifetime compared with the short lifetimes observed in vivo in the human retina by the pioneering work of Schweitzer, Zinkernagel, Hammer, and their colleagues, and thus a large enough effect size to resolve the HAP from background by fluorescence lifetime imaging. APPROACH: We stained authentic HAP with tetracyclines and measured the lifetime(s) by phase fluorometry, and stained aged, fixed human cadaver retinas with drusen with selected tetracyclines and imaged them by fluorescence lifetime imaging microscopy (FLIM). RESULTS: We found that chlortetracycline and doxycycline exhibited substantial increase in fluorescence lifetime compared to the free antibiotics and the retinal background, and the drusen were easily resolvable from the retinal background in these specimens by FLIM. CONCLUSIONS: These findings suggest that FLIM imaging of tetracycline (and potentially other molecules) binding to HAP could become a diagnostic tool for the development and progression of AMD.

Fluorescence Turn-On Detection of Ascorbic Acid Using a Self-Assembled Lanthanide Polymer Nanoparticle.

Ascorbic acid (AA), or vitamin C, is an important reactive biological molecule in vivo, and an abnormal level of AA is associated with many diseases. Therefore, the rapid, sensitive, and selective detection of AA levels is of significance in cases of medical assay and diagnosis. Compared with other nanoparticles, lanthanide coordination polymer nanoparticles (Ln-CPs) have been demonstrated as the excellent biomolecule sensing platforms due to their unique optical properties and intrinsic porosities. In this work, the cerium coordination polymer nanoparticles ATP-Ce-Tris were synthesized in a simple and quick way. The synthesized ATP-Ce-Tris nanoparticle shows the characteristic peak of Ce3+ located at 365 nm, which is corresponding to the 4f→5d transition of Ce3+. In the presence of Fe3+, the fluorescence of ATP-Ce-Tris quenched, and the following added ascorbic acid (AA) makes it restoring effectively. Based on this, we constructed a fluorescence probe with excellent sensitivity for AA sensing in a wide linear relationship from 0.05 to 500 µM. The detection limit was as low as 18 nM (signal-to-noise ratio of three), which is one or two orders of magnitude lower than those of reported sensors. The proposed sensing systems also exhibits excellent sensitivity for AA detection in human serum sample, exploiting a valuable platform for AA analysis in clinic diagnostic and drug screening.

A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection.

A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce3+ matching to the adsorption energy of Tb3+(4fn) results in the efficient energy transfer from Ce3+ to Tb3+, thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb3+. Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce3+ in ATP-Ce/Tb-Tris CNPs to Ce4+ would interrupt the energy transfer from Ce3+ to Tb3+, leading to fluorescence quenching of Tb3+. On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H2O2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor.