Nanometer-Thick Ion-Selective Polyelectrolyte Multilayer Coatings to Inhibit the Disintegration of Inorganic Upconverting Nanoparticles

Protective and ion selective polyelectrolyte multilayer coatings from poly(sodium 4-styrenesulfonate) and poly(diallyldimethylammonium chloride) were manufactured on the NaYF4:Yb3+,Er-3+ upconverting nanoparticle surface. The ion selective coatings would be effective in hindering the disintegration of inorganic nanoparticle in an aqueous environment used in various applications such as in vitro assays and biomedical imaging. The disintegration is prominent especially in detrimental phosphate-based buffers. The effect of the used counteranion on the multilayer formation and the luminescent properties of the coated materials is discussed. The multilayer coating was confirmed with Fourier transform infrared spectroscopy, thermal analysis, and transmission electron microscopy. The behavior of the coated nanoparticles in aqueous environment was monitored by using fluoride ion selective electrode. We observed that the ion selective coatings prepared using fluoride or chloride as a counteranion were the most effective in slowing the disintegration of the nanoparticles. The deceleration in the disintegration process was observed also in phosphate-based buffer which emphasizes the ion selective properties of the multilayer coating. The upconversion luminescence measurements of the coated nanoparticles showed that coatings manufactured with bromide counteranion were most efficient in shielding the upconversion luminescence in solid state

Micro-luminescence measurement to evidence decomposition of persistent luminescent particles during the preparation of novel persistent luminescent tellurite glasses

The preparation of tellurite glasses with persistent luminescence by adding persistent luminescent particles in the glass melt is reported. Compared to phosphate glasses, the afterglow from the tellurite glasses is low, indicating that the tellurite melt is more corrosive on the particles than the phosphate melt. However, as opposed to phosphate glasses, no emission from Eu3+ was detected in the photoluminescence spectra of the glasses when crushed into powder. We show that a confocal Raman microscope can be used to evidence the presence of Eu3+ in the glass-particles interface confirming that some oxidation of Eu2+ actually takes place during the preparation of the tellurite glasses.</p

Effective Shielding of NaYF4:Yb3+,Er3+ Upconverting Nanoparticles in Aqueous Environments Using Layer-by-Layer Assembly

Aqueous solutions are the basis for most, biomedical assays, but they quench the upconversion luminescence significantly. Surface modifications of upconverting nanoparticles are vital for shielding the obtained luminescence. Modifications also provide new possibilities for further use by introducing attaching sites for biomolecule conjugation. We demonstrate the use of a layer-by-layer surface modification method combining varying lengths of negatively charged polyelectrolytes with positive neodymium ions in coating the upconverting NaYF4:Yb3+,Er3+ nanoparticles. We confirmed the formation of the bilayers and investigated the surface properties with Fourier transform infrared and reflectance spectroscopy, thermal analysis, and (zeta-potential measurements. The effect of the coating on the upconversion luminescence properties was characterized, and the bilayers with the highest improvement in emission intensity were identified. In addition, studies for the nanoparticle and surface stability were carried out in aqueous environments. It was observed that the bilayers were able to shield the materials' luminescence from quenching also in the presence of phosphate buffer that is currently considered the most disruptive environment for the nanoparticles

Single-Peptide TR-FRET Detection Platform for Cysteine-Specific Post-Translational Modifications

Post-translational modifications (PTMs) are one of the most important regulatory mechanisms in cells, and they play key roles in cell signaling both in health and disease. PTM catalyzing enzymes have become significant drug targets, and therefore, tremendous interest has been focused on the development of broad-scale assays to monitor several different PTMs with a single detection platform. Most of the current methodologies suffer from low throughput or rely on antibody recognition, increasing the assay costs, and decreasing the multifunctionality of the assay. Thus, we have developed a sensitive time-resolved Forster resonance energy transfer (TR-FRET) detection method for PTMs of cysteine residues using a single-peptide approach performed in a 384-well format. In the developed assay, the enzyme-specific biotinylated substrate peptide is post-translationally modified at the cysteine residue, preventing the subsequent thiol coupling with a reactive AlexaFluor 680 acceptor dye. In the absence of enzymatic activity, increase in the TR-FRET signal between the biotin-bound Eu(III)-labeled streptavidin donor and the cysteine-coupled AlexaFluor 680 acceptor dye is observed. We demonstrate the detection concept with cysteine modifying S-nitrosylation and ADP-ribosylation reactions using a chemical nitric oxide donor S-nitrosoglutathione and enzymatic ADP-ribosyltransferase PtxS1-subunit of pertussis toxin, respectively. As a proof of concept, three peptide substrates derived from the small GTPase K-Ras and the inhibitory alpha-subunit of the heterotrimeric G-protein G alpha i showed expected functionality in both chemical and enzymatic assays. Measurements yielded signal-to-background ratios of 28.7, 33.0, and 8.7 between the modified and the nonmodified substrates for the three peptides in the S-nitrosylation assay, 5.8 in the NAD(+) hydrolysis assay, and 6.8 in the enzymatic ADP-ribosyltransferase inhibitor dose-response assay. The developed antibody-free assay for cysteine-modifying enzymes provides a detection platform with low nanomolar peptide substrate consumption, and the assay is potentially applicable to investigate various cysteine-modifying enzymes in a high throughput compatible format

Near-infrared rechargeable glass-based composites for green persistent luminescence

The fabrication of Yb3+, Tm3+ co-doped oxyfluorophosphate glass-based composites, with green persistent luminescence after being charged with near-infrared light, is demonstrated. The mechanism responsible for the green afterglow after near-infrared illumination is unveiled. The composite is prepared using a modified melting process to limit the evaporation of fluorine during melting. Intense (blue and ultraviolet) up-conversion emission is obtained by optimizing the Yb2O3 and Tm2O3 concentrations. A heat treatment promotes volume precipitation of Yb3+, Tm3+ co-doped CaF2 crystals. Although the intensity of the blue up-conversion emission from the Tm3+ 1G4 level is lower in the highly Yb3+-concentrated glass-ceramic due to reverse energy transfer from Tm3+ to Yb3+, the heat treatment leads to an increase of the intensity of the emissions around 346 nm, 361 nm nm and 450 nm coming from the Tm3+ 1I6 and 1D2 levels. By combining the Yb3+ and Tm3+ ions with SrAl2O4:Eu2+,Dy3+crystals, green afterglow can be obtained after charging with near-infrared light.</p

Near-infrared rechargeable glass-based composites for green persistent luminescence

The fabrication of Yb3+, Tm3+ co-doped oxyfluorophosphate glass-based composites, with green persistent luminescence after being charged with near-infrared light, is demonstrated. The mechanism responsible for the green afterglow after near-infrared illumination is unveiled. The composite is prepared using a modified melting process to limit the evaporation of fluorine during melting. Intense (blue and ultraviolet) up-conversion emission is obtained by optimizing the Yb2O3 and Tm2O3 concentrations. A heat treatment promotes volume precipitation of Yb3+, Tm3+ co-doped CaF2 crystals. Although the intensity of the blue up-conversion emission from the Tm3+ 1G4 level is lower in the highly Yb3+-concentrated glass-ceramic due to reverse energy transfer from Tm3+ to Yb3+, the heat treatment leads to an increase of the intensity of the emissions around 346 nm, 361 nm nm and 450 nm coming from the Tm3+ 1I6 and 1D2 levels. By combining the Yb3+ and Tm3+ ions with SrAl2O4:Eu2+,Dy3+crystals, green afterglow can be obtained after charging with near-infrared light.publishedVersionPeer reviewe

Bioactive phosphate glass-based fiber with green persistent luminescence

The first biophotonic composite fiber with green persistent luminescence is reported. The composites were drawn from preforms prepared by remelting a bioactive glass with commercial persistent luminescent microparticles (SrAl2O4:Eu2+,Dy3+). The duration of the remelt step should be as short as possible to limit the decomposition of the micro-phosphors during glass preparation, as evidenced using electron microscopy coupled with elemental analysis. The presence of the phosphors in the glass inhibits the drawing of fibers with diameter below about 400 µm. Although the drawing process induces some changes in the Eu2+ ions’ local structure in the phosphors, the fibers still exhibit green afterglow. Despite the presence of the phosphors, the fiber still maintains its bioactive response, as characterized by the release of ions from the glass to the environment and the successive precipitation of a reactive layer within a dicalcium phosphate dehydrate composition.</p

Synthesis and Features of Luminescent Bromo- and Iodohectorite Nanoclay Materials

The smectites represent a versatile class of clay minerals with broad usage in industrial applications, e.g., cosmetics, drug delivery, bioimaging, etc. Synthetic hectorite Na-0.7(Mg5.5Li0.3)[Si8O20](OH)(4) is a distinct material from this class due to its low-cost production method that allows to design its structure to match better the applications. In the current work, we have synthesized for the first time ever nanoclay materials based on the hectorite structure but with the hydroxyl groups (OH-) replaced by Br- or I-, yielding bromohectorite (Br-Hec) and iodohectorite (I-Hec). It was aimed that these materials would be used as phosphors. Thus, OH- replacement was done to avoid luminescence quenching by multiphonon de-excitation. The crystal structure is similar to nanocrystalline fluorohectorite, having the d(001) spacing of 14.30 angstrom and 3 nm crystallite size along the 00l direction. The synthetic materials studied here show strong potential to act as host lattices for optically active species, possessing mesoporous structure with high specific surface area (385 and 363 m(2) g(-1) for Br-Hec and I-Hec, respectively) and good thermal stability up to 800 degrees C. Both materials also present strong blue-green emission under UV radiation and short persistent luminescence (ca. 5 s). The luminescence features are attributed to Ti3+/Ti-IV impurities acting as the emitting center in these materials