Dye-doped nanoparticles have been investigated as bright, luminescent labels for super-resolution microscopy via localization methods. One key factor in super-resolution is the size of the luminescent label, which in some cases results in a frame shift between the label target and the label itself. Ag@SiO 2 core–shell nanoparticles, doped with organic fluorophores, have shown promise as super-resolution labels. One key aspect of these nanoparticles is that they blink under certain conditions, allowing super-resolution localization with a single excitation source in aqueous solution. In this work, we investigated the effects of both the Ag core and the silica (SiO 2 ) shell on the self-blinking properties of these nanoparticles. Both core size and shell thickness were manipulated by altering the reaction time to determine core and shell effects on photoblinking. Size and shell thickness were investigated individually under both dry and hydrated conditions and were then doped with a 1 mM solution of Rhodamine 110 for analysis. We observed that the cores themselves are weakly luminescent and are responsible for the blinking observed in the fully-synthesized metal-enhanced fluorescence nanoparticles. There was no statistically significant difference in photoblinking behavior—both intensity and duty cycle—with decreasing core size. This observation was used to synthesize smaller nanoparticles ranging from approximately 93 nm to 110 nm as measured using dynamic light scattering. The blinking particles were localized via super-resolution microscopy and show single particle self-blinking behavior. As the core size did not impact blinking performance or intensity, the nanoparticles can instead be tuned for optimal size without sacrificing luminescence properties.
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Enhanced radioluminescence of yttrium pyrosilicate nanoparticles via rare earth multiplex doping
A series of multi-doped yttrium pyrosilicate (YPS) nanoparticles were synthesized using a high temperature multi-composite reactor, and used to explore the radioluminescent properties that have potential for biological applications. The luminescent activators explored in this work were cerium, terbium, and europium. A series of mono-doped YPS nanoparticles were synthesized that have optical and X-ray luminescent properties that span the entire visible spectrum. Energy transfer experiments were investiagted to increase the photo- and X-ray luminescence of terbium and europium. Cerium was used as a sensitizer for terbium where X-ray luminescence was enhanced. Similar results were also obtained using cerium as a sensitizer and terbium as an energy bridge for europium. By leveraging different energy transfer mechanisms X-ray luminescence can be enhanced for YPS nanoparticles.
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- Award ID(s):
- 1632881
- NSF-PAR ID:
- 10358688
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 14
- Issue:
- 33
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 12030 to 12037
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Protic ruthenium complexes using the dihydroxybipyridine (dhbp) ligand combined with a spectator ligand (N,N = bpy, phen, dop, Bphen) have been studied for their potential activity vs. cancer cells and their photophysical luminescent properties. These complexes vary in the extent of π expansion and the use of proximal (6,6′-dhbp) or distal (4,4′-dhbp) hydroxy groups. Eight complexes are studied herein as the acidic (OH bearing) form, [(N,N)2Ru(n,n′-dhbp)]Cl2, or as the doubly deprotonated (O− bearing) form. Thus, the presence of these two protonation states gives 16 complexes that have been isolated and studied. Complex 7A, [(dop)2Ru(4,4′-dhbp)]Cl2, has been recently synthesized and characterized spectroscopically and by X-ray crystallography. The deprotonated forms of three complexes are also reported herein for the first time. The other complexes studied have been synthesized previously. Three complexes are light-activated and exhibit photocytotoxicity. The log(Do/w) values of the complexes are used herein to correlate photocytotoxicity with improved cellular uptake. For Ru complexes 1–4 bearing the 6,6′-dhbp ligand, photoluminescence studies (all in deaerated acetonitrile) have revealed that steric strain leads to photodissociation which tends to reduce photoluminescent lifetimes and quantum yields in both protonation states. For Ru complexes 5–8 bearing the 4,4′-dhbp ligand, the deprotonated Ru complexes (5B–8B) have low photoluminescent lifetimes and quantum yields due to quenching that is proposed to involve the 3LLCT excited state and charge transfer from the [O2-bpy]2− ligand to the N,N spectator ligand. The protonated OH bearing 4,4′-dhbp Ru complexes (5A–8A) have long luminescence lifetimes which increase with increasing π expansion on the N,N spectator ligand. The Bphen complex, 8A, has the longest lifetime of the series at 3.45 μs and a photoluminescence quantum yield of 18.7%. This Ru complex also exhibits the best photocytotoxicity of the series. A long luminescence lifetime is correlated with greater singlet oxygen quantum yields because the triplet excited state is presumably long-lived enough to interact with 3O2 to yield 1O2.
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null (Ed.)Controlled energy transfer has been found to be one of the most effective ways of designing tunable and white photoluminescent phosphors. Utilizing host emission to achieve the same would lead to a new dimension in the design strategy for novel luminescent materials in solid state lighting and display devices. In this work, we have achieved controlled energy transfer by suppressing the host to dopant energy transfer in La 2 Hf 2 O 7 :Eu 3+ nanoparticles (NPs) by co-doping with uranium ions. Uranium acts as a barrier between the oxygen vacancies of the La 2 Hf 2 O 7 host and Eu 3+ doping ions to increase their separation and reduce the non-radiative energy transfer between them. Density functional theory (DFT) calculations of defect formation energy showed that the Eu 3+ dopant occupies the La 3+ site and the uranium ion occupies the Hf 4+ site. Co-doping the La 2 Hf 2 O 7 :Eu 3+ NPs with uranium ions creates negatively charged lanthanum and hafnium vacancies making the system highly electron rich. Formation of cation vacancies is expected to compensate the excess charge in the U and Eu co-doped La 2 Hf 2 O 7 NPs suppressing the formation of oxygen vacancies. This work shows how one can utilize the full color gamut in the La 2 Hf 2 O 7 :Eu 3+ ,U 6+ NPs with blue, green and red emissions from the host, uranium and europium, respectively, to produce near perfect white light emission.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2nr02417a
