Inert Shell Research Articles

Energy Transfer between Tm-Doped Upconverting Nanoparticles and a Small Organic Dye with Large Stokes Shift.

Lanthanide-doped upconverting nanoparticles (UCNP) are being extensively studied for bioapplications due to their unique photoluminescence properties and low toxicity. Interest in RET applications involving UCNP is also increasing, but due to factors such as large sizes, ion emission distributions within the particles, and complicated energy transfer processes within the UCNP, there are still many questions to be answered. In this study, four types of core and core-shell NaYF4-based UCNP co-doped with Yb3+ and Tm3+ as sensitizer and activator, respectively, were investigated as donors for the Methyl 5-(8-decanoylbenzo[1,2-d:4,5-d′]bis([1,3]dioxole)-4-yl)-5-oxopentanoate (DBD-6) dye. The possibility of resonance energy transfer (RET) between UCNP and the DBD-6 attached to their surface was demonstrated based on the comparison of luminescence intensities, band ratios, and decay kinetics. The architecture of UCNP influenced both the luminescence properties and the energy transfer to the dye: UCNP with an inert shell were the brightest, but their RET efficiency was the lowest (17%). Nanoparticles with Tm3+ only in the shell have revealed the highest RET efficiencies (up to 51%) despite the compromised luminescence due to surface quenching.

The role of an inert shell in improving energy utilization in lanthanide-doped upconversion nanoparticles.

Coating with an inert shell is considered an efficient approach for enhancing the emission and improving the luminescence quantum yield of lanthanide-doped upconversion nanoparticles. In this work, the role of an inert shell in the photon energy collection and energy transfer behavior is carefully studied. Our experimental results indicate that, owing to the valid energy trapping by the shell, an energy clustering effect is formed among the Yb3+ ions in the core. Such an effect reduces the total absorption and enhances the upconversion emission, especially the emission from the higher lying level of lanthanide emitters. Moreover, the morphology of the inert shell, which could be controlled during our synthesis, is deemed to be critical to the formation of energy clustering.

Resonant Plasmon-Enhanced Upconversion in Monolayers of Core-Shell Nanocrystals: Role of Shell Thickness.

The upconversion luminescence (UCL) of colloidal lanthanide-doped upconversion nanocrystals (UCNCs) can be improved either by precise encapsulation of the surface by optically inert shells around the core, by an alteration of the nearby environment via metal nanoparticles, or by a combination of both. Considering their potential importance in crystalline silicon photovoltaics, the present study investigates both effects for two-dimensional arrangements of UCNCs. Using excitation light of 1500 nm wavelength, we study the variation in the upconversion luminescence from an Er3+-doped NaYF4 core as a function of the thickness of a NaLuF4 shell in colloidal solutions as well as in spin-cast-assisted self-assembled monolayers of UCNCs. The observed UCL yields and decay times of Er3+ ions of the UCNCs increase with increasing shell thickness in both cases, and nearly no variation in decay times is observed in the transition of the UCNCs from solution to film configurations. The luminescence efficiency of the UCNC monolayers is further enhanced by electron-beam-lithographic-designed Au nanodiscs deposited either on top of or buried within the monolayer. It is observed that the improvement by the nanocrystal shells is greater than that of the Au nanodiscs.

ZrO2 nanoparticle encapsulation of graphene microsheets for enhancing anticorrosion performance of epoxy coatings

Graphene (rGO) is expected to enable an effective anti-corrosion barrier for metals owing to its chemical inertness and impermeability to gases and water. However, previous studies demonstrate limited anti-corrosion property and even corrosion enhancement of rGO on metal surfaces via micro-galvanic corrosion at the coating defects. To address the issue, in this work, sandwich-structured GZ microsheets is prepared by fully-covering the inert nanosized ZrO2 on the double-side of 2D rGO, and then incorporated into epoxy coating as filler for protecting metallic substrate against corrosion. By virtue of structural, morphological and electrochemical characterizations and analysis, we find that 0.5 wt% GZ into epoxy coating enables to form uniform and defect-free anticorrosive coating, and hence improve corrosion-protective properties in 3.5 wt% NaCl solution. The resistance of 0.5 wt% GZ in the first day immersion is 81.8 GΩ·cm2, and the metal substrate is not corroded during immersion. The attached inert ZrO2 shell on rGO effectively eliminates the rGO-metal/rGO connections, and hence prevents the local micro-galvanic corrosion.

Multicolor Tunable Upconversion Luminescence from Sensitized Seed-Mediated Grown LiGdF4:Yb,Tm-Based Core/Triple-Shell Nanophosphors for Transparent Displays

Red, green, blue, and natural white upconversion (UC) luminescence colors are realized from the tetragonal-structured LiGdF4-based core/triple-shell (C/T-S) upconversion nanophosphors (UCNPs) and the C/T-S UCNP-incorporated polymer composites. The LiYF4:Yb cores are used as sensitized seeds for the formation of LiGdF4:Yb,Tm UC shell followed by the growth of LiGdF4:Tb,Eu color tuning shell. Finally, LiYF4 inert shell is grown on the core/shell/shell UCNPs, and LiYF4:Yb/LiGdF4:Yb,Tm/LiGdF4:Tb,Eu/LiYF4 C/T-S UCNPs exhibit enhanced UC luminescence. The single tetragonal-phased C/T-S UCNPs exhibit blue, green, and red UC luminescence, which is attributed to the electronic transitions in Tm3+ via energy transfer UC process and Tb3+ and Eu3+ via energy migration UC process, respectively. The multicolor UC emissions, including natural white, medium aquamarine, purple, and thistle color, are created by fine-tuning of the ratio of Tb3+ and Eu3+ in the color tuning shell. The transparent polymer composites are prep...

Upconversion Nanoprobes: Recent Advances in Sensing Applications.

Rare earth ions doped upconversion nanoparticles (UCNPs) are capable of stepwisely converting two or more lower energy near-infrared (NIR) excitation photons into a higher energy visible and ultraviolet emission photon, resulting in a large anti-Stokes shift of several hundred nanometers. Because the f-electron configurations of lanthanide ions have abundant energy levels, and many of them possess long lifetimes, UCNPs exhibit unique optical properties including optical tunability over emission wavelengths and lifetimes, better photo-stability and improved monochromatic color-purity and spatial resolution. However, the low luminescent efficiency, largely owing to their substantially weak and narrow band absorptions, has greatly hampered the translation of UCNPs-based technologies from the academic stage to real world products. Recently, increasing efforts have been paid on boosting the upconversion luminescence brightness and efficiency, including inert shells coating, high concentration of activators dop...

Thinning shell thickness of CuInS2@ZnS quantum dots to boost detection sensitivity

Quantum dots (QDs), drawing large attention during the past three decades, have been extensively applied in lighting, display, and biodetection. However, the mechanism for their ability in biodetection, especially in recognizing toxic metal ions, has scarcely been explored. In this work, three sets of CuInS2@ZnS QDs systems with inert shell thickness varying from 1.1 to 4.1 nm have been performed. As the shrinkage of inert shell, QDs not only show red-shift emission but also demonstrate more sensitive and higher response to the added Cd2+. The thin-shell CuInS2@ZnS QDs could detect 0.91 nM Cd2+, and could further detect 4.36 nM Cd2+ when integrated with paper-based platform. Importantly, thin-shell CuInS2@ZnS QDs combined with paper-based platform can detect 105.86 nM Cd2+ even just applying mobile phone as detector and hand-held UV lamp as excitation resource. The mechanism is further proposed based on the energy transfer routes. The thin inert shell can not completely protect the emissive core away from the surface defects, but it can neither exclude the energy transfer from the surface to the emissive core. The added Cd2+ would facilitate the formation of CdS on the surface of QDs, which not only can alleviate the surface defects but also can transfer energy to emissive CuInS2, thus thinning the thickness of inert shell greatly boost the detection sensitivity.

Concentration dependent optical transition probabilities in ultra-small upconversion nanocrystals.

Transition probability is of vital importance for luminescence process, whereas the effects of doping concentration have not been explored in the Er3+:NaGdF4. In this work, we investigate the radiative transition probabilities of Er3+ highly doped NaGdF4 sub 10 nm nanocrystals using J-O theory. It is found that the transition probabilities vary with changing Er3+ concentration, especially altering the ratio of Er3+ 2H11/2 to 4S3/2 level, which is highly useful for optical thermometers as they are thermally coupled. To validate the concentration dependent transition probabilities, significant enhancements of upconversion luminescence are achieved by epitaxial growth of the inert shell, and thermal sensing behaviors are investigated using the improved samples.

Single upconversion nanoparticle imaging at sub-10 W cm-2 irradiance.

Lanthanide-doped upconversion nanoparticles (UCNPs) are promising single-molecule probes given their non-blinking, photobleach-resistant luminescence upon infrared excitation. However, the weak luminescence of sub-50 nm UCNPs limits their single-particle detection to above 10 kWcm-2 that is impractical for live cell imaging. Here, we systematically characterize single-particle luminescence for UCNPs with various formulations over a 106 variation in incident power, down to 8 Wcm-2. A core-shell-shell (CSS) structure (NaYF4@NaYb1-xF4:Erx@NaYF4) is shown to be significantly brighter than the commonly used NaY0.78F4:Yb0.2Er0.02. At 8 Wcm-2, the 8% Er3+ CSS particles exhibit a 150-fold enhancement given their high sensitizer Yb3+ content and the presence of an inert shell to prevent energy migration to defects. Moreover, we reveal power-dependent luminescence enhancement from the inert shell, which explains the discrepancy in enhancement factors reported by ensemble and previous single-particle measurements. These brighter probes open the possibility of cellular and single-molecule tracking at low irradiance.

Low irradiance multiphoton imaging with alloyed lanthanide nanocrystals

Multiphoton imaging techniques that convert low-energy excitation to higher energy emission are widely used to improve signal over background, reduce scatter, and limit photodamage. Lanthanide-doped upconverting nanoparticles (UCNPs) are among the most efficient multiphoton probes, but even UCNPs with optimized lanthanide dopant levels require laser intensities that may be problematic. Here, we develop protein-sized, alloyed UCNPs (aUCNPs) that can be imaged individually at laser intensities >300-fold lower than needed for comparably sized doped UCNPs. Using single UCNP characterization and kinetic modeling, we find that addition of inert shells changes optimal lanthanide content from Yb3+, Er3+-doped NaYF4 nanocrystals to fully alloyed compositions. At high levels, emitter Er3+ ions can adopt a second role to enhance aUCNP absorption cross-section by desaturating sensitizer Yb3+ or by absorbing photons directly. Core/shell aUCNPs 12 nm in total diameter can be imaged through deep tissue in live mice using a laser intensity of 0.1 W cm−2.

Efficient Erbium‐Sensitized Core/Shell Nanocrystals for Short Wave Infrared Bioimaging

AbstractThe 1500–1700 nm spectral range in short wave infrared (SWIR) region allows for biological imaging with large imaging depth, high contrast and resolution. However, very few SWIR imaging probes exist, and rarely reported probes (e.g., rare‐earth‐based ones with excitation at 980 nm) are often associated with biological heating effect. Here, a class of erbium (Er3+)‐sensitized core–shell nanocrystals of NaErF4:Yb3+@NaLuF4, which emit efficient SWIR luminescence peaked at 1525 nm under 808 nm excitation, without producing any local heating, is described. The inert shell inhibits concentration‐dependent quenching and allows for an enriched incorporation of 100% Er3+ into the core, yielding about ≈650‐fold higher SWIR luminescence than parent core nanocrystals. Importantly, an appropriate doping of ytterbium (Yb3+) (optimized concentration, 20%) into the core is shown to further enhance SWIR luminescence (by twofold), endowing the nanocrystals with a high quantum yield of 11%. This Yb3+‐mediated enhancement is possibly due to the suppression of upconverting pathways and the formation of energy trapping centers that prevent the energy migration to intrinsic lattice defects. These bright SWIR core/shell nanocrystals allow high contrast in vitro imaging of HeLa cells and in vivo through‐skull imaging of blood vasculature in the mouse brain.

Gadolinium-Encapsulated Graphene Carbon Nanotheranostics for Imaging-Guided Photodynamic Therapy.

Photosensitizers (PS) are an essential component of photodynamic therapy (PDT). Conventional PSs are often porphyrin derivatives, which are associated with high hydrophobicity, low quantum yield in aqueous solutions, and suboptimal tumor-to-normal-tissue (T/N) selectivity. There have been extensive efforts to load PSs into nanoparticle carriers to improve pharmacokinetics. The approach, however, is often limited by PS self-quenching, pre-mature release, and nanoparticle accumulation in the reticuloendothelial system organs. Herein, a novel, nanoparticle-based PS made of gadolinium-encapsulated graphene carbon nanoparticles (Gd@GCNs), which feature a high 1 O2 quantum yield, is reported. Meanwhile, Gd@GCNs afford strong fluorescence and high T1 relaxivity (16.0 × 10-3 m-1 s-1 , 7 T), making them an intrinsically dual-modal imaging probe. Having a size of approximately 5 nm, Gd@GCNs can accumulate in tumors through the enhanced permeability and retention effect. The unbound Gd@GCNs cause little toxicity because Gd is safely encapsulated within an inert carbon shell and because the particles are efficiently excreted from the host through renal clearance. Studies with rodent tumor models demonstrate the potential of the Gd@GCNs to mediate image-guided PDT for cancer treatment. Overall, the present study shows that Gd@GCNs possess unique physical, pharmaceutical, and toxicological properties and are an all-in-one nanotheranostic tool with substantial clinical translation potential.

Photostable and efficient upconverting nanocrystal-based chemical sensors

Chemical sensing in living systems demands optical sensors that are bright, stable, and sensitive to the rapid dynamics of chemical signaling. Lanthanide-doped upconverting nanoparticles (UCNPs) efficiently convert near infrared (NIR) light to higher energy emission and allow biological systems to be imaged with no measurable background or photobleaching, and with reduced scatter for subsurface experiments. Despite their advantages as imaging probes, UCNPs have little innate chemical sensing ability and require pairing with organic fluorophores to act as biosensors, although the design of stable UCNP-fluorophore hybrids with efficient upconverted energy transfer (UET) has remained a challenge. Here, we report Yb3+- and Er3+-doped UCNP-fluorophore conjugates with UET efficiencies up to 88%, and photostabilities 100-fold greater by UET excitation than those of the free fluorophores under direct excitation. Despite adding distance between Er3+ donors and organic acceptors, thin inert shells significantly enhance overall emission without compromising UET efficiency. This can be explained by the large increase in quantum yield of Er3+ donors at the core/shell interface and the large number of fluorophore acceptors at the surface. Sensors excited by UET show increases in photostability well beyond those reported for other methods for increasing the longevity of organic fluorophores, and those covalently attached to UCNP surface polymers show greater chemical stability than those directly coordinated to the nanocrystal surface. By conjugating other fluorescent chemosensors to UCNPs, these hybrids may be extended to a series of NIR-responsive biosensors for quantifying the dynamic chemical populations critical for cell signaling.

NaYF4 :Yb,Er/NaYF4 Core/Shell Nanocrystals with High Upconversion Luminescence Quantum Yield.

Upconversion core/shell nanocrystals with different mean sizes ranging from 15 to 45 nm were prepared via a modified synthesis procedure based on anhydrous rare-earth acetates. All particles consist of a core of NaYF4 :Yb,Er, doped with 18 % Yb3+ and 2 % Er3+ , and an inert shell of NaYF4 , with the shell thickness being equal to the radius of the core particle. Absolute measurements of the photoluminescence quantum yield at a series of different excitation power densities show that the quantum yield of 45 nm core/shell particles is already very close to the quantum yield of microcrystalline upconversion phosphor powder. Smaller core/shell particles prepared by the same method show only a moderate decrease in quantum yield. The quantum yield of 15 nm core/shell particles, for instance, is reduced by a factor of three compared to the bulk upconversion phosphor at high power densities (100 W cm-2 ) and by approximately a factor of 10 at low power densities (1 W cm-2 ).

Structure, magnetic and cytotoxic behaviour of solvothermally grown Fe3O4@Au core-shell nanoparticles

Magnetic nanoparticles (MNPs) have demonstrated their potential in a wide variety of biomedical applications including in tumour hyperthermia. However, highly reactive nature and aggregation affinity of these nanostructures are the principal limitations for such applications. To overcome these limitations, those MNPs should be covered with an inert shell in order to protect the magnetic core against chemical alterations. Considering the noble, chemically inert nature of gold, which also has good biocompatibility, we fabricated chemically stable gold-coated Fe3O4 (Fe3O4@Au) nanoparticles of 20–50 nm size range with considerable saturation magnetization, though a simple one-pot solvothermal method. The morphology, elemental distribution and the structure of the core-shell nanoparticles were characterized using aberration-corrected (Cs) Scanning transmission electron microscopy (STEM), and compared with their simulated images. Cytotoxicity assay in MDCK cell line was performed to evaluate the biocompatibility of the nanoparticles. The results showed higher cell viability for the Fe3O4@Au nanoparticles, suggesting their good biocompatibility and potentials for biomedical applications.

Barium in High Oxidation States in Pressure-Stabilized Barium Fluorides

The oxidation state of an element influences its chemical behavior of reactivity and bonding. Finding unusual oxidation state of elements is a theme of eternal pursuit. As labeled by an alkali-earth metal, barium (Ba) invariably exhibits an oxidation state of +2 by a loss of two 6s valence electrons while its inner 5p closed shell is known to remain intact. Here, we show through the reaction with fluorine (F) at high pressure that Ba exhibits a hitherto unexpected high oxidation state greater than +2 in three pressure-stabilized F-rich compounds BaF3, BaF4, and BaF5, where Ba takes on the role of a 5p element by opening up its inert 5p shell. Interestingly enough, these pressure-stabilized Ba fluorides share common structural features of Ba-centered polyhedrons but exhibit a diverse variety of electronic properties showing semiconducting, metallic, and even magnetic behaviors. Our work modifies the traditional knowledge on the chemistry of alkali-earth Ba element established at ambient pressure and highli...

Probing Interaction Distance of Surface Quenchers in Lanthanide-Doped Upconversion Core–Shell Nanoparticles

Core–shell structures, which employ an optically inert shell to physically separate the emitting core from the surface quenchers, are often designed to optimize the emission efficiency of nanoscale emitters. However, it remains unclear that at what distance the effects of different surface quenchers, such as defects and adsorbed moieties, can be completely screened by the shell. Here, in a model upconversion system, we examine the interaction distance of surface quenchers in core–shell nanoparticles by using upconversion spectroscopy. Steady-state as well as time-resolved spectra show that the quenching effect of surface-adsorbed hydroxyl (OH) group diminishes at a distance (shell thickness) of 3.5 nm in diameter and 8.0 nm in length, which is larger than that for oleate-capped counterparts. With the increase of pumping density, the interaction distance of the surface quenchers does not apparently change, whereas saturation of the surface-related states notably reduces the optimal shell thickness for surf...

Quantum Yields, Surface Quenching, and Passivation Efficiency for Ultrasmall Core/Shell Upconverting Nanoparticles.

We synthesized and characterized a set of ultrasmall hexagonal-phase NaGdF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles with core diameters of 3.7 ± 0.5 nm. In order to assess passivation effects and the influence of possible core-shell intermixing and to identify optimum particle structures for combined imaging in the visible and near-infrared (vis-NIR: 410-850 nm) and short-wave infrared (SWIR: 1520 nm), NaYF4 shells of varying thicknesses (monolayer to 10 nm) were introduced and the influence of this parameter on the upconversion and downshifting photoluminescence of these particles was studied at different excitation power densities. This included excitation power-dependent emission spectra, slope factors, quantum yields, and excited state decay kinetics. These measurements revealed enhancement factors of the upconversion quantum yield of >10 000 in the low power region and an excitation power density-independent quantum yield of the downshifted emission at 1520 nm between 0.1 and 14%. The optimized shell thickness for combined vis and SWIR imaging was identified as 5 nm. Moreover, lifetimes and quantum yields can be continuously tuned by shell thickness which can be exploited for lifetime multiplexing and encoding. The fact that we did not observe a saturation of the upconversion quantum yield or the excited state decay kinetics with increasing shell thickness is ascribed to a strong intermixing of the active core with the inert shell during the shelling procedure. This indicates the potential of spectroscopic tools to detect cation intermixing.

Mesoporous luminescent GdF3:Tb@LaF3@SiO2 nanorods: comparative structural and optoelectronic studies

Terbium doped gadolinium fluoride (GdF3:Tb) nanorods (core-NRs) subsequently covered by inert LaF3 and silica shells to form the GdF3:Tb@LaF3@SiO2 core–shell–SiO2-NRs type structure was synthesized by polyol based co-precipitation and sol–gel process. X-ray diffraction pattern confirmed the crystal structure and grain size of the materials. FETEM, EDX and FTIR spectral studies show the successful amorphous silica surface coating surrounding the core–shell NRs. The reduction in energy band gap from core to core–shell–SiO2-NRs could be due to increase the crystalline size of the material. In comparison with core-NRs, the excitation and emission efficiency of core–shell-NRs were remarkably increased. This obvious feature is mainly attributed to the formation of the inert LaF3 layer, which effectively protected Tb3+ ion from the surrounding environment. Spectroscopic studies clearly revealed the difference between these three type products. Silica surface modified core–shell–SiO2-NRs exhibited good dispersibility along with excellent colloidal stability in aqueous and non-aqueous solvents which is the novel character of the highly photostable luminescent nanomaterials. This novel approach of core-NRs coated with passive LaF3 and silica shell has potential applications in photonic based bio-medical sciences.

Quantitative investigation on the critical thickness of the dielectric shell for metallic nanoparticles determined by the plasmon decay length

Inert dielectric shells coating the surface of metallic nanoparticles (NPs) are important for enhancing the NPs’ stability, biocompatibility, and realizing targeting detection, but they impair NPs’ sensing ability due to the electric fields damping. The dielectric shell not only determines the distance of the analyte from the NP surface, but also affects the field decay. From a practical point of view, it is extremely important to investigate the critical thickness of the shell, beyond which the NPs are no longer able to effectively detect the analytes. The plasmon decay length of the shell-coated NPs determines the critical thickness of the coating layer. Extracting from the exponential fitting results, we quantitatively demonstrate that the critical thickness of the shell exhibits a linear dependence on the NP volume and the dielectric constants of the shell and the surrounding medium, but only with a small variation influenced by the NP shape where the dipole resonance is dominated. We show the critical thickness increases with enlarging the NP sizes, or increasing the dielectric constant differences between the shell and surrounding medium. The findings are essential for applications of shell-coated NPs in plasmonic sensing.