A UV-blocking polymer shell prevents one-photon photoreactions while allowing multi-photon processes in encapsulated upconverting nanoparticles.

Sun block for nanoparticles: Unintentional photorelease triggered by UV light is a problem in photodynamic therapy. Encapsulating upconverting nanoparticles containing photoswitches in a UV-blocking amphiphilic polymer shuts down the one-photon process and only allows two-photon-driven photochemistry. Thus, UV light is blocked while NIR light can reach the nanoparticle core and trigger photorelease.

Near infrared light triggered release of biomacromolecules from hydrogels loaded with upconversion nanoparticles.

Using a photosensitive hybrid hydrogel loaded with upconversion nanoparticles (UCNPs), we show that continuous-wave near-infrared (NIR) light (980 nm) can be used to induce the gel-sol transition and release large, inactive biomacromolecules (protein and enzyme) entrapped in the hydrogel into aqueous solution "on demand", where their bioactivity is recovered. This study is a new demonstration and development in harnessing the unique multiphoton effect of UCNPs for photosensitive materials of biomedical interest.

Multimodal fluorescence modulation using molecular photoswitches and upconverting nanoparticles.

The intensity and colour of the light emitted from upconverting nanoparticles is controlled by the state of photoresponsive dithienylethene ligands decorated onto the surface of the nanoparticles. By selectively activating one or both ligands in a mixed, 3-component system, a multimodal read-out of the emitted light is achieved.

Near-infrared light-triggered dissociation of block copolymer micelles using upconverting nanoparticles.

We demonstrate a novel strategy enabling the use of a continuous-wave diode near-infrared (NIR) laser to disrupt block copolymer (BCP) micelles and trigger the release of their "payloads". By encapsulating NaYF(4):TmYb upconverting nanoparticles (UCNPs) inside micelles of poly(ethylene oxide)-block-poly(4,5-dimethoxy-2-nitrobenzyl methacrylate) and exposing the micellar solution to 980 nm light, photons in the UV region are emitted by the UCNPs, which in turn are absorbed by o-nitrobenzyl groups on the micelle core-forming block, activating the photocleavage reaction and leading to the dissociation of BCP micelles and release of co-loaded hydrophobic species. Our strategy of using UCNPs as an internal UV or visible light source upon NIR light excitation represents a general and efficient method to circumvent the need for UV or visible light excitation that is a common drawback for light-responsive polymeric systems developed for potential biomedical applications.

Two-way photoswitching using one type of near-infrared light, upconverting nanoparticles, and changing only the light intensity.

Only one type of lanthanide-doped upconverting nanoparticle (UCNP) is needed to reversibly toggle photoresponsive organic compounds between their two unique optical, electronic, and structural states by modulating merely the intensity of the 980 nm excitation light. This reversible "remote-control" photoswitching employs an excitation wavelength not directly absorbed by the organic chromophores and takes advantage of the fact that designer core-shell-shell NaYF(4) nanoparticles containing Er(3+)/Yb(3+) and Tm(3+)/Yb(3+) ions doped into separate layers change the type of light they emit when the power density of the near-infrared light is increased or decreased. At high power densities, the dominant emissions are ultraviolet and are appropriate to drive the ring-closing, forward reactions of dithienylethene (DTE) photoswitches. The visible light generated from the same core-shell-shell UCNPs at low power densities triggers the reverse, ring-opening reactions and regenerates the original photoisomers. The "remote-control" photoswitching using NIR light is as equally effective as the direct switching with UV and visible light, albeit the reaction rates are slower. This technology offers a highly convenient and versatile method to spatially and temporally regulate photochemical reactions using a single light source and changing either its power or its focal point.

Absolute quantum yield measurements of colloidal NaYF4: Er3+, Yb3+ upconverting nanoparticles.

In this communication we describe a technique for measuring the absolute quantum yields (QYs) of upconverting nanomaterials based on the use of a commercially available fluorimeter and an integrating sphere. Using this setup, we have successfully acquired luminescence efficiency data (pump laser, absorbed pump, and visible emitted intensities) for lanthanide-doped upconverting nanoparticles. QYs in the range of 0.005% to 0.3% were measured for several NaYF(4): 2% Er(3+), 20% Yb(3+) nanoparticles with particle sizes ranging from 10 to 100 nm while a QY of 3% was measured for a bulk sample.

Facile ligand-exchange with polyvinylpyrrolidone and subsequent silica coating of hydrophobic upconverting beta-NaYF(4):Yb(3+)/Er(3+) nanoparticles.

A facile ligand-exchange strategy with a water-soluble polymer, i.e. polyvinylpyrrolidone (PVP), to replace the surface passivating oleate ligands on the beta-NaYF(4) nanoparticle surface is reported. Highly monodisperse oleate-stabilized beta-NaYF(4) nanoparticles were synthesized and the oleates were exchanged with a commercially available PVP allowing the phase transfer of these nanoparticles. The exchanged nanoparticles are readily dispersible in water and other polar solvents. To show the effectiveness of the exchange reaction we used the affinity of the PVP chains to silica and coated the nanoparticles with a uniform, thin silica shell. The PVP exchanged and silica-coated nanoparticles show longer colloidal stability and no surfactant related problems as compared to the reverse microemulsion-based silica-coated nanoparticles, which show a high tendency to aggregate, when removed from the microemulsion. The optical properties of the ligand-exchanged nanoparticles dispersed in water were compared with that of the oleate-stabilized nanoparticles in organic solvents. A decrease in the upconversion emission intensity and a different relative ratio of the green and red upconverted light were observed for the particles dispersed in water after ligand-exchange. PVP is a highly biocompatible polymer and is reported to have a longer blood circulation time and very low accumulation in vital organs, two highly desired properties for in vivo studies. This ligand-exchange strategy opens a new pathway to study the use of beta-NaYF(4) for biological applications in vivo.

Surface modification of upconverting NaYF4 nanoparticles with PEG-phosphate ligands for NIR (800 nm) biolabeling within the biological window.

We present a technique for the replacement of oleate with a PEG-phosphate ligand [PEG = poly(ethylene glycol)] as an efficient method for the generation of water-dispersible NaYF(4) nanoparticles (NPs). The PEG-phosphate ligands are shown to exchange with the original oleate ligands on the surface of the NPs, resulting in water-dispersible NPs. The upconversion intensity of the NPs in aqueous environments was found to be severely quenched when compared to the original NPs in organic solvents. This is attributed to an increase in the multiphonon relaxations of the lanthanide excited state in aqueous environments due to high energy vibrational modes of water molecules. This problem could be overcome partially by the synthesis of core/shell NPs which demonstrated improved photophysical properties in water over the original core NPs. The PEG-phosphate coated upconverting NPs were then used to image a line of ovarian cancer cells (CaOV3) to demonstrate their promise in biological application.

Hard proof of the NaYF(4)/NaGdF(4) nanocrystal core/shell structure.

Hexagonal-phase NaYF(4)/NaGdF(4) core/shell nanocrystals were synthesized and investigated by X-ray photoelectron spectroscopy (XPS) using tunable synchrotron radiation. Based on the ratio of the Y(3+) 3d to Gd(3+) 4d core level intensities at varying photoelectron kinetic energies, we conclude that Gd(3+) resides predominantly at the surface of the nanocrystals, proving a core/shell structure. These nanocrystals show potential for use as contrast agents in magnetic resonance imaging (MRI) applications and optical imaging.

Remote-control photoswitching using NIR light.

Near-infrared (NIR) light is used to toggle photoswitches back and forth between their two isomers even though the chromophores do not significantly absorb this type of light. The reactions are achieved through a "remote control" process by using photon upconverting hexagonal NaYF(4) nanocrystals doped with lanthanide ions. These nanoparticles absorb 980 nm light and convert it to wavelengths that can be used to trigger the photoswitches offering a practical means to potentially achieve 3D-data storage, drug-delivery, and photolithography.

Synthesis of colloidal upconverting NaYF4: Er3+/Yb3+ and Tm3+/Yb3+ monodisperse nanocrystals.

The synthesis, characterization, and spectroscopy of upconverting lanthanide-doped NaYF4 nanocrystals (NCs) is presented. The monodisperse cubic NaYF4 NCs were synthesized via a thermal decomposition reaction of trifluoroacetate precusors in a mixture of technical grade chemicals, octadecene and the coordinating ligand oleic acid. In this straightforward method, the dissolved precursors are added slowly to the reaction solution through a stainless-steel canula resulting in highly luminescent nanocrystals with an almost monodisperse particle size distribution. The NCs were characterized through the use of transmission electron microscopy, selected area electron diffraction, 1H NMR, powder X-ray diffraction, and high-resolution luminescence spectroscopy. The NaYF4 NCs are capable of being of dispersed in nonpolar organic solvents thus forming colloidally stable solutions. The colloids of the Er3+, Yb3+ and Tm3+, Yb3+ doped NCs exhibit green/red and blue upconversion luminescence, respectively, under 980 nm laser diode excitation with low power densities.

Synthesis of colloidal upconverting NaYF4 nanocrystals doped with Er3+, Yb3+ and Tm3+, Yb3+ via thermal decomposition of lanthanide trifluoroacetate precursors.

Upconverting lanthanide-doped nanocrystals were synthesized via the thermal decomposition of trifluoroacetate precursors in a mixture of oleic acid and octadecene. This method provides highly luminescent nanoparticles through a simple one-pot technique with only one preparatory step. The Er3+, Yb3+ and Tm3+, Yb3+ doped cubic NaYF4 nanocrystals are colloidally stable in nonpolar organic solvents and exhibit green/red and blue upconversion luminescence, respectively, under 977 nm laser excitation with low power densities.

A spectroscopic analysis of blue and ultraviolet upconverted emissions from Gd3Ga5O12:Tm3+, Yb3+ nanocrystals.

The spectroscopic behavior of gadolinium gallium garnet (Gd3Ga5O12, GGG) nanocrystals codoped with 1% each of Tm3+ and Yb3+ prepared via a solution combustion synthesis procedure was investigated. Initial excitation of the codoped nanocrystals with 465.8 nm (into the 1G4 state) showed a dominant blue-green emission ascribed to the 1G4-3H6 transition as well as red and NIR emissions from the 1G4-3F4 and 1G4-3H5/3H4-3H6 transitions, respectively. Excitation at this wavelength (465.8 nm) showed the existence of a Tm3+ --> Yb3+ energy transfer process evidenced by the presence of the 2F5/2-2F7/2 Yb3+ emission in the NIR emission spectrum. The decay time constants proved that the transfer of energy occurred via the 3H4 state. Following excitation of the Yb3+ ion with 980 nm, intense upconverted emission was observed. Emissions in the UV (1D2-3H6), blue (1D2-3F4), blue-green (1G4-3H6), red (1G4-3F4), and NIR (1G4-3H5/3H4-3H6) were observed and were the direct result of subsequent transfers of energy from the Yb3+ ion to the Tm3+ ion. Power dependence studies showed a deviation from expected values for the number of photons involved in the upconversion thus indicating a saturation of the upconversion process. An energy transfer efficiency of 0.576 was determined experimentally.