Frank C. J. M. van Veggel

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.

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.

Self-focusing by Ostwald ripening: a strategy for layer-by-layer epitaxial growth on upconverting nanocrystals.

We demonstrate a novel epitaxial layer-by-layer growth on upconverting NaYF(4) nanocrystals (NCs) utilizing Ostwald ripening dynamics tunable both in thickness and composition. Injection of small sacrificial NCs (SNCs) as shell precursors into larger core NCs results in the rapid dissolution of the SNCs and their deposition onto the larger core NCs to yield core-shell structured NCs. Exploiting this NC size dependent dissolution/growth, the shell thickness can be controlled either by manipulating the number of SNCs injected or by successive injection of SNCs. In either of these approaches, the NCs self-focus from an initial bimodal distribution to a unimodal distribution (σ <5%) of core-shell NCs. The successive injection approach facilitates layer-by-layer epitaxial growth without the need for tedious multiple reactions for generating tunable shell thickness, and does not require any control over the injection rate of the SNCs, as is the case for shell growth by precursor injection.

Broadband sensitizers for erbium-doped planar optical amplifiers: review

Three different broadband sensitization concepts for optically active erbium ions are reviewed: 1) silicon nanocrystals, with absorption over the full visible spectrum, efficiently couple their excitonic energy to Er3+, 2) silver-related defect states in sodalime silicate glass have absorption in the blue and transfer energy to Er3+, and 3) organic cage complexes coordinated with well-chosen chromophores serve as broadband sensitizers in the visible. Energy transfer rates, efficiencies, and limiting factors are addressed for each of these sensitizers. Implications of the use of strong sensitizers for planar waveguide design are illustrated by using a model for the sensitizing effect of ytterbium.

Hard Proof of the NaYF4/NaGdF4 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.

Transition Metal Complexes as Photosensitizers for Near‐Infrared Lanthanide Luminescence

We thank Roel Fokkens and Nico Nibbering (University of Amsterdam) for recording and discussing the MALDI-TOF mass spectra. Martijn Werts (University of Amsterdam) is gratefully acknowledged for his support with the time-resolved luminescence measurements. This research has been financially supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO).

Subtissue Thermal Sensing Based on Neodymium-Doped LaF3 Nanoparticles

In this work, we report the multifunctional character of neodymium-doped LaF₃ core/shell nanoparticles. Because of the spectral overlap of the neodymium emission bands with the transparency windows of human tissues, these nanoparticles emerge as relevant subtissue optical probes. For neodymium contents optimizing the luminescence brightness of Nd³⁺:LaF₃ nanoparticles, subtissue penetration depths of several millimeters have been demonstrated. At the same time, it has been found that the infrared emission bands of Nd³⁺:LaF₃ nanoparticles show a remarkable thermal sensitivity, so that they can be advantageously used as luminescent nanothermometers for subtissue thermal sensing. This possibility has been demonstrated in this work: Nd³⁺:LaF₃ nanoparticles have been used to provide optical control over subtissue temperature in a single-beam plasmonic-mediated heating experiment. In this experiment, gold nanorods are used as nanoheaters while thermal reading is performed by the Nd³⁺:LaF₃ nanoparticles. The possibility of a real single-beam-controlled subtissue hyperthermia process is, therefore, pointed out.

Surface Eu3+ ions are different than “bulk” Eu3+ ions in crystalline doped LaF3 nanoparticles

Distinct surface effects on the luminescence properties of highly crystalline LaF3:Eu nanoparticles have been demonstrated, by incorporating different ligands on their surface as well as forming core–shell nanoparticles (i.e. doped LaF3:Eu core with an undoped LaF3 shell). These studies have established that the surface Eu3+ ions have a less symmetric crystal field than the “bulk”, and that they are responsible for the ligand induced changes in the asymmetric ratio, which is determined from the relative intensity ratio of the 5D0 → 7F2 (612 and 618 nm) and 5D0 → 7F1 (591 nm) transitions. This surface effect can very effectively be reduced by forming core–shell particles. The multi-exponential luminescent decay curves observed for these nanoparticles have been fitted using a three-parameter model involving the radiative decay constant of the nine inner shells (kR), the radiative decay constant of the outermost shell (kR10), and a parameter C, which describes the quenching, and is a function of the particular luminescent lanthanide ion, the type and amount of quenchers on or near the surface. The model accounts well for the observed changes in the asymmetric ratio of luminescence of these nanoparticles brought about by the ligands used to stabilise them.

Cation Exchange in Lanthanide Fluoride Nanoparticles

Cation exchange in lanthanide fluoride nanoparticles is reported. Typically, dispersible LnF(3) nanoparticles were exposed to another lanthanide ion that was roughly 5 times the amount of Ln(3+) in the nanoparticles. Results show that cation exchange of GdF(3) nanoparticles with La(3+) was almost complete in 1 min, and it also happens reversibly although the degree of exchange is not as much as the forward reaction. However, cation exchange with lanthanide ions close to each other, such as GdF(3) with Eu(3+) and NdF(3) with La(3+), did not end up with nearly full exchange, but with a significant amount of the two lanthanides. A relatively small driving force for the cation exchange is suggested by the experimental results, which is also confirmed by calculations based on a thermodynamic cycle. This unprecedented finding in the field of lanthanide-based nanoparticles raises the question whether reported core-shell structures were indeed made and, at the same time, it opens up new pathways to make nanomaterials that cannot be made directly.

Neodymium-Doped LaF (3) Nanoparticles for Fluorescence Bioimaging in the Second Biological Window

The future perspective of fluorescence imaging for real in vivo application are based on novel efficient nanoparticles which is able to emit in the second biological window (1000-1400 nm). In this work, the potential application of Nd(3+) -doped LaF(3) (Nd(3+) :LaF(3) ) nanoparticles is reported for fluorescence bioimaging in both the first and second biological windows based on their three main emission channels of Nd(3+) ions: (4) F(3/2) →(4) I(9/2) , (4) F(3/2) →(4) I(11/2) and (4) F(3/2) →(4) I(13/2) that lead to emissions at around 910, 1050, and 1330 nm, respectively. By systematically comparing the relative emission intensities, penetration depths and subtissue optical dispersion of each transition we propose that optimum subtissue images based on Nd(3+) :LaF(3) nanoparticles are obtained by using the (4) F3/2 →(4) I11/2 (1050 nm) emission band (lying in the second biological window) instead of the traditionally used (4) F(3/2) →(4) I(9/2) (910 nm, in the first biological window). After determining the optimum emission channel, it is used to obtain both in vitro and in vivo images by the controlled incorporation of Nd(3+) :LaF(3) nanoparticles in cancer cells and mice. Nd(3+) :LaF(3)nanoparticles thus emerge as very promising fluorescent nanoprobes for bioimaging in the second biological window.