Cytotoxic interactions of bare and coated NaGdF4:Yb(3+):Er(3+) nanoparticles with macrophage and fibroblast cells.

The lanthanide nano-compounds are well suited to serve as fluorescent and magnetic contrast agents and luminescent labels. Although they are considered as promising materials for bio-imaging and bio-sensors in vivo or in vitro, the amount of data is still insufficient for deep understanding the toxicity of these nanomaterials. This knowledge is of great importance in the light of growing use of the biofunctionalized nanoparticles, which raises some questions about safety of these materials. Despite lanthanide-doped NaGdF4 nanocrystals are considered as non-toxic, here we present the data showing the fatal effect of newly synthetized NaGdF4:Yb(3+):Er(3+) on chosen types of cells. Our studies were performed on two cell lines NIH3T3 fibroblasts, and RAW264.7 macrophages. Cytotoxic properties of NaGdF4:Yb(3+):Er(3+) nanoparticles and their biological effects were studied by assessing cell culture viability (MTS), proliferation and apoptosis. Bare NaGdF4:Yb(3+):Er(3+) nanocrystals were cytotoxic and induced apoptosis of both NIH3T3 and RAW264.7 cells. Their cytotoxicity was reduced by PEGylation, at the expense of minimizing direct interactions between the compound and the cell. On the other hand, coating with silica reduced cell death induced by Yb(3+):Er(3+) codoped NaGdF4 nanocrystals (but proliferation was still inhibited). The NH2-modified silica coated nanoparticles were clearly less cytotoxic than pristine nanoparticles, which suggests that both, silica and PEG coatings are reasonable approaches to decrease cytotoxicity of the nanocrystal labels. The silica and PEG shell, should also enable and simplify further bio-functionalization of these luminescent labels. The authors acknowledge the financial support from: Institute of Immunology and Experimental Therapy, Polish Academy of Sciences (IITD PAN) grant no. 3/15, Polish Ministry of Science and Higher Education, Grant N N507 499538 and from the Wroclaw Research Centre EIT+ within the project "The Application of Nanotechnology in Advanced Materials" - NanoMat (POIG.01.01.02-02-002/08) financed by the European Regional Development Fund (Operational Program Innovative Economy, 1.1.2).

Interaction of lanthanide ß-diketonate complexes with polyvinylpyrrolidone: proton-controlled switching of Tb3+ luminescence.

In the present study the interaction of lanthanide ß-diketonate complexes with polyvinylpyrrolidone (PVP) has been systematically investigated using fluorescence spectroscopy. The emission of terbium complexes with hexafluoroacetylacetone (hfa) ligands is almost completely quenched by PVP in the absence of H(+) ions, while it is enhanced by more than 30 times in the presence of H(+) ions. Conversely, the H(+) ions increase the quenching efficiency of terbium complex with acetylacetone ligands. The strikingly different behavior of complexes with fluorinated and nonfluorinated ß-diketonates is accounted for by the interaction mechanism, in which the important role of hydrogen bonds is indicated. The proposed mechanism includes ion-dipol Coulombic interactions between negative charge localized on ligands O-C-CH2-C-O group and positive charge induced in N atom of PVP pyrrolidone group, as well as interactions through hydrogen bonds formed between ligand C-O groups and PVP, occurring directly or through solvent molecules. Additional stabilizing effect, significantly influencing the binding strength of ligands with PVP, results from hydrogen bonds formed by terminal (CF3 or CH3) substituents of ligands with C-O group of PVP. Importantly, the quenching and enhancement of luminescence of terbium complexes with hfa ligands in PVP solution is a reversible process. This enables one to obtain the emission switch-OFF-ON system triggered externally by H(+) ions, which can find possible application in the development of molecule-based devices.

A general and versatile procedure for coating of hydrophobic nanocrystals with a thin silica layer enabling facile biofunctionalization and dye incorporation.

Here we report a method for coating of hydrophobic nanocrystals (NCs) with a thin silica layer. By using this approach 11 nm NaGdF4 NCs were coated with a mesoporous silica shell thinner than 20 nm resulting in highly monodisperse core-shell nanocomposite particles smaller than 50 nm. The synthetic protocol used here is based on the two-phase system that ensures high repeatability of the nanoparticle morphology and can be conveniently adapted for large-scale production. The use of an organic solvent as a diluent for tetraethoxysilane allows us to control not only the thickness, but also the porosity of the uniform silica shell. This procedure can be applied for coating NCs of various sizes and can be generalized to encapsulate other nanocrystals, e.g. semi-conductor quantum dots, into silica spheres. Furthermore, it allows facile surface modification with -NH2 groups that can be then used to conjugate biomolecules to the nanoparticle surface, as well as straightforward incorporation of various organic molecules (e.g. dyes or drugs) into the silica shell during its growth. To demonstrate potential applications up-converting NaGd0.80Yb0.18Er0.02F4 NCs were used as cores and zinc phthalocyanine was incorporated into the silica shell as a photosensitizer. Under irradiation with a 980 nm laser diode efficient generation of singlet oxygen was observed indicating that such nanocomposite particles have the capability to be used for photodynamic therapy.

Optical spectra and energy levels analysis of the 4f(N) ions doped into Ba2YCl7.

Absorption emission and excitation spectra are measured and analyzed to achieve assignments of energy levels for 4f(N) ions in Ba(2)YCl(7):RE(3+) (RE = Pr, Nd, Tb, Dy, Ho, Er, and Tm) crystals. The experimental energy levels were analyzed in terms of the usual free-ion parameters and the crystal field (CF) ones, B(kq), in the Wybourne notation. The orthorhombic C(2v) symmetry is shown to be a good approximation of the actual triclinic C(1) site symmetry at the metal center. The starting values of the CF parameters B(kq) used for fittings for the studied crystals were obtained from superposition model analysis. A good agreement between the calculated and experimental energy levels was obtained with rms deviations in the range from 6.8 cm(-1) (for Ho(3+)) to 14.1 cm(-1) (for Pr(3+)). The fitted sets of B(kq) parameters are, in general, consistent across the 4f(N) series. This study has enabled determination and discussion of the trends in variation of the free-ion parameters and CF ones across the 4f(N) series. The CF parameter set and energy level structure obtained for Nd(3+) ion in Ba(2)YCl(7) crystal are consistent with those for Nd(3+) in structurally related RbY(2)Cl(7) crystal. This systematic analysis of CF parameters is one of only few such studies encompassing nearly whole series of RE(3+) ions.

Optimisation of ligand exchange towards stable water suspensions of crystalline NaYF4: Er3+, Yb3+ nanoluminophors.

NaYF4: 2%Er3+, 20%Yb3+ nanoparticles were synthesized through a wet chemical route. In order to transfer the nanoparticles from chloroform to aqueous solution an oleic acid to 3-mercaptopropionic acid ligand exchange process has been performed and optimized. The influence of temperature and atmosphere onto the NaYF4:2%Er3+, 20%Yb3+ nanoparticles water suspensions dispersibility and stability after replacing oleic acid with 3-mercaptopropionic acid ligands has been investigated. The results revealed an improvement of nanoparticles water suspension transparency and luminescence yield after ligand exchange process performed under inert atmosphere and at elevated temperature.

Energy levels and crystal field parameters for Nd3+ ions in BaY2F8, LiKYF5, and K2YF5 single crystals.

The available experimental energy levels of Nd(3+) ions doped into single crystals of BaY(2)F(8), LiKYF(5), and K(2)YF(5), which exhibit low site symmetry, are reanalyzed. A combined approach based on the ascent/descent in symmetry (ADS) method, the superposition model (SPM) analysis, and the pseudosymmetry axes method (PAM) is utilized to extract the crystal field (CF) parameters, B(kq), from experimental spectra. Corresponding sets of the free-ion parameters are also fitted. The crystallographic data are used to establish the axis systems most appropriate for approximation of the actual monoclinic C(2) site symmetry to higher orthorhombic D(2) and tetragonal D(4) symmetry used in CF calculations for BaY(2)F(8). Similarly, for triclinic C(1) site symmetry in LiKYF(5) and K(2)YF(5) approximation to monoclinic C(2) and orthorhombic D(2) symmetry for LiKYF(5), whereas the monoclinic C(s) symmetry for K(2)YF(5), are considered. It is shown that the C(2v) approximation used previously for K(2)YF(5):Nd(3+) is not suitable. SPM enables to calculate for the unapproximated and idealized polyhedrons YF(8) in a given ion-host system of the combined coordination factors Sg(k,q) expressed in the modified crystallographic axis system CAS* and approximated symmetry adapted axis systems, respectively. The quantities Sg(k,q) serve as input for PAM calculations for independent determination of the axis system appropriate for higher symmetry approximations. The pseudosymmetry axes represent the axis system that reflects most closely the approximated higher symmetry of the nearest ligands in a paramagnetic complex embodied in the 4th-rank CF parameters. The combined ADS/SPM/PAM approach provides sets of starting CF parameters (CFPs) in well-defined axis systems. Multiple fittings starting from different points in the CF parameter space yield converging solutions, thus increasing the reliability of the final optimized solutions, which may be then considered as the global minima. The present CF analysis, unlike the previous ones, takes into account the low symmetry aspects inherent in the CF Hamiltonian and optical spectra. The improved and more reliable sets of CFPs are generated as well as modified assignments of the CF energy levels are proposed for BaY(2)F(8):Nd(3+). The present considerations enable also clarification of some ambiguous points occurring in previous studies.

Spectroscopy of gadolinium gallium garnet crystals doped with Yb(3+) revisited.

The optical spectroscopy measurements of gadolinium gallium garnet (GGG) crystals doped with Yb show evidence of the presence of non-equivalent optical centers with very similar radiative decay rates. The energy level schemes of those centers have been determined on the basis of optical absorption, luminescence and Raman experiments. Crystal field fitting resulted in two sets of slightly different crystal field parameters for two non-equivalent Yb centers. Both sets of parameters describe perfectly the experimentally detected Yb(3+) energy levels. Correlation between systematic trends in the experimental energy level schemes and crystal field parameters is discussed.