Circularly Polarized Luminescence from Pure and Eu-Doped Trigonal TbPO4·nH2O Nanocrystals.

In this contribution, we describe the preparation, by means of a precipitation reaction from aqueous solution at 40 °C, and the structural characterization of nanocrystalline powders of trigonal Tb1-xEuxPO4·nH2O (with x = 0, 0.005, 0.01, 0.05, and 0.1; n tentatively assigned as 0.67) which crystallize in the two possible P3121 or P3221 enantiomorphic space groups. While the volume of the crystal lattice is not significantly affected by the Tb3+/Eu3+ substitution, the average crystallite size seems to depend on the Eu3+ dopant concentration and ranges from 13 to 30 nm. The desired handedness of the crystals has been induced by using, during the synthesis, one of the two possible enantiomers of tartaric acid (l or d). The analysis of the luminescence excitation and emission spectra, together with the decay kinetics of the 5D4 Tb3+ excited state, suggests the presence of a very efficient Tb3+ → Eu3+ energy transfer process in the Eu3+-doped orthophosphates. Upon excitation of Tb3+ ions at 368 nm, the enantiomorphic powders grown with l- or d-tartaric acid (i.e., l-TbPO4·0.67H2O/d-TbPO4·0.67H2O, l-Tb0.995Eu0.005PO4·0.67H2O/d-Tb0.995Eu0.005PO4·0.67H2O, and l-Tb0.9Eu0.1PO4·0.67H2O/d-Tb0.9Eu0.1PO4·0.67H2O) exhibited mirror circularly polarized luminescence signals in the visible spectral region (in the green and/or in the red).

Circularly Polarized Luminescence from New Heteroleptic Eu(III) and Tb(III) Complexes.

The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S1 and T1 ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (ηsens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕovl = 55%; ηsens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of glum (0.26) and a good quantum yield (26%) were measured.

Ln(III) Complexes Embedded in Biocompatible PLGA Nanoparticles as Potential Vis-to-NIR Optical Probes.

In this contribution, we present the spectroscopic study of two NIR emitting hydrophobic heteroleptic (R,R)-YbL1(tta) and (R,R)-NdL1(tta) complexes (with tta = 2-thenoyltrifluoroacetonate and L1 = N,N'-bis(2-(8-hydroxyquinolinate)methylidene)-1,2-(R,R or S,S)-cyclohexanediamine), both in methanol solution and embedded in water dispersible and biocompatible poly lactic-co-glycolic acid (PLGA) nanoparticles. Thanks to their absorption properties in a wide range of wavelengths extending from the UV up to the blue and green visible regions, the emission of these complexes can be effectively sensitized using visible radiation, which is much less harmful to tissues and skin than the UV one. The encapsulation of the two Ln(III)-based complexes in PLGA allows us to preserve their nature, making them stable in water and to test their cytotoxicity on two different cell lines, with the aim of using them in the future as potential bioimaging optical probes.

γ-BaFe2O4: a fresh playground for room temperature multiferroicity.

Multiferroics, showing the coexistence of two or more ferroic orderings at room temperature, could harness a revolution in multifunctional devices. However, most of the multiferroic compounds known to date are not magnetically and electrically ordered at ambient conditions, so the discovery of new materials is pivotal to allow the development of the field. In this work, we show that BaFe2O4 is a previously unrecognized room temperature multiferroic. X-ray and neutron diffraction allowed to reveal the polar crystal structure of the compound as well as its antiferromagnetic behavior, confirmed by bulk magnetometry characterizations. Piezo force microscopy and electrical measurements show the polarization to be switchable by the application of an external field, while symmetry analysis and calculations based on density functional theory reveal the improper nature of the ferroelectric component. Considering the present findings, we propose BaFe2O4 as a Bi- and Pb-free model for the search of new advanced multiferroic materials.

Efficient 1400-1600†nm Circularly Polarized Luminescence from a Tuned Chiral Erbium Complex.

Novel chiral Er complexes based on both enantiomers of extended i PrPyBox (2,6-Bis[4-isopropyl-4,5-dihydrooxazol-2-yl)]pyridine) show strong near-infrared circularly polarized luminescence (CPL) within the 1400 to 1600 nm spectral region under 450 nm irradiation. CPL activity in this region, despite being particularly rare, would open the way to potential applications in the domain, e.g., of fiber-optic telecommunications and free-space long-distance optical communications employing circularly polarized light. Moreover, the long wavelength excitation is advantageous for applications in the field of (circularly polarized) microscopy and bioimaging.

Near Infared Circularly Polarized Luminescence From Water Stable Organic Nanoparticles Containing a Chiral Yb(III) Complex.

We report the first example of very efficient NIR Circularly Polarized Luminescence (CPL) (around 970 nm) in water, obtained thanks to the combined use of a chiral Yb complex and of poly lactic-co-glycolic acid (PLGA) nanoparticles. [YbL(tta)2 ]CH3 COO (L=N, N'-bis(2-pyridylmethylidene)-1,2-(R,R+S,S) cyclohexanediamine and tta=2-thenoyltrifluoroacetonate) shows good CPL in organic solvents, because the tta ligands efficiently sensitize Yb NIR luminescence and the readily prepared chiral ligand L endows the complex with the necessary dissymmetry. PLGA nanoparticles incorporate the complex and protect the metal ion from the intrusion of solvent molecules, while ensuring biocompatibility, water solubility and stability to the complex. Hydrophilic NIR-CPL optical probes can find applications in the field of NIR-CPL bio-assays.

Synthesis, characterization and optical spectroscopy of GdPO4 :Er3.

A series of Er3+ -doped GdPO4 phosphors was synthesized using a conventional solid-state reaction. The monazite structure (space group P121 /n1 ) of the obtained materials was confirmed using X-ray diffraction and Fourier transform infrared spectroscopy. Their optical spectra (excitation, emission, absorption, decay curves) were measured at room temperature in the visible and near-infrared (NIR) regions. The UV-visible-NIR optical absorption spectrum of GdPO4 :7% Er3+ was analyzed based on Judd-Ofelt (J-O) theory and the J-O intensity parameter (Ω2 , Ω4 , Ω6 ) was calculated. J-O intensity parameters were used to evaluate spontaneous emission properties such as branching ratios, transition probabilities, and radiative lifetime. The calculated quantum efficiency of the 1.5 µm emission (4 I13/2 -4 I15/2 ) was calculated to be 89%. This result proved that GdPO4 :Er3+ is suitable for use in optical amplifiers and is a potential host for laser applications. The most interesting transitions, located at about 540 nm, and 1.0 and 1.5 µm were investigated as a function of doping level and of temperature, to assess the conditions needed for the highest emission performance and to explore the range of application, in particular in the fields of lighting, thermal sensing, and of phosphors for bio-imaging.

Nanophotonic rare-earth quantum memory with optically controlled retrieval.

Optical quantum memories are essential elements in quantum networks for long-distance distribution of quantum entanglement. Scalable development of quantum network nodes requires on-chip qubit storage functionality with control of the readout time. We demonstrate a high-fidelity nanophotonic quantum memory based on a mesoscopic neodymium ensemble coupled to a photonic crystal cavity. The nanocavity enables >95% spin polarization for efficient initialization of the atomic frequency comb memory and time bin-selective readout through an enhanced optical Stark shift of the comb frequencies. Our solid-state memory is integrable with other chip-scale photon source and detector devices for multiplexed quantum and classical information processing at the network nodes.

Tunable luminescence of Bi(3+)-doped YP(x)V(1-x)O4 (0 ≤ x ≤1).

A systematic investigation of the luminescence spectroscopy of Y(P,V)O4:Bi(3+) is presented. The emission spectra and the decay curves are measured as a function of the host morphology, composition, temperature, excitation wavelength, and doping concentration. On this basis, the nature of the excited states and the radiative and non-radiative relaxation processes are discussed. Colour coordinates and quantum yield measurements are also carried out to provide information about the potential applications of the studied materials.

Luminescence dynamics in Tb(3+)-doped CaWO(4) and CaMoO(4) crystals.

Single crystals of CaWO(4) and CaMoO(4) doped with Tb(3+) have been grown by the flux growth method. Their luminescence properties have been investigated in the 10-600 K temperature range under different experimental conditions. In spite of very similar spectra at low temperature upon excitation at 365 nm, the crystals show a very different behavior as the temperature is raised or the excitation wavelength is changed. These differences have been accounted for on the basis of models that take into consideration the position of the energy levels of the rare earth relative to the bandgap of the host material.

Lanthanide 4f-level location in AVO(4):Ln(3+) (A = La, Gd, Lu) crystals.

The spectral properties of LaVO(4), GdVO(4) and LuVO(4) crystals doped with Ce(3+), Pr(3+), Eu(3+) or Tb(3+) have been investigated in order to determine the position of the energy levels relative to the valence and conduction bands of the hosts along the trivalent and divalent lanthanide series. Pr(3+) and Tb(3+) ground state levels are positioned based on the electron transfer energy from those states to the conduction band, the so-called intervalence charge transfer (IVCT). This approach is compared with an alternative model that is based on electron transfer from the valence band to a lanthanide.

Information security concepts and practices: the case of a provincial multi-specialty hospital.

In recent years, major and widely accepted information security understandings and achievements confirm that the problem is complex. They clarify that technologies are fundamental tools, but management processes have even bigger relevance, as also prestigious international magazines dossier clearly explained recently. Such a magazine attention outlines the wide impact that the subject has on watchful decision makers. ISO17799 is an emerging standard in information security. In principle there are no reasons for considering it not applicable to the health care sector. In practice, because of both the just conceptual level of the standard and the peculiarities of the health care data and institutions, a lot of analysis and design work need to be invested any time a health care institution decides to deal with the subject. CEN/ENV 12924 is another emerging standard certainly more on the spot of the health care. Nevertheless, it also asks for evident further investigation. The practical case of information security design, implementation, management, and auditing inside a multi-specialty provincial Italian hospital will be described.