Excitation-Controlled Host-Guest Multicolor Luminescence in Lanthanide-Doped Calcium Zirconate for Information Encryption.

Efficient control over lanthanide luminescence by regulating excitations offers a real-time and reversible luminescence-managing strategy, which is of great importance and highly desirable for various applications, including multicolor display and information encryption. Herein, we studied the crystal structure, luminescence properties, and mechanisms of undoped and Tb3+/Eu3+-doped CaZrO3 in detail. The intrinsic purple-blue luminescence from host CaZrO3 and the introduced green/red luminescence from guest dopants Tb3+/Eu3+ were found to have different excitation mechanisms and, therefore, different excitation wavelength ranges. This enables the regulation of luminescent color through controlling the excitation wavelengths of Tb3+/Eu3+-doped CaZrO3. Furthermore, preliminary applications for information encryption with these materials were demonstrated using portable UV lamps of 254 and 302 nm. This study not only promotes the development of multicolor luminescence regulation in fixed-composition materials, but also advances the practical applications of lanthanide luminescent materials in visually readable, high-level anti-counterfeiting and information encryption.

Intravenous Hemostats: Foundation, Targeting, and Controlled-Release.

Uncontrollable blood loss is the greatest cause of mortality in prehospital patients and the main source of disability and death in hospital care. Compared with external hemostats, intravenous hemostats are more appropriate for preventing and treating uncontrolled bleeding in vivo and large bleeding on the body surface. This Review initially establishes intravenous hemostats' response basis, including the coagulation mechanism, fibrinolytic pathway, and protein corona. Second, the study of advancement of intravenous hemostat targeting was expanded from two perspectives, cellular hemostatic agents and synthetic hemostatic agents. Meanwhile, after discussing the progress of controlled-release intravenous hemostats with platelets as the stimuli, this Review offers insight into the possibility of controlled-release intravenous hemostats with microenvironment as the stimuli, combining the studies of controlled-release targeted thrombolysis.

Energy Transfer from Pr3+ to Gd3+ and Upconversion Photoluminescence Properties of Y7O6F9:Pr3+, Gd3.

Upconversion materials have numerous potential applications in light energy utilization due to their unique optical properties. The use of visible light excitation to obtain ultraviolet emission is a promising technology with broad application prospects, while relevant research is absent. A series of Pr3+, Gd3+ doped Y7O6F9 phosphors were synthesized by traditional solid-state reaction. X-ray diffraction, scanning electronic microscopy, steady-state photoluminescence spectra, a decay dynamic, and upconversion emission spectra of the samples were studied. Under the excitation of 238 nm, the energy transfer from Pr3+ to Gd3+ was realized and a strong ultraviolet B emission due to the 6P7/2→8S7/2 transition of the Gd3+ ions was achieved. Under the excitation of a 450 nm blue laser, Pr3+ absorbed two blue photons to realize the upconversion process and then transferred the energy to Gd3+ to obtain the ultraviolet B emission.

One ion to catch them all: Targeted high-precision Boltzmann thermometry over a wide temperature range with Gd3.

Ratiometric luminescence thermometry with trivalent lanthanide ions and their 4fn energy levels is an emerging technique for non-invasive remote temperature sensing with high spatial and temporal resolution. Conventional ratiometric luminescence thermometry often relies on thermal coupling between two closely lying energy levels governed by Boltzmann's law. Despite its simplicity, Boltzmann thermometry with two excited levels allows precise temperature sensing, but only within a limited temperature range. While low temperatures slow down the nonradiative transitions required to generate a measurable population in the higher excitation level, temperatures that are too high favour equalized populations of the two excited levels, at the expense of low relative thermal sensitivity. In this work, we extend the concept of Boltzmann thermometry to more than two excited levels and provide quantitative guidelines that link the choice of energy gaps between multiple excited states to the performance in different temperature windows. By this approach, it is possible to retain the high relative sensitivity and precision of the temperature measurement over a wide temperature range within the same system. We demonstrate this concept using YAl3(BO3)4 (YAB):Pr3+, Gd3+ with an excited 6PJ crystal field and spin-orbit split levels of Gd3+ in the UV range to avoid a thermal black body background even at the highest temperatures. This phosphor is easily excitable with inexpensive and powerful blue LEDs at 450 nm. Zero-background luminescence thermometry is realized by using blue-to-UV energy transfer upconversion with the Pr3+-Gd3+ couple upon excitation in the visible range. This method allows us to cover a temperature window between 30 and 800 K.

Citrate-Complexation Synthesis and Photoluminescence Properties of Y6MoO12:Eu Nanocrystalline.

Y6MoO12 doped with Eu3+ was synthesized using a citrate-complexation route, and was calcined at 800 °C and 1400 °C, respectively. The structure, morphology and photoluminescence (PL) properties of the samples, and their dependence on the crystallite size were investigated. XRD patterns indicate that the Y6MoO12:Eu3+ powder was obtained at both calcination temperatures, and had a cubic structure. The results also suggest that Y6MoO12:Eu3+ calcined at 800 °C was in the nanocrystalline phase, which was confirmed by the SEM microimage. The crystalline size was about 140 nm. Both phosphors could be excited via three channels: f-f excitation of Eu3+ by blue light, MoO groups excitation by near-UV light, and charge transfer state excitation of Eu3+ by UV light. Both samples yielded red light emissions dominated by the 5D0-7F2 transition at 613 nm. The excitation efficient of the three channels depended on the calcination temperature. The energy transfer from the MoO groups to the Eu3+ ions was more effective in the nanocrystalline phase. The temporal decay feature of the phosphor was also characterized.

Wide-band excited Y6(WMo)(0.5)O12:Eu red phosphor for white light emitting diode: structure evolution, photoluminescence properties, and energy transfer mechanisms involved.

Y6(WMo)(0.5)O12 activated with Eu(3+) ions was investigated as a red-emitting conversion phosphor for white light emitting diodes (WLEDs). The phosphors were synthesized by calcining a citrate-complexation precursor at different temperatures. The photoluminescence properties of the phosphors and the energy transfer mechanisms involved were studied as a function of structure evolution. It was found that the host lattices were crystallized in a cubic or a hexagonal phase depending on the synthesis conditions. Although all the phosphors showed intensive red emission under an excitation of near-UV or blue light due to energy transfer from the host lattices to Eu(3+) ions, the photoluminescence spectra and temporal decay features were found to vary significantly with the structure and crystallinity of the host lattice. The mechanisms of the energy transfer from the host lattices to Eu(3+) ions and energy quenching among Eu(3+) ions were discussed on the basis of structure evolution of the host lattice. Phosphors calcined at 800 and 1300 °C were suggested to be promising candidates for blue and near-UV light excited WLEDs, respectively.

Crystal structure, electronic structure, and optical and photoluminescence properties of Eu(III) ion-doped Lu6Mo(W)O12.

Lu(6)WO(12) and Lu(6)MoO(12) doped with Eu(3+) ions have been prepared by using a citrate complexation route, followed by calcination at different temperatures. The morphology, structure, and optical and photoluminescence properties of the compounds were studied as a function of calcination temperature. Both compositions undergo transitions from a cubic to a hexagonal phase when the calcination temperature increases. All the compositions have strong absorption of near-UV light and show intense red luminescence under a near-UV excitation, which is related to the transfer of energy from the host lattices to dopant Eu(3+) ions. Density functional theory calculations have also been performed. The calculation reveals that hexagonal Lu(6)WO(12) and Lu(6)MoO(12) are indirect bandgap materials, and the near-UV excitations are due to the electronic transitions from the O-2p orbitals to W-5d and Mo-4d orbitals, respectively. The lattice parameters and bandgap energies of hexagonal Lu(6)WO(12) and Lu(6)MoO(12) were determined.

Bonding characteristics, thermal expansibility, and compressibility of RXO(4) (R = rare earths, X = P, As) within monazite and zircon structures.

Systematically theoretical research was performed on the monazite- and zircon-structure RXO(4) (R = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; X = P, As) series by using the chemical bond theory of dielectric description. The chemical bond properties of R-O and X-O bonds were presented. In the zircon phase, the covalency fractions of X-O bonds increased in the order of V-O < As-O < P-O, which was in accordance with the ionic radii and electronegative trends, and the covalency fractions of R-O bonds varied slightly due to the lanthanide contraction. While in the monazite phase, both R-O and X-O bonds were divided into two groups by their covalency fractions. The contributions from the bond to the lattice energy, linear thermal expansion coefficient (LTEC), and bulk modulus were explored. The X-O bonds with short bond lengths and high chemical valence made greater contributions to the lattice energy and performed nearly rigidly during the deformation. A regular variation of lattice energy, LTEC, and bulk modulus with the ionic radii of the lanthanides was observed in both monazite and zircon phases.

Investigation of chemical bond characteristics, thermal expansion coefficients and bulk moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by using a dielectric chemical bond method.

Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy.

Investigation of thermal expansion and compressibility of rare-earth orthovanadates using a dielectric chemical bond method.

The chemical bond properties, lattice energies, linear expansion coefficients, and mechanical properties of ReVO 4 (Re = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y) are investigated systematically by the dielectric chemical bond theory. The calculated results show that the covalencies of Re-O bonds are increasing slightly from La to Lu and that the covalencies of V-O bonds in crystals are decreasing slightly from La to Lu. The linear expansion coefficients decrease progressively from LaVO 4 to LuVO 4; on the contrary, the bulk moduli increase progressively. Our calculated results are in good agreement with some experimental values for linear expansion coefficients and bulk moduli.

Self-assembled 3D architectures of LuBO3:Eu(3+): phase-selective synthesis, growth mechanism, and tunable luminescent properties.

Rhombohedral-calcite and hexagonal-vaterite types of LuBO(3):Eu(3+) microparticles with various complex self-assembled 3D architectures have been prepared selectively by an efficient surfactant- and template-free hydrothermal process for the first time. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, photoluminescence, and cathodoluminescence spectra as well as kinetic decays were used to characterize the samples. The pH, temperature, concentration, solvent, and reaction time have a crucial influence on the phase formation, shape evolution, and microstructure. The reaction mechanism is considered as a dissolution/precipitation process; it is proposed that the self-assembly evolution occurs by homocentric layer-by-layer growth. Under UV excitation and low-voltage electron beam excitation, calcite-type LuBO(3):Eu(3+) particles show a strong orange emission corresponding to the (5)D(0)-->(7)F(1) transition of Eu(3+) whereas vaterite-type LuBO(3):Eu(3+) particles exhibit a strong red emission with much higher R/O values (that is, chromatically redder fluorescence than that of crystals grown from a direct solid-state reaction). The tunable luminescent properties have potential applications in fluorescent lamps and field emission displays.

Calculation of the bulk modulus of simple and complex crystals with the chemical bond method.

The relation between the lattice energies and the bulk moduli on binary inorganic crystals was studied, and the concept of lattice energy density is introduced. We find that the lattice energy densities are in good linear relation with the bulk moduli in the same type of crystals, the slopes of fitting lines for various types of crystals are related to the valence and coordination number of cations of crystals, and the empirical expression of calculated slope is obtained. From crystal structure, the calculated results are in very good agreement with the experimental values. At the same time, by means of the dielectric theory of the chemical bond and the calculating method of the lattice energy of complex crystals, the estimative method of the bulk modulus of complex crystals was established reasonably, and the calculated results are in very good agreement with the experimental values.