Search

In this paper, a series of Tb 3+ /Dy 3+ /Mn 2+ doped CePO 4 downconversion nanophosphors (DCNPs) were prepared by a one-pot hydrothermal process. The obtained DCNPs presented monoclinic and hexagonal phase structure with wire-like shape. The photoluminescence (PL) properties and the energy transfer (ET) mechanism of these DCNPs were investigated in detail. The ET mechanism of Ce 3+ /Tb 3+ in CePO 4 host was calculated by means of concentration quenching and spectral overlapping, and calculation results revealed that dipole–dipole interactions should be more responsible. The maximum value of ET efficiency was measured to 87.4% for Tb 3+ doped CePO 4 system. In addition, owing to the efficient ET between Ce 3+ and Tb 3+ /Dy 3+ /Mn 2+ , these as-prepared DCNPs exhibit tunable multi-color output under ultra-violet (UV) light excitation. More importantly, the intense cold and warm white emissions can be realized by singly doping 2%Dy 3+ and 20%Mn 2+ in CePO 4 host under UV irradiation, respectively. The corresponding CIE 1931 coordinates were calculated to be (0.30, 0.30) and (0.30, 0.32), respectively, which are closed to the standard white emission (0.33, 0.33). These findings demonstrate the efficient white light emission by singly doped Dy 3+ or Mn 2+ in CePO 4 system for the first time, which is different from commonly used co-doped or tri-doped system. The multicolor tuning and white emission make these Tb 3+ /Dy 3+ /Mn 2+ doped CePO 4 DCNPs potential phosphors in the fields of displays, lighting, and field-emission devices.

In this paper, the monodispersed NaErF 4 :Yb, Mn nanoparticles (NPs) were successfully synthesized by a simple and mild solvothermal method. The as-prepared NPs were characterized by X-ray diffraction, transmission electron microscopy, and spectrophotometer. The crystal phase, size, morphology, and upconversion (UC) properties of these NPs can be readily tuned by doping Mn 2+ . With increasing Mn 2+ contents, the crystal phase of NaErF 4 :Yb NPs was transferred from hexagonal to cubic, and then a new orthorhombic phase NaMn 3 F 10 appeared. The morphology of NaErF 4 :Yb was tuned from nanodisks to nanocubes and then to large nanoflakes with increasing Mn 2+ dopant contents. Moreover, the UC luminescence (UCL) intensity can be enhanced by increasing Mn 2+ content. Interestingly, single-band red emission can be achieved when the Mn 2+ content reaches 20%. This is mainly ascribed to the efficient energy transfer between Er 3+ and Mn 2+ . The enhanced UCL intensity and single-band red UCL make these NaErF 4 :Yb/Mn NPs ideal probes for optical bioimaging owing to the low tissue absorption and deep tissue penetration of red light.

A strategy is demonstrated for simultaneous phase/size manipulation, multicolor tuning, and remarkably enhanced upconversion luminescence (UCL), particularly in red emission bands in fixed formulae of general lanthanide-doped upconverting nanoparticles (UCNPs), namely NaLnF4:Yb/Er (Ln: Lu, Gd, Yb), simply through transition metal Mn2+-doping. The addition of different Mn2+ dopant contents in NaLnF4:Yb/Er system favors the crystal structure changing from hexagonal (β) phase to cubic (α) phase, and the crystal size of UCNPs can be effectively controlled. Moreover, the UCL can be tuned from green through yellow and to dominant red emissions under the excitation of 980 nm laser. Interestingly, a large enhancement in overall UCL spectra of Mn2+ doped UCNPs (∼59.1 times for NaLuF4 host, ∼39.3 times for NaYbF4 host compared to the UCNPs without Mn2+ doping) is observed, mainly due to remarkably enhanced luminescence in the red band. The obtained result greatly benefits in vitro and in vivo upconversion bioimaging with highly sensitive and deeper tissue penetration. To prove the application, a select sample of nanocrystal is used as an optical probe for in vitro cell and in vivo bioimaging to verify the merits of high contrast, deeper tissue penetration, and the absence of autofluorescence. Furthermore, the blood vessel of lung of a nude mouse with the injection of Mn2+-doped NaLuF4: Yb/Er UCNPs can be readily visualized using X-ray imaging. Therefore, the Mn2+ doping method provides a new strategy for phase/size control, multicolor tuning, and remarkable enhancement of UCL dominated by red emission, which will impact on the field of bioimaging based on UCNP nanoprobes.

In this paper, the lanthanide (Ln) doped fluorescent/magnetic NaYbF 4 microtubes with hexagonal phase were synthesized via a hydrothermal method using oleic acid as a capping ligand and surface modifier. The as-prepared samples were characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), upconversion luminescence (UCL) spectra, and vibrating sample magnetometer (VSM). The TEM and FE-SEM observations revealed that the NaYbF 4 microtubes present high quality hexagonal prism shape. Under the excitation of a 980 nm laser diode (LD) with a power density of 0.5 W cm −2 , the UCL colors can be tuned from purplish blue to blue, greenish white, and further to yellowish green by adjusting the Tm 3+ and Ho 3+ content in NaYbF 4 system. Moreover, the brighter greenish white light can be readily achieved via increasing excitation power. The UCL mechanisms for the white emission were proposed based on the spectral and pumping power dependence analyses. Moreover, these as-prepared NaYbF 4 microtubes exhibit excellent paramagnetic property at room temperature. The magnetic mass susceptibility and magnetization are measured to 4.17 × 10 −5 emu/gOe and ∼0.84 emu g −1 at 20 kOe, respectively. Therefore, these NaYbF 4 microtubes with hexagonal prism shape, tunable multicolor UCL and excellent paramagnetic property imply that NaYbF 4 is an excellent host material and may find applications in flat-panel displays, lasers photonics and dual-modal bioprobes.

Herein, a series of hexagonal phase lanthanide (Ln3+, Ln3+ = Eu3+, Dy3+, Tb3+) doped NaCeF4 nanorods (NRs) with uniform morphology and monodispersity have been successfully synthesized via a typical hydrothermal method using oleic acid as the capping agent. The crystal phase and microstructure of the obtained NRs were analyzed by X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM). The down conversion (DC) luminescence properties and mechanisms of the as-prepared NaCeF4:Ln3+ NRs have been discussed in detail. The as-prepared samples show the characteristic f–f transition of Ln3+ (Ln3+ = Eu3+, Dy3+, Tb3+). The decay time and quantum yield of these obtained NRs are also studied. Moreover, tunable multicolor, especially white emissions, can be successfully achieved via varying the doping ions and doping concentration. By increasing the content of Eu3+, the emission colors vary from light green to white and finally to light red under the excitation of 395 nm. The calculated CIE coordinates of the obtained white emissions are (0.33, 0.31), which are very close to the standard white light located at (0.33, 0.33). This is the first time to demonstrate that white light emission is achieved via only singly-doping Eu3+ into the NaCeF4 system. In addition, the multicolor output changes from yellowish-green to yellow under the excitation at 261 nm, which was also obtained by only tuning the doped content of Dy3+ in the NaCeF4 host. As for Tb3+, bright yellowish green emissions were obtained under excitation at 261 nm. Moreover, the cathodoluminescence (CL) spectra demonstrate that these NRs can emerge as ideal nanophosphors under electron beam excitation. Therefore, the as-prepared NaCeF4:Ln3+ NRs with tunable multicolor output and bright white emissions might be applied in field-emission devices, multicolor displays and solid state lasers.

Small-sized BaLaF5:Mn/Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized for dual-modal X-ray and upconversion (UC) luminescence bioimaging by a simple solvothermal method. The size, shape, and UC luminescence intensity of the as-prepared UCNPs can be readily modified by changing the contents of Mn2+. The size of BaLaF5 UCNPs doped with Mn2+ decreased largely compared with Mn-free UCNPs. When increasing the content of Mn2+ from 5% to 20%, the size of UCNPs was gradually increased from 6.5 nm to 9.7 nm. The as-prepared BaLaF5 UCNPs doped with 20% Mn2+ present intense UC luminescence. The in vitro UC luminescence imaging of HeLa cells and localized spectra detected from HeLa cells and the background based on these BaLaF5:Mn/Yb/Er (20/20/2%) UCNPs indicate that this sample can serve as an ideal bioprobe with the absence of autofluorescence under the excitation of 980 nm laser. Moreover, an obvious UC signal was observed in in vivo UC bioimaging, demonstrating that these BaLaF5:Mn/Yb/Er (20/20/2%) UCNPs can also be used as bioprobes for whole body optical bioimaging. In addition, owing to the high X-ray mass absorption coefficients of Ba2+, La3+ and the doped Yb3+, the simultaneous X-ray and UC in vivo bioimaging of a nude mouse further demonstrate that the as-prepared UCNPs can be successfully used as dual-modal bioprobes. Ex vivo UC bioimaging revealed that these UCNPs gathered at the lung of a mouse at the initial time, demonstrating that this sample was suitable for the detection of the lung diseases. In addition, the cytotoxicity test showed that the UCNPs possessed little toxicity. Therefore, the small-sized BaLaF5:Yb/Er/Mn UCNPs are ideal nanoprobes for dual-modal UC luminescence/X-ray bioimaging with non-autofluorescence, and enhanced detection of the lung diseases.

In this paper, we report a self-sacrificing route for fabrication of the Ce/Tb co-doped GdPO4 hollow spheres under hydrothermal conditions using the Gd(OH)CO3:Ce/Tb precursor as a template and NH4H2PO4 as a phosphorus source. The X-ray diffraction (XRD) patterns show the amorphous crystal nature of the precursor and pure hexagonal phase of the hollow spheres. The microstructures of the as-prepared precursor and hollow spheres were characterized by transmission electron microscopy (TEM) and scanning TEM (STEM) assays. The results reveal the urchin-like morphology of the solid precursor and hollow spheres. Bright green emissions of the spheres have been detected using an ultraviolet (UV) lamp at 288 nm and the calculated CIE coordinates are (0.289, 0.491). The energy transfer mechanism of Ce and Tb ions in the GdPO4 host has been investigated. The quantum efficiency of the hollow spheres was measured to be 61% and the lifetime calculated as 6.94 ms. In addition, the magnetic mass susceptibilities and magnetization of the spheres are found to be 6.39 × 10−5 emu gOe−1 and 1.27 emu g−1 at 20 kOe, respectively. Owing to their excellent downshift luminescence properties, the as-prepared GdPO4:Ce/Tb hollow spheres have been successfully applied in in vivo luminescence and X-ray bioimaging for the first time. Moreover, three-dimensional (3D) in vivo X-ray bioimaging of the mouse can provide the accurate location from multiple directions. The high contrast ratio makes the spheres a promising X-ray contrast agent. Due to the hollow structure, these GdPO4:Ce/Tb hollow spheres were also used as drug delivery systems for doxorubicin (DOX) loading and release. The drug loading efficiency was measured to be 17% at a pH value of 7.4, and the pH-dependent drug release was studied. 47% of the loaded DOX was released within 10 h when pH = 5, while there was only 30% during the same time at pH = 7.4 and it took nearly 48 h to reach a comparable level. The different release nature gives these spheres a promising application in targeted therapy of tumors.

Yb/Er codoped Gd(OH)3was synthesized firstly via a simple hydrothermal treatment of the corresponding nitrate in the presence of alkali by tuning the pH values. The Gd2O3:Yb/Er nanocrystals were obtained via sintering the corresponding hydroxides precursors. The as-prepared samples were characterized by the typical X-ray diffraction, energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), high-resolution TEM, and spectrophotometer. The results revealed that two shapes of the as-prepared Gd2O3:Yb/Er nanocrystals can be readily tuned from lemon-like particle to rod-like structure via tuning pH values from 7 to 14. Moreover, compared with the samples prepared at pH 7, the Gd2O3:Yb/Er nanocrystals prepared at pH 14 exhibit enhanced red upconversion emission and higher upconversion luminescence intensity under the excitation of 980 nm laser.

In this work, we developed a novel and biocompatible dual-modal nanoprobe based on single-phase amine-functionalized BaYF5:Yb/Er nanoparticles (NPs) for upconversion (UC) fluorescence and in vivo computed X-ray tomography (CT) bioimaging for the first time. High-quality water-soluble amine-functionalized BaYF5:Yb/Er NPs with an average size of 24 nm were synthesized by a facile environmentally friendly hydrothermal method for simultaneous synthesis and surface functionalization. Structure investigation based on the Rietveld refinement method revealed that the as-synthesized BaYF5:Yb/Er NPs present a cubic phase structure, which differs from the previously reported tetragonal structure. Under 980 nm excitation, high-contrast green and red UC emissions were observed from HeLa cells incubated with these amine-functionalized NPs. The UC spectra measured from the NPs incubated with HeLa cells presented only green and red UC emissions without any autofluorescence, further revealing that these NPs are ideal candidates for fluorescent bioimaging. In addition, the cell cytotoxicity test showed low cell toxicity of these NPs. These amine-functionalized NPs were also successfully used as CT agents for in vivo CT imaging because of the efficient X-ray absorption efficiency of Ba and doped Yb ions. A prolonged (2 h) signal enhancement of the spleen in a mouse was observed in CT imaging, which can improve the detection of splenic diseases. More importantly, the simultaneous X-ray and UC in vivo bioimaging was demonstrated in a nude mouse for the first time, indicating the as-prepared UCNPs can be successfully used as dual-modal bioprobes. These results demonstrate that BaYF5:Yb/Er NPs are ideal nanoprobes for dual-modal fluorescent/CT bioimaging with low cytotoxicity, non-autofluorescence, and enhanced detection of the spleen.