The quantum cutting of Tb(3+) in Ca(6)Ln(2)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) under VUV-UV excitation: with and without Gd(3+)

The VUV-vis spectroscopic properties of Tb(3+) activated fluoro-apatite phosphors Ca(6)Ln(2-x)Tb(x)Na(2)(PO(4))(6)F(2) (Ln = Gd, La) were studied. The results show that phosphors Ca(6)Gd(2-x)Tb(x)Na(2)(PO(4))(6)F(2) with Gd(3+) ions as sensitizers have intense absorption in the VUV range. The emission color of both phosphors can be tuned from blue to green by changing the doping concentration of Tb(3+) under 172 nm excitation. The visible quantum cutting (QC) via cross relaxation between Tb(3+) ions was observed in cases with and without Gd(3+). Though QC can be realized in phosphors Ca(6)La(2-x)Tb(x)Na(2)(PO(4))(6)F(2), we found that Gd(3+)-containg phosphors have a higher QC efficiency, confirming that the Gd(3+) ion indeed plays an important role during the quantum cutting process. In addition, the energy transfer process from Gd(3+) to Tb(3+) as well as (5)D(3)-(5)D(4) cross relaxation was investigated and discussed in terms of luminescence spectra and decay curves.     

Highly uniform and monodisperse Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres: solvothermal synthesis and luminescence properties

Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres were successfully prepared through a facile and mild solvothermal method followed by a subsequent heat treatment. X-ray diffraction (XRD) results demonstrate that all the diffraction peaks of the samples can be well indexed to the pure hexagonal phase of Gd(2)O(2)S. The energy dispersive spectroscopy (EDS), element analysis, and FT-IR results show that the precursors are composed of the Gd, Eu, O, S, C, H, and N elements. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that these spheres are actually composed of randomly aggregated nanoparticles. The formation mechanism for the Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres has been proposed on an isotropic growth mechanism. Under ultraviolet excitation, Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres show red and green emission corresponding to the (5)D(0)→(7)F(2) transition of the Eu(3+) ions and the (5)D(4)→(7)F(5) transition of the Tb(3+) ions. Furthermore, this synthetic route may have potential applications for fabricating other lanthanide oxysulfides.     

Patterning of Gd2(WO4)3:Ln3+ (Ln=Eu, Tb) luminescent films by microcontact printing route

Gd(2)(WO(4))(3) doped with Eu(3+) or Tb(3+) thin phosphor films with dot patterns have been prepared by a combinational method of sol-gel process and microcontact printing. This process utilizes a PDMS elastomeric mold as the stamp to create heterogeneous pattern on quartz substrates firstly and then combined with a Pechini-type sol-gel process to selectively deposit the luminescent phosphors on hydrophilic regions, in which a Gd(2)(WO(4))(3):Ln(3+) (Ln=Eu, Tb) precursor solutions were employed as ink. X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectra, as well as low voltage cathodoluminescence (CL) spectra were carried out to characterize the obtained samples. Under ultraviolet excitation and low-voltage electron beams excitation, the Gd(2)(WO(4))(3):Eu(3+) samples exhibit a strong red emission arising from Eu(3+)(5)D(0,1,2)-(7)F(1,2) transitions, while the Gd(2)(WO(4))(3):Tb(3+) samples show the green emission coming from the characteristic emission of Tb(3+) corresponding to (5)D(4)-(7)F(6,5,4,3) transitions. The results show that the patterning of rare earth-doped phosphors through combining microcontact printing with a Pechini-type sol-gel route has potential for field emission displays (FEDs) applications.     

W-Band pulse EPR distance measurements in peptides using Gd(3+)-dipicolinic acid derivatives as spin labels

We present high field DEER (double electron-electron resonance) distance measurements using Gd(3+) (S = 7/2) spin labels for probing peptides' conformations in solution. The motivation for using Gd(3+) spin labels as an alternative for the standard nitroxide spin labels is the sensitivity improvement they offer because of their very intense EPR signal at high magnetic fields. Gd(3+) was coordinated by dipicolinic acid derivative (4MMDPA) tags that were covalently attached to two cysteine thiol groups. Cysteines were introduced in positions 15 and 27 of the peptide melittin and then two types of spin labeled melittins were prepared, one labeled with two nitroxide spin labels and the other with two 4MMDPA-Gd(3+) labels. Both types were subjected to W-band (95 GHz, 3.5 T) DEER measurements. For the Gd(3+) labeled peptide we explored the effect of the solution molar ratio of Gd(3+) and the labeled peptide, the temperature, and the maximum dipolar evolution time T on the DEER modulation depth. We found that the optimization of the [Gd(3+)]/[Tag] ratio is crucial because excess Gd(3+) masked the DEER effect and too little Gd(3+) resulted in the formation of Gd(3+)-tag(2) complexes, generating peptide dimers. In addition, we observed that the DEER modulation depth is sensitive to spectral diffusion processes even at Gd(3+) concentrations as low as 0.2 mM and therefore experimental conditions should be chosen to minimize it as it decreases the DEER effect. Finally, the distance between the two Gd(3+) ions, 3.4 nm, was found to be longer by 1.2 nm than the distance between the two nitroxides. The origin and implications of this difference are discussed.     

Host sensitization of Tb3+ ions in tribarium lanthanide borates Ba3Ln (BO3)3 (Ln = Lu and Gd)

The vacuum-ultraviolet (VUV) spectroscopic properties of undoped and Tb(3+)-doped borates Ba(3)Ln(BO(3))(3) (Ln = Lu and Gd) with different crystal structures were investigated by using synchrotron radiation. Ba(3)Lu(BO(3))(3) (BLB) crystallizes in a hexagonal structure, whereas Ba(3)Gd(BO(3))(3) (BGB) crystallizes in a trigonal structure. The maximum host absorption for BLB and BGB was found to locate at ~179 and ~195 nm, respectively. Upon host excitation, BLB exhibits an intrinsic broad UV emission centered at 339 nm, which is attributed to the recombination of self-trapped excitons that may presumably be associated with band-gap excitations or molecular transitions within the BO(3)(3-) group. In contrast to BLB, no broad emission but line emission ascribed to a Gd(3+)(6)P(J)-(8)S(7/2) transition was observed in the emission spectrum of BGB. Upon doping of Tb(3+) ions into the hosts of BLB and BGB, an efficient energy transfer from the host excitations to Tb(3+) via host/Gd(3+) emission was observed, showing that host sensitization of Tb(3+) occurs in these rare-earth borates.     

Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study

Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.     

A luminescent and mesoporous core-shell structured Gd2O3 : Eu(3+)@nSiO2@mSiO2 nanocomposite as a drug carrier

In this paper, Gd(2)O(3) : Eu(3+) nanospheres have been encapsulated with nonporous silica and further layer of ordered mesoporous silica through a simple sol-gel process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N(2) adsorption/desorption, photoluminescence (PL) spectra, and kinetic decay were used to characterize the sample. The results indicate that the nanocomposite with general 50 nm shell thickness and 270 nm core size shows typical ordered mesoporous characteristics (2.4 nm) and has spherical morphology with a smooth surface and narrow size distribution. Additionally, the obtained inorganic nanocomposite shows the characteristic emission of Eu(3+) ((5)D(0)→(7)F(1-4)) even after the loading of drug molecules. The biocompatibility test on L929 fibroblast cells using MTT assay reveals low cytotoxicity of the system. Most importantly, the nanocomposite can be used as an effective drug delivery carrier. A typical anticancer drug, doxorubicin hydrochloride (DOX), was used for drug loading, and the DOX release, cytotoxicity, uptake behavior and therapeutic effects were examined. It was found that DOX is shuttled into the cell by the nanocomposite and released inside cells after endocytosis and that the DOX-loaded nanocomposite exhibited greater cytotoxicity than free DOX. These results indicate that core-shell structured Gd(2)O(3) : Eu(3+)@nSiO(2)@mSiO(2) nanocomposite has potential for drug loading and delivery into cancer cells to induce cell death.     

Luminescence and microstructures of Eu(3+)-doped Ca9LiGd(2/3)(PO4)7

A red-emitting phosphor, Eu(3+)-doped Ca(9)LiGd(2/3)(PO(4))(7), was synthesized by the conventional high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirmed the pure crystalline phase of Whitlockite-type structure. The excitation spectra of Eu(3+) doped Ca(9)LiGd(2/3)(PO(4))(7) were measured in the VUV and UV region indicating an efficient energy transfer process from the host and Gd(3+) to Eu(3+) ions. Upon excitation with VUV and UV radiation, the phosphor showed strong red emission around 611 nm corresponding to the forced electric dipole (5)D(0)→(7)F(2) transition of Eu(3+) ions. The VUV- and UV-excited luminescence spectra of Ca(9)LiGd(2/3)(PO(4))(7):Eu(3+) together with the dependence of the integrated emission intensities on the doping levels were investigated. The Eu(3+) ions were investigated by a tunable laser as an excitation source. The excitation spectra of (7)F(0)→(5)D(0) transitions suggest that there are two families of inequivalent sites for Eu(3+) in this host. The concentration quenching and crystallographic site-occupancy of Eu(3+) ions in Ca(9)LiGd(2/3)(PO(4))(7) host were discussed on the basis of the site selective excitation and emission spectra, the luminescence decay and its crystal structure.     

Preparation of Gd(2)O(3) : Eu(3+) and Gd(2)O(2)S : Eu(3+) phosphor fine particles using an emulsion liquid membrane system

Size- (submicrometer-sized) and morphology- (spherical) controlled composite Gd-Eu oxalate particles were prepared in an emulsion liquid membrane (water-in-oil-in-water emulsion) system. The oxalate particles thus prepared were calcined in air to obtain Gd(2)O(3) : Eu(3+) phosphor particles and in sulfur atmosphere to obtain Gd(2)O(2)S : Eu(3+) phosphor particles. These submicrometer-sized spherical phosphor particles showed photoluminescence properties with emission peak at 614 nm for Gd(2)O(3) : Eu(3+) and 628 nm for Gd(2)O(2)S : Eu(3+).     

Color-tunable Upconversion Properties of Tb~(3+)/Er~(3+)/Yb~(3+) Tri-doped Na_5Gd(WO_4)_4 Crystals

In this work, novel phosphors Na5Gd(WO4)4: Tb^3+/Yb^3+ and Na5Gd(WO4)4: Tb^3+/Er^3+/Yb^3+ phosphors were synthesized by the solid state reaction method. The photoluminescence properties were investigated. The introduction of Er^3+ to NGW: Tb^3+/Yb^3+ was used to modify the chromaticity coordinates, then providing a good color tunable property. The change in the chromaticity coordinates induces the shift of emission color from yellow-green to blue-green for NGW: Tb^3+/Er^3+/Yb^3+ as the temperature increases. All the results indicate that the NGW: Er^3+/Tb^3+/Yb^3+ phosphors may be used as optical temperature sensing materials.     

水热法制备多层核壳结构Gd_2O_3:Eu~(3+)空心微球

以稀土硝酸盐-葡萄糖的混合溶液作为前驱体,采用一步水热法和随后的热处理得到了多层核壳结构Gd_2O_3:Eu~(3+)空心微球,并用X-射线衍射(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、X-射线能量色散光谱(EDS)和荧光光谱等测试手段对所得样品进行了表征.结果表明:所得空心球样品为纯的立方相的Gd_2O_3.具有规则的多层核壳空心结构,空心球的直径在2～3μm左右,壁厚约为100 nml,并且Gd_2O_3:Eu~(3+)空心球是由尺寸约为30 nm的球形纳米颗粒白组装而成.样品中含有Gd、Eu、O元素.该空心球样品具有强的Eu~(3+)的特征红光发射以及长的荧光寿命,可以用来作为时间分辨荧光标记物.     

Distance measurements in Au nanoparticles functionalized with nitroxide radicals and Gd(3+)-DTPA chelate complexes

Nanosized gold particles were functionalised with two types of paramagnetic surface tags, one having a nitroxide radical and the other one carrying a DTPA complex loaded with Gd(3+). Selective measurements of nitroxide-nitroxide, Gd(3+)-nitroxide and Gd(3+)-Gd(3+) distances were performed on this system and information on the distance distribution in the three types of spin pairs was obtained. A numerical analysis of the dipolar frequency distributions is presented for Gd(3+) centres with moderate magnitudes of zero-field splitting, in the range of detection frequencies and resonance fields where the high-field approximation is only roughly valid. The dipolar frequency analysis confirms the applicability of DEER for distance measurements in such complexes and gives an estimate for the magnitudes of possible systematic errors due to the non-ideality of the measurement of the dipole-dipole interaction.     

Preparation of Self-assembled Eu^3＋：BaMoO4 Nanostructures with Lotus Leaf-shaped Morphology

The Eu^3＋：BaMoO4 nanostructures were synthesized by a simple hydrothermal method,and characterized by XRD,transmission electron microscopy,high-resolution transmission electron microscopy,excitation and emission spectra. Eu^3＋：BaMoO4 nanostructures show a lotus leaf-shaped morphology,and exhibit a strong red emission at 612 nm,which may afford an opportunity for the development of other nanostructure materials.     

Amplified surface plasmon resonance based DNA biosensors, aptasensors, and Hg2+ sensors using hemin/G-quadruplexes and Au nanoparticles

Thiolated nucleic acid hairpin nanostructures that include in their stem region a "caged" G-quadruplex sequence, and in their single-stranded loop region oligonucleotide recognition sequences for DNA, adenosine monophosphate (AMP), or Hg(2+) ions were linked to bare Au surfaces or to Au nanoparticles (NPs) linked to Au surfaces. The opening of the hairpin nanostructures associated with the bare Au surface by the complementary target DNA, AMP substrate, or Hg(2+) ions, in the presence of hemin, led to the self-assembly of hemin/G-quadruplexes on the surface. The resulting dielectric changes on the surface exhibited shifts in the surface plasmon resonance (SPR) spectra, thus providing a readout signal for the recognition events. A similar opening of the hairpin nanostructures, immobilized on the Au NPs associated with the Au surface, by the DNA, AMP, or Hg(2+) led to an ultrasensitive SPR-amplified detection of the respective analytes. The amplification originated from the coupling between the localized surface plasmon associated with the NPs and the surface plasmon wave, an effect that cooperatively amplifies the SPR shifts that result from the formation of the hemin/G-quadruplexes. The different sensing platforms reveal impressive sensitivities and selectivities toward the target analytes.     

Growth and Spectroscopic Properties of Nd3＋：Sr3Gd2（BO3）4 Crystal

<正>This paper reports the growth,X-ray diffraction and spectroscopy of Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal.A Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal with dimensions ofφ20×45 mm~3 has been grown by the Czochralski method.Nd~(3+):Sr_3Gd_2(BO_3)_4 crystal belongs to the orthorhombic system,space group Pnma(D_(2h))with a=0.7401,b=1.604 and c=0.8755 nm.The absorption and emission spectra of Nd~(3+):Sr_3Gd_2(BO_3)_4 were investigated.The absorption cross sectionσ_a is 3.11×10~(-20)cm~2 at 808 nm. The absorption transition at 808 nm has an FWHM of 14 nm.The luminescence lifetimeτ_f is 51.7 us.The emission cross sectionσ_e at 1064 nm wavelength is 1.09×10~(-19)cm~2.     

Organosulfur-functionalized Au, Pd, and Au-Pd nanoparticles on 1D silicon nanowire substrates: preparation and XAFS studies

A hybrid preparative method was developed to prepare organosulfur-functionalized Au nanoparticles (NPs) on silicon nanowires (SiNWs) by reacting HAuCl(4) with SiNW in the presence of thiol. A number of organosulfur molecules-dodecanethiol, hexanethiol, 1,6-hexanedithiol, and tiopronin-were used to functionalize the Au surface. Size-selected NPs ranging from 1.6 to 7.5 nm were obtained by varying the S/Au ratio and the concentration of HAuCl(4). This method was further extended to the preparation Pd and Pd-Au bimetallic NPs on SiNWs. The morphology of the metal nanostructures was examined by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The local structure and bonding of the SiNW-supported metal nanostructures were studied using X-ray absorption fine structures (XAFS) [including both X-ray near-edge structures (XANES) and extended X-ray absorption fine structures (EXAFS)] at the Au L(3)-, Pd K-, S K-, and Si K-edges. It was also found that the annealing of the thiol-capped Au NPs up to 500 degrees C transforms the surface of the thiol-capped NPs to gold sulfide, as identified using Au L(3)- and S K-edge XANES. We also illustrate that this preparative approach can be used to form size-controllable Au NPs on carbon nanotubes.     

Synthesis and Characterization of Highly Efficient Photoluminescence Gd doping Hexagonal CePO_4 (One-dimensional Nanowires)

Rare earth phosphates have been used extensively in luminescent phosphors. Hexagonal Ce_(1-x)Gd_xPO_4 with crystal field manipulation was successfully synthesized using a hydrothermal method. The photoluminescence emission intensity of hexagonal CePO_4 was obviously enhanced by the crystal structure manipulation with gadolinium ions codoping. Compared to pure CePO_4, the intensity photoluminescence was enhanced about 15 folds with x = 0.05. The effect of gadolinium doping was systematically investigated by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. Crystal field asymmetry can be effectively tuned by different amount of Gd~(3+) codoping, and the crystal field asymmetry is conductive to electron population of high energy level of Ce~(3+) ions. This material has potential applications in optics, electronics fields, and so on. Meanwhile, the method can be extended to another kind of high performance photoluminescence materials preparation.     

Bifunctional Mixed-Lanthanide Cyano-Bridged Coordination Polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), Tb(3+)/Sm(3+))

A new family of mixed-lanthanide cyano-bridged coordination polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (where Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), and Tb(3+)/Sm(3+)) containing two lanthanide and one transition metal ions were obtained and characterized by X-ray diffraction, photoluminescence spectroscopy, magnetic analyses, and theoretical computation. These compounds are isotypical and crystallize in the tetragonal system P4/nmm forming two-dimensional grid-like networks. They present a magnetic ordering at low temperature and display the red Eu(3+) ((5)D(0) → (7)F(0-4)) and green Tb(3+) ((5)D(4) → (7)F(6-2)) characteristic photoluminescence. The Tb(0.5)Eu(0.5)(H(2)O)(5)[W(CN)(8)] compound presents therefore green and red emission and shows Tb(3+)-to-Eu(3+) energy transfer.     

Crystal Growth,Structure, and Spectral Properties of Cr~(4+):Ca_2(Al_(1.8)Ga_(0.2))SiO_7

A new crystal, Ca_2(Al_(1.8)Ga_(0.2))SiO_7, was obtained by substituting Ga~(3+) ions for some Al~(3+) ions in Ca_2Al_2SiO_7 crystal. The growth, structure and optical spectroscopic properties of Cr~(4+)-doped Ca_2(Al_(1.8)Ga_(0.2))SiO_7 were studied. It shows strong absorption at 693 and 762 nm and a broad emission band with peak wavelength at 1223 nm. Both the absorption and emission peaks of Cr_(4+)-doped Ca_2(Al_(1.8)Ga_(0.2))SiO_7 crystal are red-shifted in comparison with that of Cr~(4+)-doped Ca_2Al_2SiO_7 crystal due to its weaker lattice field. The investigation results show that there is only one kind of tetrahedral site for Cr~(4+) occupation in the lattice of Ca_2(Al_(1.8)Ga_(0.2))SiO_7 crystal.     

铽-铕共掺杂的硅酸铝钠荧光体的光致发光性能及能量传递

采用温和的固相反应法合成了具有四方相结构的铽一铕共掺杂的硅酸铝钠(NaAlSiO_4:Tb~(3+),Eu~(3+))发光材料.利用粉末X射线衍射(XRD)、荧光光谱(PL)、时间分辨光谱(TRPL)以及荧光寿命等手段对合成的样品进行表征.研究结果表明:通过改变NaAlSiO_4:Tb~(3+),Eu~(3+)中Eu~(3+)离子的掺杂浓度,可实现其绿光及红光发射的调控;由于Tb~(3+),Eu~(3+)离子间的有效能量传递,Tb~(3+)离子的共掺杂可显著增强该基质中Eu~(3+)离子的发光性能;该能量传递现象可由TRPL光谱等手段进行证实,根据荧光寿命的数值计算可知,从Tb3~(3+)向Eu~(3+)离子的能量传递效率高达95%.