Ga3+ as a functional substitute for Fe3+: preparation and characterization of the Ga3+Fe2+ and Ga3+Zn2+ forms of bovine spleen purple acid phosphatase

A general method has been developed that allows the specific substitution of both iron atoms in the enzyme bovine spleen purple acid phosphatase (BSPAP), which possesses a dinuclear iron center at the active site. The approach is demonstrated by the preparation and characterization (atomic absorption spectrometry, enzyme kinetics, optical spectroscopy, and electron paramagnetic resonance spectroscopy) of two metal-substituted forms in which the ferric iron has been replaced by Ga3+: Ga3+Fe2+-BSPAP and Ga3+Zn2+-BSPAP. Both forms are colorless but exhibit enzymatic activity comparable to that of the native Fe3+Fe2+-BSPAP. Small but consistent changes in kinetics parameters and pH profiles were detected both upon substitution of Fe3+ by Ga3+ and upon substitution of Fe2+ by Zn2+. These results constitute the first evidence that the diamagnetic Ga3+ ion can serve as a functional analogue of Fe3+ in an enzyme, and suggest a novel approach for the study of the role of Fe3+ in other iron enzymes.     

Photoluminescence of BaGdB9O（16）：Eu^3＋ co-doped Al^3＋ or Sc^3＋ under UV-VUV excitation

Single phase of BaGd0.9-xMxEu0.1B9O16 (M=Al or Sc, 0≤x≤0.3) powder was prepared by the solid-state reaction and its photoluminescence (PL) properties were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) excitation. Monitored with 613 nm emission, the excitation spectra of BaGd0.9-xMxEu0.1B9O16 consisted of three broad bands peaking at about 242, 208, and 142 nm, respectively. The one at about 242 nm originated from the charge transfer band (CTB) of O2-→Eu3+. The other two were assigned to the absorption of the host, which was overlapped with absorptions among borate groups, f→d transition of RE3+ (RE=Gd, Eu), and the charge transfer transition of O2-→Gd3+. The maximum emission peak was observed at about 613 nm in the emission spectra of BaGd0.9-xMxEu0.1B9O16 under both 254 and 147 nm excitation, which originated from the electric dipole 5D0→7F2 transition of Eu3+. When excited with 254 nm, the integral emission intensity of Eu3+ increased after Al3+ or Sc3+ substituting Gd3+ partly in BaGd0.9Eu0.1B9O16. Under 147 nm excitation, the integral emission intensity of Eu3+ decreased after some Gd3+ was replaced by Sc3+, but increased after adding appropriate Al3+ into BaGd0.9Eu0.1B9O16.     

Energy transfer between Gd^3＋ and Tb^3＋ in phosphate glass

The phosphate glass doped with Gd3+,Tb3+ and Gd3+/Tb3+ were prepared by high temperature melting.The photo-luminescence behavior of Gd3+ and Tb3+ in phosphate glass were investigated by absorption,excitation,and emission spectroscopy.Energy transfer between Gd3+ and Tb3+ in phosphate glass was studied,and it was found that there were two energy transfer mechanisms between Gd3+ and Tb3+ in phosphate glass: one was from 4f7 level of Gd3+ to the 4f8 level of Tb3+,and the other was from 5d level of Tb3+ to 4f7 level of Gd3+.The new findings would be beneficial for the study of Tb3+-doped scintillating phosphate glass.     

Cr3+或V3+替代Mn3+对La0.4Ca0.6MnO3电荷有序相的影响

用固相反应法制备了La0.4 Ca0.6 Mn1 -xCrxO3(LCMCO)和La0.4Ca0.6Mn1-yVyO3 (LCMVO)(x,y=0.00,006,0.08)多晶样品.通过XRD、M-T曲线、ESR谱线,研究了Cr3+或V3+替代Mn3+对La0.4Ca0.6MnO3电荷有序相的影响.实验结果表明:电荷有序相随着Cr掺杂浓度的增加而被破坏,在LCMCO体系中电荷有序相几乎完全消失;而当V掺杂时,虽然电荷有序相随着V成分的增加会逐渐变弱,但电荷有序相依然存在于LCMVO体系中.用V3+替代Mn3+只是对于长程的电荷有序仅仅起了隔断的作用;用Cr3+替代Mn3+破坏了CE型反铁磁的自旋序从而引起电荷序的融化.从实验上证明了电荷序CE型反铁磁体系中,电荷序和自旋序存在强耦合相互作用.     

Promising light converting BaMoO4:Er3+-Tm3+-Yb3+ phosphors for display and optical temperature sensing

Er³⁺-Tm³⁺-Yb³⁺ tri-doped BaMoO₄ phosphors were synthesized by co-precipitation technique and characterized by X-ray diffraction analysis, absorption study and field emission scanning electron microscopy analysis. Upconversion as well as downconversion luminescence studies were performed by using near infrared (980 nm) and ultraviolet (380 nm) excitations. Energy level diagram, pump power dependence and colour coordinate study were utilized to describe the multicolor upconversion emission properties. Under single 980 nm diode laser excitation the dual mode sensing behaviour is realized via Stark sublevels and thermally coupled energy levels of the Tm³⁺ and Er³⁺ ions in the prepared tri-doped phosphors. A comparative fluorescence intensity ratio analysis for integrated emission intensities arising from the Stark sublevels {¹G_4(a) and ¹G_4(b)} and thermally coupled energy levels {²H_11/2 and ⁴S_3/2} of the Tm³⁺ and Er³⁺ ions, respectively was carried out in the prepared tri-doped BaMoO₄ phosphors. The maximum sensitivity for thermally coupled energy levels of the Er³⁺ and Stark sublevels of the Tm³⁺ ion was reported. The developed phosphors could be useful in the display devices and optical thermometric applications.     

在甲基苯甲酰甲基亚砜高氯酸体系中Tm3+、Pr3+对Eu3+的荧光增强效应

合成了不同摩尔比的甲基苯甲酰甲基亚砜高氯酸铕、铥异核配合物和高氯酸铕、镨异核配合物(Eu1-xREx)(ClO4)3·L5·C2H5OH(RE=Tm、Pr,x=0.000～0.200,L=C6H5COCH2SOCH3).红外光谱及摩尔电导表明,配体通过亚砜基上的氧原子与稀土离子配位,羰基氧不参与配位,三个ClO4-有两个在内界参与了配位,而另一个在外界不参与配位.荧光光谱表明,当Tm3 和Pr3 的掺入量分别在0.001mol～0.01mol和0.001mol～0.100mol之间时,对Eu3 的荧光产生敏化作用,且Tm3 和Pr3 的掺入量都为0.001mol时,敏化强度最大,分别可使Eu3 荧光强度增加109%和137%.     

Combustion synthesis of Ce~（3＋）, Eu~（3＋） and Dy~（3＋） activated NaCaPO_4 phosphors

The preparation of NaCaPO4 doped with rare earth (RE) ions Ce3+, Eu3+ and Dy3+ by combustion method was described. Under UV excitation (251 nm) of NaCaPO4:Ce3+ showsd emission (367 nm) in UV range. When NaCaPO4:Dy3+ phosphor was excited at 349 nm, the emission spectrum showed intense bands at 482 nm (blue) and 576 nm (yellow). In Eu activated NaCaPO4 phosphor, the emission spectrum showed a dominant peak at 594 nm (orange) while others were at 614 and 621 nm (red) when excited at 393 nm. The prepared phosph...     

Up-Conversion Properties of Oxy-Fluoride Glasses Co-Doped with Ho3+ and Yb3+

Oxy-fluoride glasses with composition of 25SiO2-65PbF2-9.4AlF3-0.1HoF3-0.5YbF3 were prepared. Their up-conversion fluorescence characteristics were investigated by 980 nm laser. Two emission peaks were observed at 540 and 650 nm. The up-conversion mechanism and processes were analyzed. The relationship between pumping power and relative intensity of emissions was discussed. From the dependence, it is known that the emissions centered at 540 and 650 nm are both attributed to two-photon process.     

Bi3+ assisted luminescence in SrMoO4:Sm3+ red phosphors

In this paper, we report synthesis of pure SrMoO₄, Sm³⁺ (1 at%–5 at%) doped SrMoO₄ and Bi³⁺ (1 at%–3 at%) co-doped in 4 at% Sm³⁺ doped SrMoO₄ (SrMoO₄:4Sm³⁺) phosphors by solution combustion method. The X-ray diffraction (XRD) analysis reveals the tetragonal phase of all samples, also Bi³⁺ co-doping supports crystallite size growth and reduces lattice strain. Absorption analysis of Sm³⁺ doped SrMoO₄ ascertains a decrease in band gap and Bi³⁺ co-doping confirms the emergence of an absorbance peak at around 308 nm attributed to Bi³⁺ energy levels. Photoluminescence (PL) analysis ascertains an increase in emission peaks for Sm³⁺ doped SrMoO₄ up to 4% concentration, which are attributed to an electron transition from ⁴G_5/2 to ⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) energy levels of Sm³⁺ ions. We have explained the effects of Bi³⁺ co-doping on the luminescence of Sm³⁺ doped SrMoO₄. The reduced microstrain and increased crystallinity of the phosphors as a result of Bi³⁺ co-doping and their correlation with the luminescence of Sm³⁺ ions are discussed.     

Up-Conversion Emission of Er3+ Ions in Yb3+ Sensitized Oxide Crystals

Most of the up-conversion lasers operated at room temperature are realized with heavy metal fluorides, In this paper the Judd-Ofelt parameters Ωλ ( λ = 2,4,6 ) were calculated for Er3+ ions in Yb3 + sensitized LiNbO3 and YVO4 crystals at room temperature, together with the radiative transition probabilities, non-radiative transition probabilities and resonant transition probabilities of Er3+ ions. Taking into account the energy transfer from Yb3 + to Er3 +, the rate equations are given for Er3 + ions. We obtained from a solution of the rate equations that Yb3 + sensitized YVO4 crystal is more efficient than Yb3 + sensitized LiNbO3 crystal in the up-conversion of 550 nm of Er3+ emission, which is consistent with our observation.     

Effects of Ce3＋ , Nd3＋ , Gd3＋, Tb3＋ and Lu3＋ ions on Formation of CaCO3

The effects of lanthanides at various concentrations on CaCO3 crystal growth were studied by X-ray diffraction (XRD), infrared spectra (IR), X-ray photoelectric energy spectra (XPS) and inductively coupled plasma mtms spectrometry (ICP-MS). It was found that the calcite, a stable form of CaCO3 in thermodynamics, is the predominant species. The research indicates that lanthanide ions (Ln3 ) can partly substitute the Ca2 in the lattice of CaCO3 crystals, and change the crystal characterization and direct the ordinal growth of CaCO3 crystals.     

A comparison research on replacements of Ba2+ by Lu3+ and Ba2+-Si4+ by Lu3+-Al3+ in BaSi2O2N2:Eu phosphors

As a cyan-emitting oxonitridosilicate phosphor,BaSi₂O₂N₂:Eu²⁺can be used as a competent cyan compensator to improve the color rendering index of white light-emitting diodes(WLEDs).However,low luminescence efficiency and poor thermal stability of this type of phosphor seriously suppress its actual application in full-spectrum lighting.The replacements of Ba²⁺by Lu³⁺and Ba²⁺-Si⁴⁺by Lu³⁺-Al³⁺can greatly increase the luminescence intensity and improve the thermal stability at the same time.With Lu³⁺doping,the internal quantum efficiencyηIQE Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺is 24.08%higher than that of Ba_0.97Si₂O₂N₂:0.03 Eu²⁺.After Al³⁺co-doping,theηIQE is further increased by 10.31%compared to Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺.When the temperature rises to 473 K,the luminescence intensity of Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺maintains 62.32%of that at room temperature,which increases by 17.35%in relative to the Ba_0.97Si₂O₂N₂:0.03 Eu²⁺,while the luminescence intensity of Ba_0.925Si_1.97O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺,0.03 Al³⁺keeps 73.87%of the initial value,which increases by18.52%compared to Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺.The mechanisms for luminescence and thermal stability improvement are proposed.The Ba_0.925Si_1.97O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺,0.03 Al³⁺cyan phosphor,Y3 Al5 O12:Ce3+yellow phosphor and CaAlSiN3:Eu²⁺red phosphor are mixed thoroughly and coated on a blue LED(450 nm)to assemble a WLED.The WLED demonstrates a color rendering index(Ra)of 97.1 at150 mA,and the R1-R15 values are all above 90.The results indicate that as an effective cyan compensator in WLED,the BaSi₂O₂N₂:Eu²⁺,Lu³⁺,Al³⁺phosphor has great application prospect in the field of full-spectrum lighting.     

Upconversion hollow nanospheres CeF3 co-doped with Yb3+ and Tm3+ for photocatalytic nitrogen fixation

Solar driven nitrogen (N₂) fixation to synthesize ammonia is a potential alternative for the traditional Haber-Bosch approach to meeting industrial demand, but is largely hampered by the difficulties in the harvesting of solar energy and activating inert N₂. In this work, hollow CeF₃ nanospheres co-doped with activator Tm³⁺ and sensitizer Yb³⁺ (Yb³⁺:Tm³⁺:CeF₃) were prepared by microwave hydrothermal method. The product was employed as a catalyst for photo-driven N₂ fixation by adjusting the molar ratio of Ce³⁺:Yb³⁺:Tm³⁺. Results show that the porous hollow structure enhances the light-harvesting by physical scattering and reflection. In addition, heteroatom doping generates abundant fluorine vacancies (F_V) which provide abundant active sites for adsorption and activation of N₂. The sample with molar ratio of CeF₃:Yb³⁺:Tm³⁺ at 178:20:2 demonstrates the highest utilization of solar energy attributed to the strongest upconversion capability of near-infrared (NIR) light to visible and ultraviolet (UV) light, and the NH₄⁺ concentration achieves the highest value of 15.06 μmol/(g_cat?h) under simulated sunlight while nearly 6.22 μmol/(g_cat?h) under NIR light. Current study offers a promising and sustainable strategy for the fixation of atmospheric N₂ using full-spectrum solar energy.