Thermoluminescence studies of LiBa2B5O10 : RE3+ (RE = Dy, Tb and Tm)

LiBa2B5O10:RE3+ (RE = Dy, Tb and Tm) was synthesized by the method of high-temperature solid-state reaction and the thermoluminescence (TL) properties of the samples under the irradiation of the gamma-ray were studied. The result showed that Dy3+ ion was the most efficient activator. When the concentration of Dy3+ was 2 mol%, LiBa2B5O10:Dy3+ exhibited a maximum TL output. The kinetic parameter of LiBa2B5O10:0.02Dy was estimated by the peak shape method, for which the average activation energy was 0.757 eV and the frequency factor was 1.50 x 10(7) s(-1). By the three-dimensional (3D) TL spectrum, the TL of the sample was contributed to the characteristic f-f transition of DY3+. The dose-response of LiBa2B5O10:0.02Dy to gamma-ray was linear in the range from 1 to 1000 mGy. In addition, the decay of the TL intensity of LiBa2B5O10:0.02Dy was also investigated.

Gadolinium heteropoly complex K-17[Gd(P2W17O61)(2)] as a potential MRI contrast agent

Gadolinium heteropoly complex K-17[Gd(P2W17O61)(2)] has been evaluated by in vitro and in vivo experiments as a potential contrast agent for magnetic resonance imaging (MRI). The thermal analysis and conductivity study indicate that this complex has good thermal stability and wide pH stability range. The T-1 relaxivity is 7.59 mM(-1) s(-1) in aqueous solution and 7.97 mM(-1) s(-1) in 0.725 mmol l(-1) bovine serum albumin (BSA) solution at 25degreesC and 9.39 T, respectively. MR imaging of three male Sprague-Dawley rats showed remarkable enhancement in rat liver after intravenous injection, which persisted longer than with Gd-DTPA. The signal intensity increased by 57.1 +/- 16.9% during the whole imaging period at 0.082 mmol kg(-1) dose. Our preliminary in vitro and in vivo studies indicate that K-17[Gd(P2W17O61)(2)] is a potential liver-specific MRI contrast agent.

Ti_(0.17)Zr_(0.08)V_(0.34)Nb_(0.01)Cr_(0.1)Ni_(0.3)氢化物电极合金微观结构及电化学性能研究

采用XRD、FESEM-EDS、ICP及EIS等方法研究了Ti0.17Zr0.08V0.34Nb0.01Cr0.1Ni0.3氢化物电极合金微观结构和电化学性能。X射线衍射分析表明:该合金由体心立方结构(bcc)的V基固溶体主相和少量六方结构的C14型Laves相组成;FESEM及EDS分析表明:V基固溶体主相形成树枝晶,C14型Laves相呈网格状围绕着树枝晶的晶界,元素在两相中的分布呈现镜像关系。电化学性能测试结果表明:该合金的氢化物电极在303￣343K较宽的温度区间内,表现出较高的电化学容量,在303K和343K时,电化学容量分别为337.0mAh·g-1和327.9mAh·g-1。在303K循环100周后,容量为282.7mAh·g-1。ICP分析结果表明,氢化物电极在充放电循环过程中,V及Zr元素向KOH电解质中的溶出较为严重。EIS研究表明,金属氢化物电极表面电化学反应的电荷转移电阻(RT)随循环次数的增加而增加,相应的交换电流密度则随循环次数的增加而降低。氢化物电极循环过程中RT的增大以及V和Zr元素的溶解,可能是导致电极容量衰减的主要原因。

BaMgAl_(10)O_(17)∶R~(2+)(R=Eu,Mn)的真空紫外光谱特性

采用高温固相反应法合成了BaMgAl10 O17∶R(R =Eu ,Mn)荧光体 ,测量了荧光体的真空紫外激发光谱和相应的发射光谱 ,观察到基质吸收带位于 16 5nm附近 ,Mn2 + 离子的吸收位于 170～ 2 40nm范围 ,Eu2 + 离子的 4f→ 5d吸收位于 2 10～ 40 0nm范围。真空紫外光谱特性的研究表明基质与激活离子之间存在较好的能量传递。

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

Separation of heavy rare earth elements with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

This paper presents the results of the adsorption of heavy rare earth ions (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 30 degreesC by the extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA), which has higher steric hindrance, higher selectivities and lower extraction and stripping acidity than di(2-ethylhexyl)phosphoric acid (DERPA) or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH/EHP). The dependence of acid concentration, flow rate and amounts of rare earth ions sorbed on the separation of Er-Tm, Tm-Yb and Er-Tm-Yb mixtures has been studied. The baseline chromatographic separation of Er-Tm-Yb mixture has been observed. Satisfactory results with purity and yield of Tm2O3>99.71% and >71.25%, Er2O3>99-81% and >94.17%, and Yb2O3>99.74% and >89.83%, respectively, have been obtained. The parameters such,as resolution, separation factors and efficiencies have been determined as a function of acidity, loading of rare earth elements and flow rates. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Polishable amperometric hydrogen peroxide sensor based on sol-gel-derived conductive composite containing vanadium-17-molybdodiphosphate

A new kind of conductive vanadium-17-molybdodiphosphate/graphite/methylsilicate composite was firstly prepared by the sol-gel technique and used as electrode material for the fabrication of amperometric hydrogen peroxide sensor. The remarkable advantage of the sensor is its excellent reproducibility of surface renewal by simple mechanical polishing.

Preparation of borates doped with divalent rare earth ions (RE2+) in air and spectroscopy of divalent rare earth ions (RE2+ = Sm, Eu, Tm, Yb)

The spectroscopic feature of divalent Sm2+, Eu2+, Tm2+ and Yb2+ is discussed in this paper. Especially the spectroscopic properties of some berates containing tetrahedral BO4 group such as SrB4O7, SrB6O10 and BaB8O13 doped with these divalent ions are reported. When the divalent alkaline earth ion in these berates is replaced partially by the above trivalent rare earth ion, the charge carried in the produced defects can be used as reductant to reduce the doped rare earth ion into divalent state at high temperature even in air. Therefore, a convenient and safe method is provided to prepared phosphors doped with these divalent rare earths.

BaMAl_(10)O_(17)(M=Be,Mg,Ca,Zn,Cd,Mn,Co,Li)体系的合成、结构和Eu~(2+)在其中的发光

在BaMAl10O17 体系中 ,将M扩大到除镁以外的其它离子 ,研究和讨论了离子半径与基质结构的形成关系 ,提出能稳定(形成)尖晶石结构的M离子有相应的磁铅矿或β Al2O3 结构的化合物存在的思想 ,并研究了Eu2 +在体系中的发光性能。结果表明 ,M=Zn,Cd,Mn,Co,Li时可形成 β Al2O3 结构化合物 ,M=Ca,Be时不能形成这类结构 ,Ca形成多相共存 ,Be形成一未知相 ;Eu2 +在M=Li,Be,Zn体系中具有良好的发光性能 ,发射波长450nm ,半高宽在50nm附近 ,将是一类很有前途的新的蓝色发光材料 ,Eu2 +在M=Mn的体系中存在Eu2 +和Mn2 +的同时发射 ,在M=Cd体系中 ,Eu2 +产生一双重宽带发射。对实验结果进行了合理的解释

在空气下制备掺二价稀土的硼酸盐及二价稀土离子(RE~(2+)=Sm,Eu,Tm,Yb)的光谱特征

本文讨论了Sm2 + 、Eu2 + 、Tm2 + 、Yb2 + 等二价稀土离子的光谱特征 ,特别是在一些含四面体硼酸根的硼酸盐如SrB4 O7、SrB6 O10 和BaB8O13中它们的光谱性质。当以三价稀土离子取代化合物中的二价碱土离子时 ,利用不等价取代而产生的缺陷所带的电荷 ,可在高温的空气下使上述的稀土离子还原成二价 ,不需加入化学还原剂 ,从而提出了一个简便、安全的制备含二价稀土离子发光材料的方法

Electrochemical and in situ spectroelectrochemical behavior of 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and (Zn(II)OHTTAP)

The characterization of free base porphyrin 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and its zinc(II) complexes [Zn(II)OHTTAP] containing eight thioether groups at the beta -pyrrole positions of the macrocycle was reported. Results obtained by cyclic voltammetry and differential pulse voltammetry indicated a five-electron reduction in five steps for each complex. They were oxidized in two single-electron-transfer steps to yield pi -cation radicals and dications and reduced in three single-electron-transfer steps to yield pi -anion radicals, dianions and trianions, respectively. The redox property of H(2)OHTTAP was unusual as compared to porphyrins (PPs) and phthalocyanines (Pcs). Each process was monitored by in situ thin-layer spectroelectrochemistry, which indicated that only the Ligand was electroactive. The existence of the eight hexylthio groups was responsible for the intrastack interactions and enhanced intracolumnar and intercolumnar electron motions, resulting in improved conductivity. Copyright (C) 2001 John Wiley & Sons, Ltd.

Calculation of chemical bond parameters in RBa2Cu4O8(R = Dy,Ho,Er,Tm,Yb) and Y2Ba4Cu7O14.3

Chemical bond parameters in RBa2Cu4O8(R = Dy, Ho, Er, Tm, Yb) and Y2Ba4Cu7O14.3 were calculated by using complex chemical bond theory. The results indicated that the bond covalency in CuO chain was larger than that in CuO2 plane. For metal atoms, the bond covalency of five coordinated case was larger than that of six coordinated case.

RBa_2Cu_4O_8(R=Dy,Ho,Er,Tm,Yb)和Y_2Ba_4Cu_7O_(14.3)的化学键参数计算

使用复杂晶体上化学键理论计算了 RBa2 Cu4 O8(R=Dy,Ho,Er,Tm ,Yb)和 Y2 Ba4 Cu7O14 .3 的化学键参数 .结果表明 ,Cu O链上的 Cu O键共价性大于它们在 Cu O2 面的共价性 .当金属元素与氧形成五配位时 ,其共价性的数值大于这些元素在六配位时的情形

The reduction of RE3+ in SrB6O10 prepared in air and the luminescence of SrB6O10 : RE2+ (RE=Eu, Sm, Tm)

The reduction of RE3+ to RE2+ (RE=Eu, Sm and Tm) in SrB6O10 prepared in air by high-temperature solid state reaction was observed. The luminescent properties of Eu2+ and Tm2+ show f-d transition and Sm2+ shows f-f transition at room temperature. Three crystallographic sites for Sm2+ in matrix are available. Vibronic transition of D-5(0)-F-7(0) of Sm2+ was studied. The coupled phonon energy about 108 cm(-1), was determined: from the vibronic transition. Due to the thermal population from D-5(0) level, (D1-FJ)-D-5-F-7 (J=0, 1, 2) transitions of Sm2+ were observed at room temperature. A charge compensation mechanism is proposed as a possible explanation.