二苯基亚砜、苯甲酸与重稀土高氯酸四元配合物的合成及Tb3+、Dy3+光致发光

合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的六种四元配合物.经元素分析、差热-热重分析,表明四元配合物组成为[REL5L′(ClO4)](ClO4)(RE=Tb,Dy,Ho,Er,Tm,Yb;L=C6H5SOC6H5,L′=C6H5COO-).IR、1 HNMR表明,第一配体二苯基亚砜通过一个亚砜基氧原子、第二配体苯甲酸脱质子以阴离子形式通过一个羧基氧原子单齿与稀土离子配位.摩尔电导率表明配合物为1:1型,两个 ClO4-无机抗衡阴离子,其中一个在内界,一个在外界;配合物的荧光光谱表明,Tb3+、Dy3+四元配合物的荧光强度分别比二苯基亚砜与高氯酸稀土二元配合物的荧光强度提高226%和422%.磷光光谱表明第二配体的加入提高了配体的三重态能级与稀土离子激发态能级的匹配程度.铽配合物的电子顺磁共振谱在g=1.9920处出现一个单峰,表明该配合物具有成单电子,是顺磁性物质.     

苯基乙酰甲基亚砜与重稀土高氯酸配合物的合成、表征及铽(Ⅲ)配合物光致发光

合成了六种重稀土高氯酸盐与苯基乙酰甲基亚砜(L)的配合物RE(C lO4).L5.2H2O(RE=T b,D y,E r,Tm,Y b,Y),该系列配合物可溶于水,红外光谱及摩尔电导表明,配体通过亚砜基团上的氧原子与稀土离子配位,羰基氧不参与配位,三个高氯酸根离子有两个在内界与稀土离子配位,另一个在外界不参与配位。测定了配体的磷光光谱,对配合物进行了元素分析、热重等表征。荧光激发和发射光谱测定结果表明:铽(Ⅲ)配合物的发光机理属于M→M发光[1]。     

轻稀土高氯酸盐甲基苯甲酰甲基亚砜配合物的合成及表征

合成了5种甲基苯甲酰甲基亚砜与轻稀土高氯酸盐配合物RE(ClO4)3·L5·C2H5OH(RE=La,n,Nd,Sm,Eu;L=C6H5COCH2SOCH3),经元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成,测定了配体及配合物的的IR谱、1HNMR及铕配合物的磷光光谱、荧光激发和发射光谱,根据磷光发射光谱数据计算了配体的三重态能级值.荧光发射光谱表明,配体可有效的向Eu3+离子传能使其发射较强荧光.     

铕、铽-2-噻吩甲酸-1,10-菲咯啉三元配合物的合成及荧光性质的研究

同时合成了高氯酸铕、铽与2-噻吩甲酸、1,10-菲咯啉(phen)的三元配合物和高氯酸铕、铽与2-噻吩甲酸的二元配合物,对配合物进行了元素分析、稀土络合滴定、红外光谱、摩尔电导测定,确定了配合物组成分别为REL3·2H2O及REL3L'·C2H5OH(RE=Eu,Tb;L=2-噻吩甲酸,L'=1,10-菲咯啉).摩尔电导数据表明,此类配合物为非电解质.红外光谱测定表明,配体2-噻吩甲酸羧基氧与稀土离子配位,配体1,10-菲咯啉两个氮原子与稀土离子配位.荧光光谱实验表明,1,10-菲咯啉加入到铕-2-噻吩甲酸二元配合物和铽-2-噻吩甲酸二元配合物中形成三元配合物后它们的荧光明显增强.     

2,4,6-三吡啶基三嗪稀土配合物的红外光谱和荧光性能

首次合成了以 2,4,6-三吡啶基三嗪(TPTZ)为配体,以钐、铕、铽和镝为中心的稀土配合物.经元素分析、红外光谱和摩尔电导率测试表明,配合物的组成为RE(TPTZ)2·(ClO4)3(RE=Sm, Eu,Tb, Dy),稀土离子与2个TPTZ的6个氮原子和1个高氯酸根离子配位,另2个高氯酸根离子在外界未参与配位. 荧光光谱的测试表明,Tb3 配合物具有较强的特征荧光发射,位于490.4nm的5D4→7F6跃迁很强,接近5D4→7F5跃迁.     

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%.     

低温固相反应合成苯羟乙酸稀土配合物及其性质研究

利用低温固相反应合成了4种苯羟乙酸稀土配合物:RE(L)3·4H2O[RE＝La,Nd,Eu,Tb; L= C6H5CH(OH)COO-],并通过元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成.红外光谱、核磁共振氢谱表明,苯羟乙酸稀土配合物中配体通过羧基以羧基氧负离子和醇羟基同时参与稀土离子(Ⅲ)配位,两分子水也参与稀土的配位.铕(Ⅲ)、铽(Ⅲ)配合物的荧光光谱和配体的磷光光谱表明,配体对铕(Ⅲ)、铽(Ⅲ)的荧光具有一定的敏化作用.     

在苯基羧甲基亚砜体系中高氯酸铒对高氯酸铽的荧光增强效应

合成了不同摩尔比的苯基羧甲基亚砜高氯酸铽、铒异核配合物,对配合物进行了组成分析,确定了配合物组成为Tb1-xErxL2ClO4·2H2O(x=0.000～0.200,L=C6H5SOCH2COO-)。通过IR光谱的测定以及摩尔电导推测了配位情况。荧光光谱实验表明:当x=0.001～0.010时铒对铽的荧光均产生敏化增强效应,当x=0.001时敏化强度最大,可使Tb3+荧光强度增加142%。     

钐(Ⅲ)在二苯甲酰基甲基亚砜体系中的发光

合成并表征了钐(Ⅲ)的高氯酸盐与二苯甲酰基甲基亚砜(C6H5COCH2SOCH2COC6H5)的固态配合物,对配合物进行了摩尔电导率、元素分析和稀土络合滴定,确定了配合物的组成为SmL5(ClO4)3·3H2O( L=C6H5COCH2SOCH2COC6H5).配合物的红外光谱表明,配体通过一个亚砜基氧原子与稀土离子配位,而羰基氧未参与配位.配体的磷光光谱和配合物的荧光光谱表明,二苯甲酰基甲基亚砜配体对钐(Ⅲ)的荧光具有较好的敏化作用.还对钐(Ⅲ)配合物分子内能量传递及发光机理进行了讨论.     

稀土酪氨酸咪唑配合物的合成、表征及抑菌作用

在甲醇介质中合成了3种稀土高氯酸盐与L-酪氨酸及咪唑的三元配合物,经元素分析,摩尔电导,紫外光谱,红外光谱和差热-热重分析等手段对配合物进行了表征,确定了配合物的组成为RE(Tyr)3Im(ClO4)3·nH2O(RE=La,n=3;RE=Dy,n=4;RE=Nd,n=5).抑菌实验表明,配合物对大肠杆菌、金黄色葡萄球菌,霉菌均有不同程度的抑菌作用.且菌液浓度越低,抑菌效果越好.     

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.     

Application of monodispersive anion exchangers in sorption and separation of y3+ from Nd3+ and Sm3+ complexes with dcta

Rare earth complexes with trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (DCTA) of the Ln(dcta)- ype exhibited an unusual sequence of affinity on the polystyrene anion exchangers: pm3 >Nd3 >Sm3 >pr3 >Ce3 >Eu3 >Gd3 >La3 >Sc3 >Tb3 >Dy3 >Ho3 >y3 >Er3 >Tm3 >yb3 >Lu3 [1]. Taking into account the position of Y3 , Sm3 , and Nd3 in this affinity series, for the monodispersive polystyrene anion exchangers, Lewafit MonoPlus M 500, Lewatit MonoPlus M 600, Lewatit MonoPlus MP 500, Lewatit MonoPlus MP 64,and for the heterodispersive anion exchanger, Lewatit MP 62, the weight (Dg,) and bed (Dv) distribution coefficients of these complexes and working ion exchange capacities (Cw) were determined. Based on these values, purifications of Y3 from Nd3 and y3 from Sm3 in the macro-micro component system on these anion exchangers were studied. The application potential of this method was highlighted for the separation of yz3 in the presence of Nd3 and Sm3 . With 1 L of monodispersive and strongly basic polystyrene gel anion exchanger Lewatit MonoPlus M 500 in the acetate form, it is possible to obtain approximately 79 g Y2O3 purified from Nd2O3 and 70 g Y2O3 purified from Sm2O3 in the same process condition.     

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.     

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...     

Photoluminescent and Electroluminescent Properties of Ligand Emitting y^3＋, La^3＋, Gd^3＋ and Lu^3＋ Complexes

The photolumineseent (PL) and eleetroluminescent (EL) properties of a series of ligand emitting rare earth complexes (including y^3 , La^3 , Gd^3 and Lu^3 ) were systematically studied. These complexes have the same anionic ligand, 1-phenyt-3-methyl-4-isobutyryl-5-pyrazoloneate (PMIP), and three neutral ligands, triphenyl phosphine oxide(TPPO), 2, 2‘-dipyridine (Bipy) and phenanthroline (Phen). Measured with 60 nm thin film of these complexes vaporized in vacuum on quartz substrates, a good regularity in the PL properties was observed. For rational comparison, the same structural EL devices based on these complexes, ITO/PVK (40 nm)/the complex (80 nm)/Mg: Ag (200 nm)/Ag (100 nm), were fabricated. Excluding the exeiplex emission happens, the EL luminance usually increases with the increasing of PL efficiency.     

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.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...