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%.     

对甲苯基苯乙烯基亚砜稀土高氯酸盐体系中Tm3+→Eu3+的荧光增强效应

合成并表征了六种不同掺杂比例稀土高氯酸铕掺铥与对甲苯基苯乙烯基亚砜的固态配合物.经元素分析确定了配合物的组成为:(EuxTm1-x) (ClO4)3*L7(x=1.000,0.999,0.995,0.990,0.950,0.900; L= C6H5CH=CHSOC6H4CH3).配合物的红外光谱表明,配体通过亚砜基氧原子与稀土离子配位,烯键未参与配位.在丙酮溶液中测定的摩尔电导率表明,配合物为1∶2型电解质,三个 ClO4-无机抗衡阴离子,其中一个在内界,两个在外界.配合物的荧光发射光谱中出现了比磁偶极跃迁(5D0→7F1)强的电偶极跃迁(5D0→7F2),表明配合物不存在反演中心.掺杂配合物的荧光光谱表明,将千分之一的铥掺入后,铕离子的发光增强增加到111%.     

苯基苯甲酰甲基亚砜重稀土高氯酸配合物的合成、表征及铽、镝的发光

合成并表征了重稀土高氯酸盐与苯基苯甲酰甲基亚砜的四种固态配合物。经元素分析及差热-热重分析表明,配合物的组成为:RE(ClO4)3·L5·2H2O(RE=Tb,Dy,Er,Yb)。红外光谱及核磁共振氢谱表明,配体通过一个羰基氧和一个亚砜基氧与稀土离子配位。在丙酮溶液中测定的摩尔电导率表明,三个ClO4-,其中两个在内界,一个在外界。铽、镝配合物的荧光光谱表明,配体对铽(Ш)、镝(Ш)的荧光具有较强的敏化作用。     

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.     

二茂铁甲酰基苄基肼的稀土配合物的合成与表征

合成了新的配体二茂铁甲酰基苄基肼(L)和它的十四种高氯酸盐配合物RELx(ClO4)3·nH2O(RE=La、Ce、Pr、Nd、Sm、Eu、Tb、Dy、Er、Tm、Yb、Lu,x=4,n=1,2,4;RE=Gd、Ho,x=3,n=1)。对配体和配合物进行了元素分析、红外光谱、核磁共振氢谱和摩尔电导率表征,并对Sm、Tb、Dy的配合物进行了荧光光谱的测定。分析结果表明配体是用羰基氧原子和氮原子与稀土离子配位形成五元螯合环,配合物为电解质,高氯酸根为外界。配合物中均未出现稀土金属离子f-f跃迁的特征荧光光谱。     

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.     

对苯基苯甲酸铕、铽配合物的合成、表征及荧光性能研究

分别合成了以对苯基苯甲酸为配体,铕、铽及掺杂铕、铽为中心的固态配合物。经元素分析、摩尔电导及差热-热重分析,推测其组成分别为:铕配合物:EuL3.3H2O、Eu0.5La0.5L3.3H2O、Eu0.5Y0.5L3.3H2O;铽配合物:TbL3.2H2O、Tb0.5La0.5L3.2H2O、Tb0.5Y0.5L3.3H2O(L=■-■-COO-。红外光谱、紫外光谱及核磁共振氢谱分析表明,对苯基苯甲酸的羧基氧原子与稀土离子配位。配合物的荧光光谱测定表明,铕系列和铽系列配合物都可发出其特征荧光,铕异核稀土配合物的荧光强度与相同配体的铕配合物相比,均有不同程度提高。     

均苯三甲酸邻菲罗啉稀土配合物的合成、表征及荧光性质

分别合成了以均苯三甲酸(H3BTC)和邻菲罗啉(phen)为配体,以Sm、Eu、Tb和Dy为中心的4种稀土三元配合物,通过元素分析及稀土络合滴定确定了配合物的组成为RELL'1.5 ·2H20(L=BTC,L'= phen);配合物的红外光谱、紫外光谱和荧光光谱测定结果表明,配合物中均苯三甲酸根的羧基氧原子和邻菲罗啉的氮原子均与稀土离子配位成键;四种配合物均可发出稀土离子的特征荧光,铕、铽配合物具有良好的荧光性能,钐、镝配合物也发出较强的特征荧光.     

双苄基双亚砜高氯酸铕二元及三元配合物的合成及其与BSA的作用研究

合成并表征了双苄基双亚砜高氯酸铕二元及三元配合物,对配合物进行了稀土络合滴定、摩尔电导率和元素分析,配合物的组成为:[EuL2.5·(ClO4)](ClO4)2·3H2O和[Eu2L4·phen(ClO4)2](ClO4)4·12H2O(L=C6H5CH2SOCH2SOCH2C6H5)。配合物的荧光光谱表明,配合物均产生了Eu3+的特征荧光发射光谱,且三元配合物比二元配合物的荧光发射强度增强1.87倍。通过荧光光谱法,研究了稀土配合物与牛血清白蛋白(BSA)的相互作用。研究表明,双苄基双亚砜稀土二元、三元配合物-BSA体系的猝灭过程可能是静态猝灭,并且各配合物与BSA均具有较强的结合作用,能够被BSA储存和运输,因此,有望成为蛋白质荧光探针。     

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%。     

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.