铽—镧（镥,钇）—均苯四甲酸共发荧光体系的研究和应用

研究发现Ｌａ＾３＋（Ｌｕ＾３＋，Ｙ＾３＋）对Ｔｂ＾３＋均苯四甲酸（ＢＴＣＡ）体系具有强烈的共发荧光效应，在最佳条件下，共发光离子Ｌａ＾３＋，Ｌｕ＾３＋，Ｙ＾３＋可分别使Ｔｂ－ＢＴＣＡ体系的荧光增强３１２，１３３和１００倍，介绍了Ｔｂ－Ｌａ（Ｌｕ，Ｙ）－ＢＴＣＡ共发荧光体系的荧光特点，形成条件和影响因素，利用Ｌａ＾３＋（Ｌｕ＾３＋，Ｙ＾３＋）的增敏效应，测定了合成稀土样品和包头稀土标准氧化物中的Ｔｂ     

钇离子对人红细胞膜的作用

钇离子促进人红细胞溶血，其临界溶血浓度是３×１０－５ｍｏｌ／Ｌ，Ｙ３＋与人红细胞膜间的作用用ＳＤＳ－ＰＡＧＥ、ＣＤ和荧光光谱等方法进行研究。结果表明，高浓度Ｙ３＋可改变人红细胞膜蛋白的构象并导致膜蛋白间的交联或聚合，能淬灭膜蛋白的内源性荧光。在人红细胞膜上有两类Ｙ３＋结合部位，其结合容量分别为ｎ１＝２．１１×１０－３ｍａｌ／ｇ膜蛋白和ｎ２＝３．５６×１０－４ｍｏｌ／ｇ膜蛋白，相应的表现结合常数分别为Ｋ１＝４．５１×１０６Ｌ／ｍｏｌ和Ｋ２＝１．１８×１０６Ｌ／ｍｏｌ，表明Ｙ３＋离子可以和人红细胞膜强烈地结合并表现出明显的细胞毒性。     

镧和钙对人红细胞膜的作用

采用荧光偏振，自旋标记电子顺磁共振波谱和激光拉曼光谱等技术研究了镧和钙对人红细胞膜结构和功能的影响。结果表明，低浓度的Ｌａ＾３＋（０．５ｕｍｏｌ／Ｌ）对（Ｎａ＾＋＋Ｋ＾＋）－ＡＴＰ酶，Ｍｇ＾２＋－ＡＴＰ酶有轻微的激活作用，随着浓度的增大，则明显抑制酶的活性。Ｌａ＾２＋可降低红细胞 的膜脂充动性，使膜蛋白酰胺１’－ａ螺旋振动强度减弱；Ｃａ＾２＋对膜脂流动性和膜蛋白酰胺１’－ａ螺旋的影响比Ｌａ＾３＋小     

掺Eu3+离子Y2SiO5晶体格位选择光谱研究

分别利用白光灯、４５７－９ ｎｍ 氩离子激光、二倍频ＹＡＧ∶Ｎｄ 激光泵浦的诺丹明６Ｇ 可调谐窄线宽（０－５ ｃｍ －１） 染料激光作为光源， 以单色仪锁相放大器光电倍增管计算机数据采集系统记录光谱， 测量并研究了Ｙ２ＳｉＯ５∶Ｅｕ３ ＋ 晶体的透射光谱、荧光光谱、激发光谱和格位选择荧光光谱。５Ｄ０ →７Ｆ０，１ ，２ ，３，４ 跃迁，３０ 多根谱线（总数为５０ 根） 被观察到。在该晶体中Ｅｕ３＋ 替换Ｙ３＋ 离子， 占据两个较低对称性的光学格位， 这两个格位的５Ｄ０ ７Ｆ０ 能级跃迁谱线相隔大约只有０－２ ｎｍ ， 在室温下有一定的光谱关联。并用Ｘ射线谱对晶体的晶格常数ａ ， ｂ，ｃ 和晶面角度β进行测量， 测量结果显示掺杂后的晶格常数和未掺杂的Ｙ２ＳｉＯ５ 晶格常数基本一致。     

希土环状二茂铁基亚砜配合物研究

在丙酮介质中合成了希土与１，１′－二乙基－α，α′－硫代二茂铁－Ｓ－氧化物（Ｌ）的配合物ＬｎＬ３（ＮＯ３）３·Ｈ２Ｏ（Ｌｎ＝Ｌａ－Ｌｕ，Ｙ，仅Ｐｍ除外），通过元素分析、热谱、Ｘ射线粉末衍射图、红外光谱、Ｘ光光电子能谱和摩尔电导表征了配合物并且对配合物的光谱性质进行了讨论。     

掺Eu^3＋离子Y2SiO5晶体格拉选择光谱研究

分别利用白光灯、４５７．９ｎｍ氩离子激光、二倍频ＹＡＧＬ：Ｎｄ激光泵浦的诺丹明６Ｇ可调谐窄线宽１０．５ｃｍ＾－１）染料激光作为光源,以单色仪－锁相放大器－光电倍增管－计算机数据采集系统记录光谱,测量并研究了Ｙ２ＳｉＯ５：Ｅｕ＾３＋晶体的透射光谱、荧光光谱、激发光谱和格位选择荧光光谱。＾５Ｄ０→＾７Ｅ０,１,２,３,４跃迁,３０多根谱线（总数为５０根）被观测到。在该晶体中Ｅｕ＾３＋替换Ｙ＾３＋离子,     

稀土元素荧光增强效应的研究──RE对Eu－2－（2－二苯乙酰基）－1，3－茚二酮－十六烷基三甲基溴化铵体系的荧光增强

研究了稀土元素Ｌａ~（３＋）、Ｇｄ~（３＋）、Ｙｂ~（３＋）、Ｌｕ~（３＋）、Ｙ~（３＋）及Ｓｃ~（３＋）对Ｅｕ－２－（２－二苯乙酰基）－１，３－茚二酮－阳离子表面活性剂体系的荧光增强效应，结果表明，在上述增强离子存在下，体系的荧光强度分别增加１０、１３０、３０、５０、５２和２０倍，利用标准加入法测定了混合稀土氧化物中的铕，铕浓度在１．０×１０~（－１０）～６．０×１０~（－７）ｍｏｌ／Ｌ范围内与荧光强度呈线性关系，最低检出限为６．０×１０~（－１２）ｍｏｌ／Ｌ。     

呋喃甲酰基吡唑啉酮双席夫碱稀土配合物的合成、表征及生物活性

合成了１１种新的稀土与Ｎ,Ｎ’－双「（１－苯基－３－甲基－５－氧－４－吡唑啉基）α－呋喃次甲基」乙二亚胺（ＨＰＭαＦＰ）２ｅｎ配合物。元素分析及摩尔电导值表明配合物的组成为「ＲＥ（ＨＰＭαＦＰ）２ｅｎ（ＮＯ３）２」ＮＯ３」ＮＯ３（ＲＥ＝Ｌａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｔｂ,Ｄｙ,Ｈｏ,Ｅｒ,Ｙｂ,Ｙ）。用红外学谱、紫外学谱、磁共振谱和荧光光谱对配合物进行了表征,证实席夫碱配体以四齿形式配位,ＲＥ＾３     

2,6—二甲酸吡啶氮氧化物与稀土硝酸盐配合物的合成及表征

在无水乙醇介质中合成了２，６－二甲酸吡啶氮氧化物（Ｈ２ＰｄＣＯ）和稀土硝酸盐形成的配合物［ＲＥ（ＰｄＣＯ）·ＮＯ３·２Ｈ２Ｏ］（ＲＥ＝Ｌａ－Ｎａ，Ｓｍ，Ｅｕ，Ｔｂ，Ｈｏ，Ｅｒ，Ｙ）。通过元素分析，摩尔电导，红外光谱，紫外光谱，１Ｈ核磁共振谱及热重－差热分析等对该系列配合物进行了表征，并研究了Ｅｕ（Ⅲ），Ｔｂ（Ⅲ）配合物荧光性质。     

大孔磷酸树脂吸收镧的研究

本文测定了大孔膦酸树脂对Ｌａ＾３＋的吸附容量，介质ｐＨ、温度、吸附时间等因素对吸附的影响，测得吸附速率常数Ｋ２９８＝７．６４×１０＾－５Ｓ＾－１，树脂功能基与Ｌａ＾３＋的络合比为３：１，用化学及红外光谱等方法，得到大孔膦酸树脂吸附Ｌａ＾３＋的基本参数及其机理。     

1,2-邻苯二氧基二乙酸铕及掺杂L(L=La,Y,Yb,Nd)配合物的合成及荧光性质研究

在乙醇体系中,以氯化铕与1,2邻苯二氧基二乙酸和二苯甲酰甲烷反应合成了三元配合物Eu-BDDA-DBM以及弱荧光离子La3+,Y3-,Yb3-和Nd3+掺杂的铕配合物.通过红外、紫外-可见、热重、荧光光谱对配合物进行了表征.红外光谱表明,单一配合物和掺杂配合物具有相似的配位结构.荧光光谱表明,La3+和Nd3+离子掺杂可以大幅度提高的铕配合物的荧光强度,其中La3+掺杂荧光强度增强最明显.     

Enhanced luminescence of rare-earth complexes Tb(1-x)Eu(x)(m-NBA)3Phen in ZnS

Rare-earth ternary complexes Tb(1-x)Eu(x)(m-NBA)(3)Phen (X=1, 0.25, 0.5, 0.75, 1.0) were synthesized and characterized by IR, DTA-TG, UV, fluorescent spectra and elemental analysis. It was found that luminescence of Eu(3+) complex was enhanced by doped with Tb(3+). It is proved by TG curve that the complexes are stable, ranging from ambient temperature to 360 degrees C in air. The organic-inorganic combined structural device was fabricated, and the electroluminescence intensity of the combined structural device was improved compared with the device of the purely organic components.     

稀土配合物的研究 IV: 稀土元素与4-酰代双吡唑啉酮BPMPPD及1,10-二氮杂菲三元配合物的合成和性质的研究

4-酰代双吡唑啉酮是一类新型β双酮多啮金属离子螯合剂和萃取剂, 其性能优于单吡唑啉酮, 本文继合成1,5-双(1'-萃基-3'-甲基-5'-氧代吡唑-4')-1,5-戊二酮(BPMPPD, H2A)后, 又合成了它和1,10-二氮杂菲(Phen, P)与稀土元素形成的三元固态配合物, 并对这些新配合物的性质进行了研究。     

The behavior of mixed-metal oxides: physical and chemical properties of bulk Ce1-xTbxO2 and nanoparticles of Ce1-xTbxOy

The physical and chemical properties of bulk Ce(1-x)Tb(x)O(2) and Ce(1-x)Tb(x)O(y) nanoparticles (xTb exchange nor the introduction of oxygen vacancies in Ce(1-x)Tb(x)O(y) significantly affect the charge on the Ce cations. In contrast, the O K-edge and Tb L(III)-edge XANES spectra for Ce(1-x)Tb(x)O(y) nanoparticles show substantial changes with respect to the corresponding spectra of Ce and Tb single oxide references. The Ce(0.5)Tb(0.5)O(y) compounds exhibit a much larger Tb(3+)/Tb(4+) ratio than TbO(1.7). A comparison with the properties of Ce(1-x)Zr(x)O(y) and Ce(1-x)Ca(x)O(y) shows important differences in the charge distribution, the magnitude of the dopant induced strain in the oxide lattice, and a superior behavior in the case of the Ce(1-x)Tb(x)O(y) systems. The Tb-containing oxides combine stability at high temperature against phase segregation and a reasonable concentration of O vacancies, making them attractive for chemical and catalytic applications.     

稀土配合物的研究(Ⅴ)——稀土元素与-4-酰代双吡唑啉酮BPMPHD及α,α-联吡啶三元配合物的合成和性质

合成了14种稀土元素(R)与1,6-双(1′-苯基-3′-甲基-5′-吡唑啉酮-4′)-1,6-己二酮(BPMPHD,H_2L)和α,α-联吡啶(DPy,D)形成的新三元混配配合物R_2L_3D_2·~nH_2O(R=La,Y,n=10;R=Sm,…,Lu;n=4)及R_2L_3D·4H_2O(R=Pr,Nd),研究了配合物的红外、紫外-可见光谱、差热-热重、荧光等性质。配合物分解温度具有“四分组”效应及“双峰”性质。Nd、Ho、Er配合物有超灵敏跃迁。Sm、Eu、Tb、Dy和Tm具有线状荧光,Tb配合物荧光量子效率为0.124。     

Synthesis, infrared and fluorescence spectra of lanthanide complexes with a new amide-based 1,3,4-oxadiazole derivative

A new amide-based 1,3,4-oxadiazole derivative ligand 2,5-bis[2-(N,N-diethyl-1'-oxopropylamide)phenyl]-1,3,4-oxadiazole (L) and its complexes, Ln(NO3)3L (Ln=La, Eu, Gd, Tb, Er), were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The lanthanide ions were coordinated by O atoms from CO. The fluorescence properties of Eu(NO3)3L and Tb(NO3)3L in the solid state and in different solvents were investigated. Under the excitation of UV light, these complexes exhibit characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity were discussed.     

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.     

[（n—C4H9）4N][EuxM1—x（TTA）4]（M=La、Sm、Gd、Tb）的光致发光

合成了一类组成为[(n-C4H9)4N][EuxM1-x(TTA)4](M=La、Sm、Gd、Tb）的固体配合物，通过测定其红外光谱，X射线粉末衍射谱和荧光光谱，研究了配合物结构和发光性质随Eu^3 浓度变化的规律。红外光谱和XRD谱的分析结果表明，在体系中没有新化合物生成，而荧光光谱分析结果表明发光强度与Eu^3 浓度不成线性关系，不发光的基质配合物组分对发光有不同大小和不同类型的影响，提出一种可能的发光机制解释这一共发光现象。     

双(N-苄基)-2,7-萘-二(氧杂乙酰胺)稀土配合物的合成、表征、荧光性及其与DNA的作用

合成了2,7-二(苄胺酰乙氧基)萘(L)与稀土(RE:Y,La,Eu,Tb)苦味酸盐(pic)的配合物[RE(pic)3L2],用1H NMR、红外光谱、元素分析和摩尔电导表征了它们的结构、组成及性质。在pH=7.20的Tris-HCl缓冲溶液中用光谱法、伏安法和粘度法,测定4种配合物均以插入方式与ct-DNA发生配合作用,其作用强度为:La(Ⅲ)>Tb(Ⅲ)>Y(Ⅲ)>Eu(Ⅲ)。     

Studies on 1H NMR, infrared and fluorescence spectra of rare earth complexes with a new binaphthylamide

Solid complexes of lanthanide picrates with N,N-dibenzyl-2-[2'-[(dibenzylcarbamoyl)-methoxy]-[1,1']binaphthalenyl-2-yloxy]-acetamide (L), [Ln(pic)(3)L] (Ln = La, Nd, Eu, Gd, Tb, Dy, Y), have been prepared and characterized by elemental analysis, IR, 1H NMR, UV-Vis spectra and conductivity measurements. The fluorescence property of the europium complex in solid state and in CHCl(3), acetone, AcOEt and DMF was studied.