Synthesis, characterization, stability and relaxation behaviours of rare earth heteropolymetalates

Two rare earth heteropolymetalates K9GdW10O36 and K-11[Gd(PW11O39)(2)] have been synthesized and characterized by IR and elemental analysis. Their stability has been studied by TG - DTA. The TG - DTA analysis show that both complexes are of good thermal stability. Their relaxivity in D2O is 6.89 and 5.27 mmol(-1).s(-1) respectively. Interaction with BSA has also been investigated. The results indicate that the two rare earth heteropolymetalate may be potential contrast agent for MRI.

Recent progress in the studies of endohedral metallofullerenes

This overview presents the recent progress in the area of endohedral metallofullerenes in the past several years. The important results have been summarized as follows: (1) Many metals including Group 3 metals, most of the lanthanide series elements, and Group 2 metals have been encapsulated into a fullerene cage to form mono-, di-, and trimetallofullerenes by using the arc-evaporation technique. (2) Some endohedral metallofullerenes such as Group 3 metals, most of the lanthanide series elements, Group 2 metals, and some of their isomers have been successfully isolated and purified by a two-step or several-step HPLC technique. By using high-temperature and high-pressure extraction with pyridine, Ln@C-80, Ln@C-82, and Ln2@C-80 for most rare-earth metals have been selectively extracted in high yield (about 1% of the saw soot) from fullerenes and other size metallofullerenes. (3) The endohedral nature of metallofullerenes such as Y@C-82, Sc2@C-84, and Sc@C-82 has been finally confirmed by synchrotron X-ray powder diffraction. The symmetries and the structures of metallofullerenes such as Ca@C-82(III), La-2@C-80(I-h), Sc-2@C-84(D-2d), and Sc-2@C-84(C-s) have been confirmed by NMR measurements. (Lb) The information on the electronic structures and properties of endohedral metallofullerenes has been obtained by various spectrometric means Such as EPR, W-vis-MR, XPS, CV. It is generally accepted that three-electron transfer is favorable when M = Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu but Sc, Eu, Sm, Yb, Tm, Ca, Sr, Ba prefer to donate two electrons to the fullerene cages. (5) Several chemical reactions of endohedral metallofullerenes have been reported in which reagents are disilacyclopropane, digermacyclopropane, diphenyldiazomethane, and trifluoroacetic acid. (6) Mass spectrometry provided the crucial evidence that led to the discovery of metallofullerenes in 1985 and has always played a key role in their identification and characterization, Ion-mobility measurements of gas-phase ions have obtained the information of structures and the formation mechanism of endohedral metallofullerenes. till Theoretical calculations on the endohedral metallofullerenes have made an important contribution to the studies on the symmetry of the cage, the position of metal atom(s) inside the cage, the number of electronic transfer between metal atom(s) and fullerene cage, etc. (C) 2000 Elsevier Science S.A. All rights reserved.

钆-二乙三胺五乙酸与牛血清白蛋白作用的核磁共振研究

采用核磁共振弛豫分析法研究了造影剂母体化合物钆-二乙三胺五乙酸（Gd-DTPA）在水溶液和牛血清白蛋白溶液中的诱导弛像增强性质。Gd-DTPA络合物在水溶液中弛豫效率为5．25mmol-1·L·s-1，并发现牛血清白蛋白分子可非共价地结合Gd－DTPA络合物，这种非共价结合体的旋转相关时间明显长于自由络合物，使Gd-DTPA在蛋白质溶液中弛豫效率增高。本文结果表明该方法可以用来研究顺磁性金属络合物与蛋白质之间的相互作用情况。

人体血浆中15种超痕量稀土元素的电感耦合等离子体质谱法测定

本文用电感耦合等离子体质谱法测定了人体血浆中的稀土元素。在优化的条件下 ,以内标法测得的各种纯水溶液的检测限在 0 .7(Eu)～ 5 .4(Gd) ng·L- 1范围内。研究了 K,Na,Ca,Fe等基体元素对稀土测定的影响。以 In为内标元素补偿样品基体效应以及灵敏度飘移。比较了直接稀释、HNO3- H2 O2 消解及 HNO3-HCl O4消解 3种样品处理方法 ,用 1% HNO3直接稀释样品可满足轻稀土元素的定量分析要求 ,方法的定量测定下限≤ 1μg·L- 1。

稀土杂多配合物的合成、表征及其稳定性、弛豫性质

以N_9GdW_(10)O_(36)和K_(11)[Gd(PW_(11)O_(39)_2]作为研究对象,根据元素分析,红外光谱及差热-热重分析进行表征,对两种稀土杂多配合物的稳定性、溶解性进行了研究,并测试了其在水中及BSA溶液中的弛豫性能.其弛豫效率略高于目前临床所用的造影剂Gd-DTPA结果表明,这两种稀土杂多配合物均是比较好的潜在的磁共振成像造影剂

La_(0.5)R_(0.5)Ba_2Cu_3O_7,Pr_(0.5)R_(0.5)Ba_2Cu_3O_7以及RBa_2Cu_3O_7(R=稀土)的键共价性计算

使用复杂晶体化学键理论计算了La0 .5R0 .5Ba2 Cu3O7(R =Pr,Nd ,Sm ,Eu ,Gd ,Dy ,Y ,Ho,Er,Tm ,Yb ,Lu) (La-R12 3) ,Pr0 .5R0 .5Ba2 Cu3O7(R =La ,Nd ,Sm ,Eu ,Gd ,Dy ,Ho ,Y ,Er,Tm ,Yb ,Lu) (Pr -R12 3)以及RBa2 Cu3O7(R =La ,Pr,Nd ,Sm ,Eu ,Gd ,Dy ,Ho ,Y ,Er,Tm) (R12 3)中Cu—O键的键共价性 ,结果表明Pr-R12 3,La-R12 3,以及R12 3都应具有超导性 ,而实验结果是La0 .5Pr0 .5Ba2 Cu3O7,R0 .5Pr0 .5Ba2 Cu3O7(R =La,Nd ,Sm ,Eu ,Gd)无超导性 .产生这种矛盾的原因尚不明确 ,需要做进一步的研究.

Studies on the solution structures of lanthanide(III) complexes of DTPA-BIN by NMR

The solution structures of diamagnetic lanthanide (III) complexes of DTPA-BIN (Ln = La, Y, Lu, Sc) have been investigated by H-1 NMR, C-13 NMR and 2D NMR. For each complex, two or more species of asymmetric conformations with little distinction were identified at room temperature. And their solution structures vary with the radius of the central metals. NMR spectra support the hypothesis that Sc3+ with smaller radius formed an eight-coordinated structure with DTPA-BIN, La3+ with larger radius formed nine- or ten-coordinated structures with DTPA-BIN, and Y (DTPA-BIN) and Lu (DTPA-BIN) had nine-coordinated solution structures. The solution structure of Gd (DTPA-BIN) was obtained from the similarity of radius between Gd3+ and Y3+, which is a nine-coordinated structure formed by three nitrogens, three acetate oxygens, two acetyl oxygens, one water molecule and a gadolinium(III) cation.

A comparative study on the electroluminescence properties of some terbium beta-diketonate complexes

By comparing the phosphorescence spectra of Gd(acac)(3) (acac=acetylacetone), Gd(TFacac)3 (TFacac=1,1,1-trifluoroacetylacetone), the effects of fluorine replacement of hydrogen on the triplet state energy of the ligands were revealed. Fluorine can lower the triplet state energy of Hacac and make it more suitable for energy transfer towards the D-5(4) state of terbium. Organic electroluminescent devices (OELDs) with the corresponding trivalent terbium complexes as emissive layers were fabricated. Triple-layer-type devices with a structure of glass substrate/ITO (indium tin oxide)/PVK [poly(N-vinylcarbazole)]/PVK : Tb complex: PBD [2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole]/PBD/Al exhibit bright green luminescence upon applying a dc voltage. The luminance of a device with Tb(TFacac)(3)phen (1,10-phenanthroline) and Tb( TFacac) 3 as emissive layer is higher than that of the corresponding devices with Tb(acac)(3)(phen) and Tb(acac)(3) as emissive layers. The EL device with Tb(TFacac)(3)(phen) as emitter exhibits characteristic emission of Tb3+ ions with a maximum luminance of 58 cd m(-2) at 25 V.

Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

Luminescent properties of Gd3PO7 : Eu in UV/VUV region

The luminescent properties of Gd3PO7:Eu were investigated in W and VUV regions. This phosphor has such strong emissions around 618.5 nn under UV excitation, especially around 209nn, that it has a better colour saturation than that of Y2O3:Eu. It could be a new potential red phosphor for lamp and other applications with W-excitation source or even for displaying devices. In the VUV excitation spectrum of Eu3+ emissions, energy absorptions by Gd3+, Gd-O and PO43- have been observed, on which it can be inferred that there are three kinds of energy transferring processes to Eu-3(+) ions. The energy absorptions of Gd3+, Gd-O and PO43- are induced by 4f --> 4f transitions, a bandgap transition of Gd3PO7 and intramolecular (2t(2) --> 2a, 3t(2)) transition, respectively. The energy transfer efficiency of the PO43- intramolecular transition is lower compared with that of the bandgap transition (Gd-O).

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

铁掺杂GdBa_2Cu_3O_7的化学键性质和Mossbauer谱研究

利用电介质的平均能带模型计算了 Gd Ba2 Cu3O7的化学键参数 ,得到 Cu(1 ) - O键的平均共价性为 0 .41 6,Cu(2 ) - O键的平均共价性为 0 .2 8。应用由共价性和极化率定义的化学环境因子计算了 57Fe在 Gd Ba2 Cu3O7中的 Mossbauer同质异能位移 ,确定了 57Fe在 Gd Ba2 Cu3O7中的价态和占位情况。

核磁共振法研究DTPA-BIN稀土配合物的溶液结构

用核磁共振方法研究了抗磁稀土配合物 Ln( DTPA-BIN) ( Ln=La,Y,Lu,Sc)的水溶液结构 . 1 H和1 3 C NMR谱的谱形特征表明 ,每一种配合物在水溶液中存在着两种以上不对称的异构体 ,异构体之间的差别较小 .并由 Y3+ 与 Gd3+ 离子半径的相似性推测出 Gd( DTPA-BIN)的溶液结构 ,即 DTPA-BIN分子提供 8个配位点 :3个骨架氮、 3个乙羧基氧及 2个酰胺氧 ,1个水分子占据另一个配位点 ,从而与 Gd3+ 形成了九配位结构 .溶液结构随中心金属离子半径不同而呈规律性变化

Determination of rare earth elements in biological samples by inductively coupled plasma mass spectrometry

A method for the determiantion of rare earth elements in biological sampels by inductively coupled plasma mass spectrometry was developed. Oxide ion yield of the rare earth elements (RFE) decreased with the increasing of RF power and the sampling depth, or with the decreasing of carrier gas flow rate. The spectral interference arising from (PrO)-Pr-141-O-16 on Gd-157 must be corrected. if the concentration of Ba was high enough, it was necessary to correct the spectral interference arising from (BO)-B-135-O-16 on Eu-151, and it was not necessary to correct spectral interference arising from (NdO)-Nd-143-O-16 on Tb-159 etc. in the biological samples under the selected operation parameters. In the biological sample, the major matrix elements, such as K, Na and Ca, result in the suppression of REEs signals and the suppression degree of the Ca is grezter than that of the K and Na. The mussel sample was digested by thd dry ashing, wet digestion with HNO3 + H2O2 and HNO3 + HClO4, respectively. The analytical results of REEs were consistent with each other. Detection limits for REEs are 0.001 similar to 0.013 mu g/L. Recoveries of standard addition are 91.7% similar to 125%. REEs in biological samples were determined directly without separation and preconcentration procedure.

The channel behavior of gramicidin D in the self-assembled monolayer

It was found for the first time that gramicidin D (GD) molecules can be incorporated into the ODM monolayer which is self-assembled on the surface of the gold electrode and form monovalent cation channels.