两个氮氧双自由基桥连的稀土一维链的晶体结构、磁性和荧光性能

选用1,2-二苯氧基乙烷取代的氮氧双自由基(BNPhOEt)与稀土金属反应,得到了2例氮氧双自由基-稀土配合物[Ln(hfac)3(BNPhOEt)]·C6H14(Ln=Tb(1)、Ho(2);hfac=六氟乙酰丙酮),其均为2p-4f一维链状结构.磁性研究表明,在配合物1和2中分别存在铁磁和反铁磁耦合.此外,对2个配...     

含大环多胺的两亲性小分子的设计合成及与DNA的相互作用

本文设计合成了两个含大环多胺亲水基团和甾体亲脂结构的两亲性小分子化合物, 化合物的结构经过核磁共振谱, 红外光谱和高分辨质谱确证. 凝胶电泳实验显示这类化合物与Sn-甘油-1,2-二油酰-3-磷酰乙醇胺 (DOPE)形成的阳离子脂质体对DNA有很强包裹能力. 两种脂质体M1和M2分别在N/P比为7和5时即可完全包裹质粒DNA. 另外, 这类脂质体与DNA形成的复合物的粒径经测定在160~220 nm之间, zeta电位为+20~40 mV. 实验结果显示这类脂质体具备了作为非病毒基因载体的潜在性, 可为设计阳离子脂质提供新思路.     

Dinuclear Lanthanide Compound as a Promising Luminescent Probe for Al3+ Ions

Luminescent probes have wide applications in biological system analysis and environmental science. Here, one novel luminescent dinuclear europium compound with a crown ether analogous ligand was synthesized through a solvent–thermal reaction. Through transformation, upon the addition of Al³⁺ ions to the N,N′-dimethyl formamide solution of the europium compound, the luminescent intensity of the characteristic emission of Eu³⁺ decreased, and a new emission peak appeared at 346 nm and increased rapidly. The luminescent investigation indicated that it could act as a highly sensitive and selective luminescent probe for Al³⁺ ions. Moreover, mass spectrometry and single-crystal X-ray diffraction confirmed the formation of a new more stable trinuclear aluminium compound during the sensing process.     

含双Cyclen阳离子脂质的合成及与DNA的相互作用

设计合成了一类新型的阳离子脂质小分子化合物1.化合物1含有双cyclen亲水端和甾体疏水基团.凝胶电泳实验显示,含胆固醇和皂素的双大环多胺阳离子脂质化合物1与二油酰磷脂酰乙醇胺( DOPE)形成的阳离子脂质体能够与DNA有效作用,在氮磷比为6时即可完全包裹DNA,具有作为非病毒基因载体的潜在应用价值,为设计新型阳离子脂...     

通过稀土离子和羧酸配体组装成的两种新型的二维配位聚合物的合成、晶体结构及荧光性质

利用水热法合成了两种新型的二维（2D）稀土配位聚合物[Ln(PDC)(OH)(H2O)2]n (Ln = Eu (1) and Tb (2), H2PDC = 3,4-吡啶二羧酸),通过元素分析、红外光谱、热分析和X射线单晶衍射等技术对其进行了表征。单晶结构分析表明这两种配合物都显示出包含有一维Ln-O-Ln链的二维层状结构,层间又进一步通过 π-π 堆积和氢键作用扩展成三维超分子网络结构。此外,这两种配合物的固体在室温下都有强的荧光发射。     

新氮杂冠醚稀土配合物的制备、表征及其荧光性质

合成了一新的大环氮杂冠醚及其稀土配合物,并通过元素分析、摩尔电导、热分析及红外的测定对配合物进行了表征。结果表明,冠醚配体上的C和N原子均参与配位,并推测了配合物的可能组成。室温下研究了配合物的固体及在溶液中的荧光光谱。固态时Sm^3 ,Eu^3 ,TB^3 ,Dy^3 的冠醚配合物均有较强荧光,其中Tb^3 的荧光强度最高,表明冠醚配体三重态的能量与Tb^3 的振动能级更为匹配。在Eu^3 配合物中,强度比η(^5D0→^7F2/^5D0→^7F1)=5.3,表明Eu^3 处于一非对称配位环境中。     

Lanthanide Luminescent Nanocomposite for Non-Invasive Temperature Monitoring in Vivo

Temperature monitoring in vivo plays a vital role in the investigation of biological processes of organisms and the improvement of disease theranostic methods. The development of lanthanide luminescent nanocomposite-derived temperature probes in vivo allows accurate and reliable interrogation of biological thermodynamic processes due to their superior photostability, high sensitivity, and non-invasive sensing fashion. This concept presented an overview of the recent development of lanthanide luminescent nanocomposite which are suitable for in vivo temperature monitoring, including the thermometric principles, key features, materials designs as well as their potential biomedical applications for non-invasive temperature detection in the living body. The perspectives of these lanthanide luminescent nanocomposite thermometers for the optimization of temperature monitoring performance and potential future development are also discussed.     

Assembly and Photophysics of Ternary Luminescent Lanthanide Molecular Complex Systems

In this paper, according to the molecular fragment principle, a series of eight ternary luminescent lanthanide complex systems were assembled, and whose compositions were determined with elemental analysis and infrared spectrum: Ln(MA)₃(L)·H₂O, where Ln = Sm, Eu, Tb, Dy; HMA = α‐methylacrylic acid; L = 1,10‐phenanthroline (phen), 2,2′‐bipyridine (bipy). The photophysical properties of these functional molecular systems were studied with ultraviolet‐visible absorption spectrum, and fluorescence excitation and emission spectrum. It was found that the heterocylic compounds (phen and bipy) act as the main energy donor and luminescence sensitizer for their suitable energy match and effective energy transfer to the emission energy level of Ln³⁺ ions. MMA ligand was only used as the terminal structural ligand to influence the luminescence. Especially terbium complex systems show the strongest luminescence for the optimum energy match and transfer between phen (bipy) and Tb³⁺ ion.     

Synthesis, Crystal Structure and Luminescent Property of a One-dimensional Europium Citrate Complex

A new compound, [Eu(Hcit)(H2O)2]·H2O]n (1, Hcit3-= C(OH)(COO-)(CH2COO-)2), has been synthesized under hydrothermal reactions of europium oxide, MnCl2·4H2O and citric acid at 120 ℃ for three days. The compound was characterized by single-crystal X-ray diffraction analyses, IR and TGA. Complex 1 crystallizes in monoclinic, space group P21/n with a = 6.179(1), b = 9.688(2), c = 16.990(3) , β = 91.98(3)°, Z = 4, V = 1016.4(3) 3, C6H11EuO10, Mr = 395.11, Dc = 2.582 g/cm3, μ = 6.218 mm-1, F(000) = 760, R = 0.0183 and wR = 0.0411. Single-crystal X-ray analysis reveals that complex 1 displays 1D ladder chains along the a axis, with dinuclear Eu2O2 units serving as "steps" and carboxylate groups as "uprights", which are connected by hydrogen bonds. The solid-state luminescent property of complex 1 was investigated at room temperature. Upon excitation at 394 nm, compound 1 exhibits interesting luminescent properties with several intense bands in the visible region and the most intense and sharp emission being in the red region at 615 nm. The TGA and XRD results prove that complex 1 undergoes facile thermal decomposition to form Eu2O3 at about 870 ℃.     

近红外发光稀土配合物及杂化材料研究进展

稀土因其特殊的物理和化学性质,在信息技术、能源技术、生物技术等高科技领域及国防建设等方面都起着非常重要的作用,中国作为稀土大国,十分重视对稀土材料的研究和开发。稀土离子近红外发光(750～1700 nm)在激光和光纤通讯、医学诊断、免疫分析等热门领域的潜在应用,受到了科研人员的极大关注。稀土离子本身发光极弱,通过分子内传能有机配体可以敏化稀土离子发光,但稀土配合物常受外界干扰,其稳定性较差,若将其与凝胶、介孔材料、离子液体等无机基质复合,得到具有良好光、热稳定性和化学稳定性的有机/无机杂化材料。总结了近些年来近红外发光稀土配合物及近红外发光稀土杂化材料的研究进展,并对其发展前景进行了展望。     

Synthesis, Characterization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with 1,10-Phenanthroline

IntroductionTherehasbeenconsiderableinterestinthecoordinationchemistryoflanthanidecomplexeswithcarboxylateligandsduetotheirpotentialapplicationinmolecularassembliesandluminescentprobesinsystemsofbiologicalrelevance .1 4 Ofthenumerouslanthanidecomplexesthathavebeenwidelystudied,5 9mostofthemarefoundtoexhibitavarietyofdimericorinfinitechainstructure.RecentlywehavereportedpolymericLu(POA) 3(phen)compoundinwhichlutetiumionsforminfinitechainalongtheb axisdirectionthroughthecoordinationofbridgingc…     

4，4′-二羧基二苯基砜的镧系配合物的合成和结构

合成了V型半刚性配体4,4'-二羧基二苯基砜的3个新的镧系配合物[Nd2(dbsf)3(DMF)225(H2O)1.75·1.25DMF·0.5MeOH(1),[Yb2(dbsf)3(H2O)2]·1.5H2O(2)和[Er2(dbsf)3(H2O)2]·0.75H2O(3)(H2dbsf=4,4'-二羧基二苯基砜,DMF=N,N-二甲基甲酰胺,MeOH=甲醇),并测定了它们的晶体结构.结构表明配合物1具有一维孔道的三维镧系金属,有机骨架结构(LnOF),未配位的DMF和MeOH填充在孔道中;配合物2和3也具有三维的LnOF结构,但晶格水存在于洞穴里.它们的形成与结构特征可能与半刚性V型配体H2dbsf和镧系收缩效应有关.     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

两种具有三维孔道结构有机模板稀土硫酸盐的合成、表征及性质研究

本文分别采用水热和溶剂热的方法,以乙二胺和哌嗪为有机模板剂分别合成了两种新的三维孔道结构的稀土硫酸盐[Gd2(SO4)5(H2O)2][C2N2H10]2(1),[Eu2(SO4)5(H2O)2][C4N2H12]2(2),并且通过单晶X射线衍射、元素分析、红外、热重对两种化合物进行了表征。化合物1和2都属于单斜晶系,P21/c空间群。化合物1:a=0.652 1(4)nm,b=1.692 0(9)nm,c=2.023 3(11)nm,β=95.168(7)°,Z=4。化合物2:a=1.972 1(2)nm,b=1.927 1(2)nm,c=1.323 20(14)nm,β=92.307 0(10)°,Z=8。单晶结构分析表明,这两种化合物的无机骨架都是由SO4连接具有交替十六元环与八元环二维层形成的三维孔道结构。化合物2的固体荧光分析表明,在396 nm的激发波长下表现出Eu3+的特有发光性质。     

壳聚糖修饰PLGA阳离子型纳米微球的制备与表征

采用单乳化-溶剂(O/W)挥发技术制备表面带正电荷的壳聚糖(CHS)修饰聚乙/丙交酯(PLGA)纳米微球(PLGA/CHS), 通过正交试验优化了纳米微球的制备条件. 结果表明, 微球粒径可控制在150～200 nm内, 在pH=4时, 纳米微球表面电位最高为55 mV. 影响微球粒径的主要因素是聚合物的浓度, CHS的分子量和浓度以及介质的pH值对微球表面电位也有明显影响. 制备粒径较小而表面电位较高的PLGA/CHS纳米微球条件为: ρ(CHS)=3 mg/mL, ρ(PLGA)=10 mg/mL, Vo/Va=1/4. SEM图像显示经CHS修饰的PLGA的纳米微球形状规整, 荧光显微观察和XPS分析结果证实CHS包覆于微球表面.     

聚对苯基苯并二噻唑及聚-2,2'-间苯基-5,5'-二苯并咪唑体系发光性质的理论研究

我们利用理论计算方法对两类聚合物: 聚对苯基苯并二噻唑(PTB)和聚-2,2'-间苯基-5,5'-二苯并咪唑(PBI)进行研究, 计算两类聚合物的性质并对其共混聚合物的性质进行预测. 我们通过计算可以知道, PTB为具有良好平面性的全共轭刚性聚合物, 而PBI为卷曲型的部分共轭聚合物. 计算两类聚合物的电离能、电子亲和势. 比较后发现PTB具有较好电子注入和传输能力, 而PBI的空穴注入和传输能力比PTB稍好. 与PTB相比, PBI的吸收与发射光谱蓝移. 文章还预测PTB/PBI共混体系的发光性质. 在全共轭PTB中添加部分共轭PBI以改善加工性能的同时, 改善空穴的注入及传输能力, 但会使体系的吸收及发射光谱蓝移.     

Synthesis,Charactarization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with1,10—Phenanthroline

Three new lanthanide phenoxyacetate complexes with 1,10‐phenanthroline. [Nd(POA)₃ (phen)]₂ · 2C₂H₅OH (1), [Eu(POA)₃‐ (phen)]₂ · 2C₂H₅OH (2) and [Sm(POA)₂(DMSO)(phen)]₂‐ (ClO₄)₂ (3) (POA= phenoxyacetate, phen = 1,10‐phenanthroline, DMSO = dimethyl sulfoxide), were synthesized and characterized by elemental analyses, IR, UV‐vis and FAB‐MS spectra. Their structures were determined by single crystal X‐ray diffraction analysis. In complexes 1 and 2, the carboxylate groups are bonded to Ln³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and the bridging tridentate. In complex 3, the carboxylate groups are bonded to Sm³⁺ ion only involved in one mode: the bridging bidentate. The luminescence behavior of complex 2 was also studied by means of emission spectra.     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼(MH)为配体,通过溶剂热法合成了配位聚合物[Dy2(MH)6]n·0.5DMF(1)和[Eu2(MH)6]n(2)。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu~(3+)的5D0→7FJ(J=0~4)能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu~(3+)的5D0→7F2能级跃迁。     

两个双核稀土金属配位聚合物的溶剂热合成、晶体结构及荧光性质

以顺丁烯二酰肼（MH）为配体,通过溶剂热法合成了配位聚合物[Dy₂（MH）₆]_n·0.5DMF（1）和[Eu₂（MH）₆]_n（2）。通过红外光谱、X射线粉末衍射、X射线单晶衍射表征了2个晶体的结构。配合物1和2都是三斜晶系,P1空间群。以双核结构为顶点作图得到配合物的空间拓扑结构,拓扑类型为tsi。配合物的热重分析结果表明2个配合物在315℃左右仍有较好的热稳定性。固体荧光结果表明配合物2在激发波长为375 nm时有对应Eu³⁺的⁵D₀→⁷F_J（J=0~4）能级能量的5个发射峰,最强发射峰波长为616 nm,归属为Eu³⁺的⁵D₀→⁷F₂能级跃迁。     

新型手性稀土配合物的合成、表征及其在不对称催化反应中的应用

作为符合绿色化学标准的稀土三氟甲磺酸盐Ln(OTf)3化合物打破了传统路易斯酸催化的模式，以其在水中稳定、催化用量少(一般少于10 mol％)和可回收再用的独特性质而受到广泛关注。Ln(OTf)3化合物可以催化许多有机合成反应，得到多种多样重要的合成中间体。但是，到目前为止，手性