发光稀土配合物的生物功能分子传感研究进展

基于稀土离子独特的电子组态和有机配体的敏化作用,稀土中心发光的配合物具有发光寿命长、发射峰尖锐和Stokes位移大等特点,可在复杂环境中针对特定的分析物进行快速和便捷的检测。稀土配合物与生物功能分子如生命必需分子、疾病标志物分子和药物分子等相互作用引起其光学信息的变化可以实现对生物功能分子的快速传感,在监测生命体的生理状态和公共卫生安全等方面具有重要的意义。本文综述了稀土配合物针对生物功能分子的传感性质研究进展,讨论了设计稀土配合物材料的传感策略,提出了稀土配合物作为生物功能分子先进传感材料的发展建议。     

稀土配合物杂化发光材料的组装及光物理性质研究进展

稀土配合物兼具无机物稳定性好以及有机物荧光量子效率高的优点,而且具有可设计性,制备简便,容易修饰,荧光性质优异（发射谱带窄、色纯度高、荧光寿命长、量子产率高以及发射光谱范围覆盖可见和近红外光区等）．但配合物的光、热、化学稳定性和机械加工性能相对较差,因而限制了其在很多领域中的实际应用．近年来的研究表明,将稀土配合物引入到各种基质材料中可以改善其稳定性及机械加工性能,并对其光物理性质产生调制作用．根据基质材料的不同,杂化材料可分为无机基质、无机／有机复合基质及有机基质杂化材料．本文综述了这些不同基质稀土配合物杂化发光材料的研究进展,探讨了主客体间相互作用对杂化材料光物理性质及稳定性的影响,为实现稀土配合物杂化发光材料在光学器件领域（LED照明、光纤维、光学放大器及激光等）及生命分析领域的应用提供了重要的理论依据．     

稀土配合物发光中的能量传递研究

就稀土发光的能量传递开展了3个方面的初步研究。首先,研究了稀土镧和铕掺杂后共发光的现象和机制;其次是研究了稀土铽配合物作为能量传递桥可以将能量从导电高分子聚乙烯咔唑（PVK）有效地传递给铕配合物;第三,发现通过物理掺杂的方法可以改变稀土铕配合物的激发光谱的形状,使其向着长波长方向移动,这样可以使铕配合物的激发光谱和PVK的发射光谱发生更大的重叠,从而增强它们之间的能量传递效率。     

稀土配合物荧光探针在活细胞成像研究中的新进展

稀土配合物荧光探针在生物学研究中,尤其在活细胞成像方面的应用渐已引起人们的关注.本文就稀土配合物的发光特点及其作为荧光探针在活细胞成像研究领域的进展进行了评述.引用文献70篇.     

稀土有机配合物发光研究的新进展

本文描述了稀土有机配合物发光学基础研究及有关应用研究的国内外动态。评述了近十年来稀土-β二酮配合物发光研究的新进展及在工农业、科技方面的应用。对八十年代后期发展起来的稀土生物荧光标记、稀土离子在生物大分子结构探针研究方面也给予了综合报道。此外,对稀土-高分子有机配合物、低价态稀土-有机配合物发光研究的概况做了介绍。最后,本文还展望了稀土-有机配合物发光研究的发展趋势.     

水溶液中羟脯氨酸稀土配合物的NMR研究

测定了在11种稀土离子(La~(3+)、Pr~(3+)、Nd~(3+)、Eu~(3+)、Tb~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)、Yb~(3+)和Lu~(3+)存在下羟脯氨酸~(13)C的诱导位移和抗磁性稀土配合物体系的~(1)H化学位移与偶合常数。对配合物构象分析表明,在水溶液中羟脯氨酸以空间位阻小的“外向”构象存在,通过羧基与稀土离子形成双齿配位结构,Ln~(3+)-O键长为2.1。在水溶液中巳配位的与游离的氨基酸和水分子间的快速配位交换平衡导致稀土氨基酸配合物具有有效轴对称性。     

d-f跃迁发光稀土配合物研究进展

稀土配合物独特的发光性质使其在众多领域有很大的应用价值.其中,d-f跃迁发光稀土配合物具有跃迁宇称允许、激发态寿命短和光谱可调等特点,但相关研究还有待进一步深入.本文介绍了稀土配合物的发光机制,综述了具有d-f跃迁发光性质的稀土配合物(主要是Ce3+,Eu2+,Yb2+和Sm2+配合物)的研究进展,并初步总结了配合物分...     

稀土配合物的发光特性及其能量传递研究

利用激光诱导荧光技术研究了稀土铕等金属配合物的发光特性及其能量传递动力学过程．得到了这些稀土配合物中中心离子Eu（3 ）的激发光谱，配体的三线态发时光谱和单线态发射光谱；在实验上观察到由于中心离子Eu（3 ）的5D2←7F0马跃迁吸收造成的配体发射光谱中的凹陷行为     

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。     

多彩金纳米簇:从结构到生物传感和成像

金纳米簇是一种具有发光性能的“类分子”新兴纳米材料.通过调控金原子数目和配体组成性质,金纳米簇可以实现同激发光下不同波段发射,从而展现出“五彩缤纷”的发光特性,这使其被广泛应用于光催化、光学器件、传感和成像等多个领域.因此,开发和优化具有优异发光性能的金纳米簇一直是化学、材料和生物学科的研究热点.本文立足于金纳米簇的发...     

Synthesis and Spectroscopic and Luminescent Properties of Er,Yb and Lu Complexes with Cyano-Substituted Phthalocyanine Ligands

Based on 4,4′-[1,3/4-phenilenebis(oxy)]phthalodinitriles, the mixture of phthalocyaninates of various structures with rare-earth metals were obtained by template fusion method minimizing the side polymerization processes. Target monophthalocyaninates were isolated from the reaction mixture and purified using column and then gel permeation chromatography. The compounds were characterized by NMR, IR spectroscopy, mass spectrometry, and elemental analysis. The spectral properties were studied and the aggregation behavior of the synthesized Er, Yb, and Lu phthalocyaninates in chloroform, acetone, and tetrahydrofuran was determined. It has been shown that lutetium complexes with 3,4-dicyanophenoxyphenoxy ligands are the least stable and least resistant to aggregation in solution, while erbium and ytterbium phthalocyaninates proved to be stable in all studied media. The quantum yields and fluorescence lifetimes of the complexes in chloroform and tetrahydrofuran were calculated.     

Enantiomerically Pure Constrained Geometry Complexes of the Rare-Earth Metals Featuring a Dianionic N-Donor Functionalised Pentadienyl Ligand: Synthesis and Characterisation

We report the preparation of enantiomerically pure constrained geometry complexes (cgc) of the rare-earth metals bearing a pentadienyl moiety (pdl) derived from the natural product (1R)-(−)-myrtenal. The potassium salt 1 , [Kpdl*], was treated with ClSiMe₂NHtBu, and the resulting pentadiene 2 was deprotonated with the Schlosser-type base KOtPen/nBuLi (tPen=CMe₂(CH₂Me)) to yield the dipotassium salt [K₂(pdl*SiMe₂NtBu)] ( 3 ). However, 3 rearranges in THF solution to its isomer 3’ by a 1,3-H shift, which elongates the bridge between the pdl and SiMe₂NtBu moieties by one CH₂ unit. This is crucial for the successful formation of various monomeric C₁- or dimeric C₂-symmetric rare-earth cgc complexes with additional halide, tetraborohydride, amido and alkyl functionalities. All compounds have been extensively characterised by solid-state X-ray diffraction analysis, solution NMR spectroscopy and elemental analyses.     

Self‐Assembly of a Trinuclear Luminescent Europium Complex

Triangular luminescent box : Self‐assembly of a new multidentate receptor with europium cations results in the formation of trinuclear discrete complexes. X‐ray crystallography shows that nine‐coordinate cations are linked by ligands to provide a triangular complex in the solid state and in solution. Despite the coordinated solvent molecules, this topologically unusual complex exhibits remarkable luminescent properties.

     

Cyanine-Like Boronic Acid-Derived Salicylidenehydrazone Complexes (Cy-BASHY) for Bioimaging Applications

Boronic acid-derived salicylidenehydrazone complex (BASHY) dyes with a polymethine backbone were designed to yield efficient red-emitting and two-photon absorbing fluorophores that can be used as markers for astrocytes. The dyes are chemically stable in aqueous solution and do not undergo photodecomposition. Their photophysical properties can be electronically fine-tuned and thereby adapted to potentially different imaging situations and requirements.     

稀土上转换发光纳米材料的应用

稀土上转换发光纳米材料(简称UCNPs)不仅光稳定性强、发射带窄、荧光寿命长、化学稳定性高、潜在生物毒性低,而且采用近红外连续激发光源激发还使其具有较大的光穿透深度、无光闪烁和光漂白、无生物组织自发荧光以及对生物组织几乎无损伤等显著优点,已经成为当前很多领域乃至交叉科学的应用研究热点。由于氟化物基质的UCNPs具有较高的发光效率,本文首先归纳总结了近年来氟化物UCNPs的主要合成及表面改性方法,然后重点综述了近年来UCNPs在免疫分析及生物传感、生物成像、载药、光动力理疗及热致理疗、光导开关和信息存储以及太阳能电池等方面的研究与应用进展。     

稀土超分子配合物研究进展

超分子化学作为"广义上的配位化学",是一个充满活力的领域.基于配位自组装,设计合成具有不同拓扑结构和功能特性的超分子配合物是超分子化学的研究重点.基于稀土元素构筑的超分子配合物不仅丰富了配位超分子体系,也是制备功能性配合物的核心内容.主要从拓扑结构调控、结构修饰和功能特性等方面综述了螺旋、格子、环状和笼状等稀土超分子配...     

Side-Arm Assisted Anilido-Imine Based Rare-Earth Metal Complexes for Isoprene Stereoselective Polymerization

Anilido-imine ligands o-C₆H₄(NHAr₁)(CH=NAr₂), in which Ar₁ is 2,6-diisopropylbenzyl group and Ar₂ contains fluorine (HL₁) or methoxyl (HL₂) group on ortho-position of phenyl substituent, were synthesized for constructing rare-earth metals based complexes of 1a–1c (HL₁ based Sc, Lu, Y) and 2a–2c (HL₂ based Sc, Lu, Y). Based on their NMR spectra and X-ray single-crystal structures, the side-arm group of -F and -OMe is identified to chelate to the corresponding central metal. The twisted angles between two planes formed by chelated heteroatoms (N, N, F for HL₁ and N, N, O for HL₂) are observed, in which the largest dihedral angle (53.3°) for HL₁-Y and the smallest dihedral angle (44.32°) for HL₂-Sc are detected. After being activated by AlⁱBu₃ and [Ph₃C][B(C₆F₅)₄], these catalysts showed great activity for isoprene polymerization. Bearing the same ligand HL₁, smaller scandium based complex 1a and middle size of lutetium based 1b provided lower cis-1,4-selectivity (57.3% and 64.2%), larger yttrium complex 1c displayed high cis-1,4-selectivity (84%). Chelating by crowded HL₂, small size of scandium complex 2a provided impressive trans-1,4-selectivity (93.0%), middle lutetium based 2b displayed non-selectivity and larger yttrium complex 2c showed clear cis-1,4-selectivity (83.3%). Moreover, 2a/AlⁱBu₃ system showed the quasi-living chain transfer capability.     

发光的异核稀土配合物装饰氧化石墨烯片

采用非共价键的方法制备一种新型的高荧光性能氧化石墨烯-异核稀土杂化材料。利用苯甲酸(BA)和菲咯啉(Phen)与Sm~(3+)和Gd~(3+)配位,并作用在氧化石墨烯片(GOSs)表面,制备了一种异核稀土配合物。所制备的产物通过傅里叶变换红外光谱、X射线衍射、扫描电子显微镜、荧光光谱仪、荧光寿命和热重分析来表征。该杂化材料具有强发光强度、长的寿命和良好的热稳定性。此外,Gd~(3+)对材料具有很强的敏化作用,同时Gd~(3+)在提高发光强度方面起着重要作用。氧化石墨烯的存在不会淬灭杂化材料的荧光性能。此外,还研究了具有不同物质的量之比的Sm~(3+)和Gd~(3+)的荧光特性。     

Rational Design of Cyclometalated Iridium(III) Complexes for Three-Photon Phosphorescence Bioimaging

Compared to 2PE (two-photon excitation) microscopy, 3PE microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference. The design of suitable agents with a large Stokes shift, good three-photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is challenging. Now, two Ir^III complexes (3PAIr1 and 3PAIr2) were developed as efficient three-photon phosphorescence (3PP) agents. Calculations reveal that the introduction of a new group to the molecular scaffold confers a quadruple promotion in three-photon transition probability. Confocal and lifetime imaging of mitochondria using Ir^III complexes as 3PP agents is shown. The complexes exhibit low working concentration (50 nm ), fast uptake (5 min), and low threshold for three-photon excitation power (0.5 mW at 980 nm). The impressive tissue penetration depth (ca. 450 μm) allowed the 3D imaging and reconstruction of brain vasculature from a living specimen.