1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉的合成及锌离子探针的研究

设计合成了1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉(4), 测试了其紫外光谱和荧光光谱, 研究了其对锌离子的选择性识别作用. 结果表明, 化合物4作为锌离子荧光探针, 受常见离子的干扰较小, 对于锌离子有着较高的选择性和较低的检出限.     

5,5-二乙烯基-2,2-联吡啶:可能的新型锌离子荧光探针(英文)

生物体系里微量元素锌在发育、新陈代谢和疾病的发生等多个领域扮演了重要的角色,定性和定量测量锌的含量将帮助我们理解锌的生物学意义。我们偶然发现5,5-二乙烯基-2,2-联吡啶(DVBP)在二氧六环里对锌离子呈现出类似比例计量型荧光探针的特性:即有2个荧光发射峰而且长波长峰随锌离子的增加按比例增长。但DVBP难溶于水而且2个荧光发射峰距离太近从而相互干扰,我们尝试利用硅氢反应将DVBP固定在多孔硅上制备感应锌离子的光极,我们发现多孔硅固相载体上的联吡啶通过与锌离子的螯合后荧光增强约8倍,比DVBP在溶液里与锌离子螯合后的荧光增强(约4.5倍)还要多,联吡啶对锌离子的荧光响应是一个值得继续探索的领域。     

基于水杨醛席夫碱结构的锌离子选择性荧光探针

设计并合成了一种新型锌离子荧光探针——4-N,N-二乙胺基水杨醛-2-吡啶肼席夫碱(1).在pH为7.0的50%水/乙醇(体积比)体系中,1对锌离子表现出显著的荧光增强响应.提高体系中的乙醇含量有利于获得更高的荧光放大倍数,在纯乙醇中,1对锌离子的荧光增强可达100倍.1对锌离子的荧光检测表现出良好的选择性,尤其可以区分锌离子的常见干扰离子镉离子.其线性范围为0.1~1.0μmol/L,检测限达到35 nmol/L.同时,1被成功用于实际水样中锌离子的定量检测.     

锌离子荧光探针研究进展

锌广泛存在于人体内,具有重要生理功能。因此,对游离锌离子的选择性识别和有效检测具有重要意义。荧光探针因其设计简单、易于操作、灵敏度高、可细胞成像等诸多优点而广泛应用于锌离子的识别研究。锌离子荧光探针常见的识别机理包括光致电子转移、分子内电荷转移、荧光共振能量转移、聚集诱导荧光增强、螯合荧光增强等。其中,基于螯合荧光增强机理的锌离子探针,其荧光团通常可同时作为识别基团,因此,相比于其它探针,具有设计较为简单、合成较为便捷的优点。本文综述了近年来文献中报道的基于以上各种识别机理的锌离子荧光探针,并着重介绍了螯合荧光增强机理在锌离子识别中的应用。     

水介质中一种高灵敏识别锌离子的荧光传感器

本文利用2-氨基苯酚和5-氯水杨醛合成了一种简单的席夫碱荧光探针CP,通过氢谱和质谱表征了化合物CP的结构。在乙腈-水的混合溶液中对其进行了聚集荧光性能的测试,结果表明这种分子具有很好的聚集荧光分子的特性。纯水溶液中,CP能够高选择性识别锌离子,表现出明显的荧光增强,检测限可以达到4.5060×10~(-5)M,并且拟一级速率常数K=1.27406 S~-,表明了探针CP检测锌离子具有较高的灵敏度。     

一种新型酰肼腙类受体的合成与阳离子识别

设计合成了荧光传感分子2-吡啶甲醛-4-乙氧基苯甲酰肼腙(PAEB),采用红外光谱法、氢核磁共振和元素分析法对其结构进行了表征,用紫外可见吸收光谱和荧光发射光谱研究了PAEB对不同金属离子的配位作用的机理。结果表明:PAEB与锌(Ⅱ)形成物质的量的比为1比1配合物。由于此配合物的形成,在发射波长470nm(激发波长为400nm)处出现明显的荧光增强,且对锌(Ⅱ)而言具有较高的选择性。初步探讨了受体分子与锌(Ⅱ)的荧光增强机理。     

以3, 5-二甲基-1-羧甲基-4-吡唑甲酸为配体的两个锌的配合物的合成、晶体结构和荧光性能

以3,5-二甲基-1-羧甲基-4-吡唑甲酸和4,4′-联吡啶为配体,合成了1个单核锌(Ⅱ)配合物[Zn(4,4′-bpy)(Hcmdpca)2(H2O)3]·2H2O(1)和1个锌(Ⅱ)的一维配位聚合物[Zn(4,4′-bpy)(Hcmdpca)2(H2O)]·3H2O(2)(H2cmdpca=3,5-二甲基-1-羧甲基-4-吡唑甲酸;4,4′-bpy=4,4′-联吡啶),并用元素分析、红外光谱、X-射线单晶衍射结构分析、热重分析等对其进行了表征。配合物1和2都属于单斜晶系,空间群为P21/c。配合物1的锌离子都位于一个畸变的八面体构型中。配合物1中的独立结构单元间通过分子间氢键作用构成一个三维的超分子结构。而在2中,锌离子位于一个畸变的四方锥构型中,每个4,4′-联吡啶分子桥联2个相邻的锌(Ⅱ)离子,形成一个一维链;这些一维链和水分子通过分子间氢键进一步形成一个三维的结构。此外还考察了1和2的热稳定性和固体荧光性质。     

5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌配合物的合成表征

设计合成了5种未见文献报道的5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌金属配合物,并用IR,UV-Vis,1H NMR,元素分析以及XPS对其组成和结构进行了表征,研究了这10种酰胺基系列卟啉化合物的拉曼光谱和荧光光谱的变化.结果显示链长对荧光和拉曼光谱没有明显影响,其取代基效应基本相同,配体的荧光强度强于锌配合物的荧光强度.在拉曼光谱中,由于卟啉分子平面的对称性由D2h变为D4h群及其锌离子d轨道的电子效应,卟啉配体和锌配合物之间的拉曼光谱有很大差别.     

以3,5-二甲基-1-羧甲基-4-吡唑甲酸为配体的两个锌的配合物的合成、晶体结构和荧光性能（英文）

以3,5-二甲基-1-羧甲基-4-吡唑甲酸和4,4′-联吡啶为配体,合成了1个单核锌(Ⅱ)配合物[Zn(4,4′-bpy)(Hcmdpca)2(H2O)3]·2H2O(1)和1个锌(Ⅱ)的一维配位聚合物[Zn(4,4′-bpy)(Hcmdpca)2(H2O)]·3H2O(2)(H2cmdpca=3,5-二甲基-1-羧甲基-4-吡唑甲酸;4,4′-bpy=4,4′-联吡啶),并用元素分析、红外光谱、X-射线单晶衍射结构分析、热重分析等对其进行了表征。配合物1和2都属于单斜晶系,空间群为P21/c。配合物1的锌离子都位于一个畸变的八面体构型中。配合物1中的独立结构单元间通过分子间氢键作用构成一个三维的超分子结构。而在2中,锌离子位于一个畸变的四方锥构型中,每个4,4′-联吡啶分子桥联2个相邻的锌(Ⅱ)离子,形成一个一维链;这些一维链和水分子通过分子间氢键进一步形成一个三维的结构。此外还考察了1和2的热稳定性和固体荧光性质。     

2-羟基-萘甲醛缩对甲氧基苯甲酰腙的合成与荧光性质研究

合成了2-羟基-萘甲醛缩对甲氧基苯甲酰腙,采用元素分析和红外光谱对该化合物结构进行了表征。详细研究了该化合物在固态、不同溶剂中和有锌离子存在下的荧光光谱,探讨了溶剂极性和锌离子的存在对其荧光光谱的影响。结果表明：该化合物的固体和溶液都有很强的荧光,溶剂对其荧光性质有较大的影响,其DMF溶液在485nm处发光最强。金属锌离子具有荧光增敏性。     

4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺荧光染料的合成及其性能研究

以4-溴-1,8-萘酐为原料,合成脂溶性4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺。对其进行了1H NMR和IR表征。考察了荧光染料在DMF、乙腈、丙酮、乙酸乙酯和乙醚5种溶剂中的荧光光谱和吸收光谱,发现由于溶剂效应,随溶剂极性由小到大,荧光光谱和吸收光谱的最大峰值波长逐渐红移。考察了不同金属离子和pH对荧光染料荧光光谱的影响,结果表明荧光强度随Fe3+、Zn2+、Co2+浓度增大而逐渐增强,Fe3+的影响最为显著;当pH<7时,荧光强度随着pH的降低逐渐增强;进一步考察了Fe3+、Zn2+、Co2+对吸收光谱的影响,结果发现吸收光谱均蓝移。分析认为荧光染料的光致电子转移被阻碍,实验结果表明,合成的新型荧光染料可用于溶液中金属离子和pH的检测。     

Rhodamine-derived Schiff base for the selective determination of mercuric ions in water media

A new rhodamine-derived Schiff base (RS) was synthesized and its sensing property to metal ions was investigated by UV/vis and fluorescence spectroscopies. Addition of Hg2+ ions to the aqueous solution of RS gave a visual color change as well as significantly fluorescent enhancement, while other ions including Pb2+, Cd2+, Cr3+, Zn2+, Cu2+, Fe2+, Co3+, Ni2+, Ca2+, Mg2+, K+ and Na+ ions did not induce any distinct color/spectral changes, which constituted a Hg2+-selective fluorescent OFF-ON chemosensor. The Hg2+-induced ring-opening of spirolactam of rhodamine in RS resulted in the dual chromo- and fluorogenic observation.     

Preparation and characterization of thiacalix[4]arene coated water-soluble CdSe/ZnS quantum dots as a fluorescent probe for Cu2+ ions

Highly fluorescent water-soluble CdSe/ZnS (core/shell) quantum dots (QDs) as a fluorescent Cu2+ ion probe were synthesized using thiacalix[4]arene carboxylic acid (TCC) as a surface coating agent. Hydrophobic trioctylphosphine oxide (TOPO) capped CdSe/ZnS QDs were overcoated with TCC in tetrahydrofuran at room temperature, and deprotonation of the carboxyl groups of TCC resulted in the formation of water-soluble QDs. The surface structure of the QDs was characterized by using transmission electron microscopy (TEM) and fluorescence correlation spectroscopy (FCS). TEM images showed that TCC-coated QDs were monodispersed with the particle size (core-shell moiety) of approximately 5 nm. Hydrodynamic diameter of the TCC-coated QDs was determined to be 8.9 nm by FCS, showing that the thickness of the surface organic layer of the QDs was approximately 2 nm. These results indicate that the surface layer of TCC-coated QDs forms a bilayer structure consisting of TOPO and TCC molecules. TCC-coated CdSe/ZnS QDs were highly fluorescent (quantum yield, 0.21) compared to the QDs surface-modified with mercaptoacetic acid and mercaptoundecanoic acid. Fluorescence of the TCC-coated QDs was effectively quenched by Cu2+ ions even in the presence of other transition metal ions such as Cd2+, Zn2+, Co2+, Fe2+, and Fe3+ ions in the same solution. The Stern-Volmer plot for the fluorescence quenching by Cu2+ ions showed a linear relationship up to 30 microM of Cu2+ ions. The ion selectivity of TCC-coated QDs was determined by measurements of fluorescence responses towards biologically important transition metal ions (50 microM) including Fe2+, Fe3+, Co2+>Zn2+, Cd2+. The fluorescence of TCC-coated QDs was almost insensitive to other biologically important ions such as Na+, K+, Mg2+, and Ca2+, suggesting that TCC-coated QDs can be used as a fluorescent Cu2+ ion probe for biological samples. A possible quenching mechanism by Cu2+ ions was also discussed on the basis of a Langmuir-type adsorption isotherm.     

Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV—vis and Fluorescent Spectra

A new fluorescent compound based on calix[4] arene skeleton was synthesized.Its complexation ability with transition metal ions,such as Fe^3 ,Co^2 ,Ni^2 ,Cu^2 ,Zn^2 and Ag^ ,Was investigated by UV-vis and fluorescent spectra.     

二价金属离子对平阳霉素与DNA作用的影响

二价金属离子对平阳霉素与ＤＮＡ作用的影响王自春，黄登宇，袁静明（山西大学分子科学研究所，太原，０３０００６）关键词二价金属离子，平阳霉素，ＤＮＡ平阳霉素（简称ＢＬＭ－Ａ５）是抗肿瘤抗生素博莱霉素的成分之一，其化学结构、理化性质和药理作用虽基本相同［１...     

一种高灵敏度高选择性的荧光素基比色荧光锌传感器

本文报道了一种基于荧光素的锌离子传感器FN1,其在甲醇溶液中显示了对锌离子极高的灵敏度和选择性。随着锌离子的滴加,紫外-可见光谱中最初在371 nm处的吸收峰消失,在437 nm处出现了一个新峰。当在混合金属离子的甲醇溶液中滴加了相对于二价金属离子的等物质的量浓度的锌离子或相对于一价金属离子0.5倍物质的量浓度的锌离子后,锌离子积分荧光强度增强了近37倍（Φ=0.48,λ_max(em)=513 nm）,估算的锌离子检测限为7 μg·L^-1。基于紫外-可见光、荧光和质谱的结果,讨论了1∶1的FN1/Zn²⁺配合物的结合机理。     

Transition metal(II) complexes of (E)-cinnamoylferrocene (S)-methylcarbodithioylhydrazone

A new organometallic ligand, (E)-cinnamoylferrocene (S)-methylcarbodithioylhydrazone (HCfmc) and six transition metal(II) complexes thereof M(Cfmc)2·nH2O (M=Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+; n=0–2) have been prepared and characterized by elemetal analyses, i.r., u.v., 1H-n.m.r. spectra, electrochemical properties, fluorescence spectra and molar conductances. The HCfmc ligand acts as a bidentate donor, coordinating to the metal ions via nitrogen and sulfur atoms with a trans-configuration.     

Fluorescence sensing and binding behavior of aminobenzenesulfonamidoquinolino-beta-cyclodextrin to Zn2+

A water-soluble fluorescent zinc sensor which binds strongly to Zn2+ (log K = 12.4) was successfully synthesized under physiological conditions. This sensor exhibits a good fluorescence response to Zn2+ over a wide pH range in water. Under the same conditions, several metal ions commonly present in a physiological environment, such as Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, and Co2+, showed little interference to the fluorescence response to Zn2+. [structure: see text]     

Use of miniaturised isotachophoresis on a planar polymer chip to analyse transition metal ions in solutions from metal processing plants

An electrolyte system, using malic acid as a complexing agent, has been developed to allow the determination of transition metal cations using miniaturised isotachophoresis. The method allowed the simultaneous determination of Mn2+, Cr3+, Fe2+, Co2+, Zn2+ and Ni2+ to be made without interference from other common ions. Limits of detection were calculated to be in the range 0.5-1.0mg l(-1) for Mn2+, Cr3+ Co2+ and Zn2+ and 2.0 mg l(-1) for Fe2+ and 4.7 mg l(-1) for Ni2+. The successful analysis of five industrial samples, containing a range of these metal ions, obtained from metal processing plants were achieved in under 13 min. The separations were performed on a poly(methyl methacrylate) chip with integrated platinum wire conductivity detection electrodes.     

罗丹明类荧光探针的合成及对铜离子的检测

合成了罗丹明类Cu2+荧光增强型分子探针3',6'-双(二乙氨基)-2-(N-乙叉基氨基)螺[异吲哚-1,9'-占吨]-3-酮（RA）,并研究了它的光谱性能及对铜离子的识别作用.在乙腈/水（体积比1/1）的介质中,当加入Cu2+后探针RA显玫瑰红色,最大吸收波长为548 nm,最大发射波长为571 nm,且荧光强度显著增强,但是,其它常见离子如Na+, K+, Mg2+, Ca2+, Mn2+, Cd2+, Cr3+, Co2+, Ni2+, Ag+, Pb2+, Zn2+, Fe3+, Hg2+不引起或引起很小的紫外/可见或荧光光谱变化.RA的选择性荧光增强主要是由于Cu2+诱导分子中的酰胺闭环结构发生开环,导致分子结构的共轭程度增大.在6.5×10-8～2.9×10-6 mol?L-1范围内RA可以有效检测Cu2+,检测限为5.0×10-8 mol?L-1.RA对Cu2+的识别不可逆,而且探针RA对pH值不敏感,可以在比较宽的范围内（pH=4.1～10.5）高灵敏、高选择性检测Cu2+.