基于1,8-萘酰亚胺与罗丹明B间荧光共振能量转移的高选择性Hg2+比率荧光探针

以罗丹明B与1,8-萘二甲酰亚胺反应合成了1个高选择性Hg²⁺比率荧光探针(RN). 在甲醇/乙腈/4-羟基哌嗪乙磺酸缓冲溶液(pH=7.2, 体积比8:1:1)中, RN对Hg²⁺具有比色和比率荧光双重响应. 加入Hg²⁺后, RN的紫外-可见光谱在约556 nm处产生强吸收, 溶液由浅绿色变为橙色, 其它金属离子对RN的紫外-可见光谱几乎无影响. 无Hg²⁺存在时, RN的荧光光谱在540 nm处出现萘二甲酰亚胺荧光团的特征峰; 加入Hg²⁺后, 540 nm处的发射带逐渐消失, 同时在580 nm附近产生强荧光, 荧光颜色从绿色变为橙色. 这归因于从萘酰亚胺到开环罗丹明B的荧光共振能量转移(FRET), 探针RN对Hg²⁺的比率荧光响应具有高选择性, 不受其它共存金属离子的干扰.     

2-羟基-1-萘甲醛缩-2-萘甲酰腙对Zn2+的选择性识别

设计合成了识别Zn²⁺的荧光传感分子--2-羟基-1-萘甲醛缩-2-萘甲酰腙(3)。 通过红外光谱、核磁共振谱和质谱测试技术表征了其结构。 利用其光谱性质研究了该物质对几种过渡金属离子的识别性质,初步探讨了其结合模式。 结果表明,在乙腈介质中,受体分子3表现出对Zn²⁺良好的选择性,Zn²⁺的加入导致受体分子3的吸收光谱在435 nm处出现1新峰,其吸光度逐渐增强,同时于239、302、330、342和387 nm处观察到5个清晰的等吸收点;在516 nm处荧光增强101倍,而其它过渡金属只引起受体分子]3的荧光略微增强。 Job法实验揭示受体分子3与Zn²⁺的结合比为1∶1。     

联噻吩桥联双三联吡啶的合成、质子化及其与金属离子的配位

以2,5-二溴噻吩为底物, 经醛基化、Kröhnke吡啶合成反应、Suzuki偶联三步制备了联噻吩桥联双三联吡啶 (BTTPY,总产率13%).通过紫外吸收及荧光光谱研究了其在酸性介质中的质子化效应, BTTPY在乙酸和三氟乙酸中的吸收及荧光光谱较非质子溶剂中均有明显红移.借助紫外吸收滴定法研究了其与过渡金属离子(Ni²⁺、Zn²⁺、Cd²⁺、Cu²⁺)的配位作用.结果表明BTTPY可与这些金属离子形成1:1的配合物,原子力显微镜 (AFM)图像显示, BTTPY与铬离子所形成的配位聚合物主要呈现一维堆积.     

一种新的镧系金属有机骨架材料的合成、 结构及荧光检测性质

利用溶剂热方法合成了一种以Tb³⁺离子为中心的金属有机骨架材料［Tb₂(bpt)₂(H₂O)₂］·(DMA)_4.5, 并通过单晶X射线衍射(SXRD)、 粉末X射线衍射(PXRD)、 元素分析(EA)、 热重分析(TGA)、 傅里叶变换红外光谱 (FTIR)以及荧光光谱技术(FS)表征了该材料的结构与基本物理化学性质. 单晶衍射分析结果显示该材料具有包含一维直孔道的三维结构, 结构中孔道窗口尺寸约为1.23 nm×1.10 nm. 荧光分析测试结果表明该材料对Cr³⁺离子有荧光响应, 离子检测限低至0.22 mg/L, 同时具有良好的选择性, 在Cr³⁺离子的荧光检测领域具有重要的应用潜力.     

1-丁基-3-甲基咪唑硫酸氢盐与乙酸钠混合电解液中三价铬电镀的研究

本文研究了Cr³⁺在1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）电解液中的电沉积反应以及添加剂NaOAc对电镀铬的影响. 含Cr³⁺电解液的循环伏安结果表明,Cr(III)还原为Cr(II)的峰电位是-1.5 V (vs. Pt), 峰电位和峰电流均满足Rendle-Sevcik扩散方程,由该方程计算得到Cr³⁺的扩散系数为1.6 × 10^-8 cm²·s^-1. 铬镀层的X射线衍射和扫描电子显微镜表征结果表明镀层由纳米球状的单质铬颗粒聚集而成,其平均粒径为0.87μm. 在电解液中添加NaOAc后,Cr³⁺的还原峰电位正移了约0.25 V. 同时EDS结果表明,在NaOAc的作用下镀层中Cr/O摩尔比由4.48增加至6.28,这说明OAc^-有利于单质铬的电沉积. 当电解液中NaOAc-[BMIM]HSO₄-CrCl₃-H₂O的摩尔比为0.075:1:0.5:6时,所得的镀层最厚(63 μm)与电流效率最高(33.5%).     

同时识别Cu2+,Zn2+和Ca2+的化学传感器合成及Ca2+活体荧光成像

合成并表征了一个能同时对Cu²⁺,Zn²⁺和Ca²⁺进行识别的化学传感器L,研究了L对常见的金属离子和阴离子的吸收光谱和荧光光谱。结果发现：L可通过紫外-可见吸收光谱分别在414和328 nm处对Cu²⁺,Zn²⁺进行特异识别,L可通过在511 nm处的荧光增强对Ca²⁺进行特异识别,且其识别具有快速、可选择及可逆的特点。将L应用于药品和水体样品中Cu²⁺,Zn²⁺和Ca²⁺的检测,结果满意。L还可用荧光成像对细胞和活体中Ca²⁺进行检测。     

基于肉桂酰肼的Zn2+、Mg2+和Cd2+Turn-On型荧光探针研究

本文以肉桂酸甲酯、水合肼及水杨醛为原料,设计合成了一种“turn-on”型离子选择性荧光探针,采用NMR、IR及HRMS对其结构进行了表征,结果表明该探针为N’-[(2-羟苯基)亚甲基]-3-{2-[(2-羟苯基)亚甲基]肼-1-基}-3-苯丙酰肼(ZL)。基于其存在的酰基和邻羟苯基亚甲基胺结构,研究了其对不同金属离子的识别作用,结果Zn²⁺、Mg²⁺和Cd²⁺对探针ZL荧光表现出“turn-on”效应,其荧光分别增强了47、21、24倍,而其他金属离子对其荧光光谱及强度无影响,化合物ZL表现出对Zn²⁺、Mg²⁺和Cd²⁺的高选择性识别和高灵敏检测,其检出限分别为5.5nmol·L^-1、8.4nmol·L^-1、9.9 nmol·L^-1。通过Job’s plot实验表明ZL与Zn²⁺、Mg²⁺和Cd²⁺的结合比为1∶1,结合核...     

荧光素-层状双金属氢氧化物复合体的发光性能及对Fe3+的荧光识别

采用离子交换法合成了FLN/OS-LDH复合体(FLN: 荧光素, OS: 1-辛烷磺酸钠, LDH: 镁铝型层状双金属氢氧化物), 并研究了其光致发光和对Fe³⁺的识别性能. 固态时, FLN不发光, 而FLN/OS-LDH复合体呈黄绿色荧光(发射波长为565 nm), 是荧光素(FLN)的特征发射光. 在甲酰胺(FM)中可将该复合体方便剥离为胶状悬浮液, 其发射波长发生蓝移, 为绿光发射(531 nm). 研究了复合体剥离液对金属离子的荧光识别特性, 发现其对Fe³⁺的选择性识别能力很强, 远优于其它离子(Mg²⁺, Ni²⁺, Co²⁺, Cu²⁺, Zn²⁺, Pb²⁺, Cd²⁺和Hg²⁺). 该复合体与Fe³⁺结合发生荧光猝灭现象, 可将其用作检测Fe³⁺的荧光传感器. Fe³⁺检测限为1.27×10^-7 mol/L, 猝灭常数(K_sv)为3.44×10² L/mol.     

罗丹明-三嗪衍生物的合成及探针性质

在控制反应温度的条件下, 用罗丹明B酰肼(或罗丹明B乙二胺)选择性分步取代三聚氯氰环上的活性氯, 合成了系列罗丹明-三嗪衍生物. 考察了不同取代获得的衍生物的探针识别性能, 发现所制备的衍生物能高灵敏、高选择性地识别Al³⁺, Cr³⁺或Cu²⁺离子, 是一类性能良好的金属离子荧光和比色增强型探针.     

开链冠醚Schiff碱配体与过渡金属离子相互作用研究

合成了开链冠醚Schiff碱配体H₂L(H₂L=N,N′-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷).详细研究了该配体在不同溶剂中和过渡金属离子存在下的荧光光谱,探讨了溶剂极性和不同金属离子对其荧光光谱的影响.结果表明:溶剂的极性和金属离子对其荧光性质有较大影响,随着溶剂极性的减小,配体的荧光增强,且谱峰发生蓝移.金属离子Zn²⁺、Cd²⁺对配体具有荧光增敏作用,Ni²⁺、Cu²⁺具有荧光猝灭作用.探讨了配体与金属离子结合的pH范围,结果显示最佳pH值为7—8.     

Second chemiluminescence behavior of Fe2+, Fe3+ and Cr3+ in the luminal-KMnO4 system.

A novel flow injection chemiluminescence (CL) method has been developed for the determination of three metal ions, namely Fe2+, Fe3+ and Cr3+, based on the second CL (SCL) signal of the mixture of luminal with KMnO4 in a sodium hydroxide medium by the catalysis of Fe2+, Fe3+ or Cr3+. The possible CL mechanism of the systems, the influencing factors, and the optimum conditions for the reactions were investigated based upon the kinetic curve of the CL reaction, CL spectra, UV-visible spectra and some other experiments. Under the optimum conditions, the SCL intensity was directly proportional to the concentration of these metal ions in solution in the range of 0.10 - 100.00 mg l(-1) for Fe(2+), 0.50 - 7.50 and 7.50 - 200.00 mg l(-1) for Fe3+, 0.01 - 0.25 and 0.25 - 10.00 mg l(-1) for Cr3+. The detection limits (3 sigma/s) were 9.87 x 10(-6) g l(-1), 2.71 x 10(-6) g l(-1) and 5.25 x 10(-7) g l(-1) for Fe2+, Fe3+ and Cr3+, respectively.     

双吲哚啉螺吡喃化合物的合成及其酸和金属离子致变色性能

设计、合成了一种新型双吲哚啉螺吡喃化合物1,用核磁、红外及质谱等技术手段表征了其结构。 利用紫外可见吸收光谱研究了化合物1的酸致变色和金属离子变色性能。 结果表明,化合物1能够在氢离子或金属离子的作用下发生可逆的开环与闭环反应。 当氢离子或金属离子加入到化合物1的异丙醇溶液中,溶液颜色从无色变为红色,同时产生460 nm新吸收峰。 进一步加入氢氧根离子或EDTA溶液后,溶液颜色变回无色,460 nm处的吸收峰又消失。 该化合物的酸和金属离子致变色性质在分子传感和离子识别等领域有潜在的应用价值。     

Cu(Ⅱ)-VO(Ⅱ),Cu(Ⅱ)-Cr(Ⅲ)和Cu(Ⅱ)-Fe(Ⅲ)异双核配合物的合成及表征

合成了三种二 ( 3 羧基水杨醛叉 )缩丙撑二胺 (TS)的Cu(Ⅱ ) VO(Ⅱ )、Cu(Ⅱ ) Cr(Ⅲ )、Cu(Ⅱ ) Fe(Ⅲ )异双核配合物 ,并用元素分析、摩尔电导、IR光谱、UV光谱室温磁矩对配合物的组成和结构进行了表征。磁性研究表明 ,在Cu(Ⅱ ) Fe(Ⅲ )离子间的磁相互作用是反铁磁性的 ,而Cu(Ⅱ ) VO(Ⅱ )、Cu(Ⅱ ) Cr(Ⅲ )离子间是铁磁性相互作用。     

Reactions of atomic transition-metal ions with long-chain alkanes

Understanding metal ion interactions with long-chain alkanes not only is of fundamental importance in the areas of organometallic chemistry, surface chemistry, and catalysis, but also has significant implication in mass spectrometry method development for the analysis of polyethylene. Polyethylene represents one of the most challenging classes of polymers to be analyzed by mass spectrometry. In this work, reactions of several transition-metal ions including Cr+, Mn+, Fe+, Co+, Ni+, Cu+, and Ag+ with long-chain alkanes, C28H58 and C36H74, are reported. A metal powder and the nonvolatile alkane are co-deposited onto a sample target of a laser desorption/ionization (LDI) time-of-flight mass spectrometer. The metal ions generated by LDI react with the vaporized alkane during desorption. It is found that all these metal ions can form adduct ions with the long-chain alkanes. Fe+, Co+, and Ni+ produce in-source fragment ions resulting from dehydrogenation and dealkylation of the adduct ions. The post-source decay (PSD) spectra of the metal-alkane adduct ions are recorded. It is shown that PSD of Ag+ alkane adduct ions produces bare metal ions only, suggesting weak binding between this metal ion and alkane. The PSD spectra of the Fe+, Co+, and Ni+ alkane adduct ions display extensive fragmentation. Fragment ions are also observed in the PSD spectra of Cr+, Mn+, and Cu+ alkane adduct ions. The high reactivity of Fe+, Co+, and Ni+ is consistent with that observed in small alkane systems. The unusually high reactivity of Cr+, Mn+, and Cu+ is rationalized by a reaction scheme where a long-chain alkane first forms a complex with a metal ion via ion/induced dipole interactions. If sufficient internal energy is gained during the complex formation, metal ions can be inserted into C-H and C-C bonds of the alkane, followed by fragmentation. The thermal energy of the neutral alkane is believed to be the main source of the internal energy acquired in the complex. Finally, the implication of this work on mass spectrometry method development for polyethylene analysis is discussed.     

低压离子分离-化学发光在线检测过渡金属离子

 研究了低压离子 (LPIC)分离 柱后鲁米诺化学发光 (CL)检测方法 ,并分离测定了Cu2 + ,Co2 + ,Cr3 + ,Fe2 + ,Mn2 + 等 5种过渡金属离子。以草酸 柠檬酸混合溶液作为洗脱液 ,Luminol H2 O2 Mn + 作为化学发光检测体系 ,对过渡金属离子进行在线检测。测定的线性范围分别为 (mg·L-1) :Co2 + ,0 0 0 1～ 0 .1;Cu2 + ,0 1～ 6 ;Mn2 + ,0 0 6～ 4 ;Fe2 + ,0 0 3～ 5 ;Cr3 + ,0 0 2 5～ 1。检测限分别为 (μg·L-1) :Co2 + ,0 85 ;Cu2 + ,85 ;Mn2 + ,4 2 ;Fe2 + ,2 1;Cr3 + ,2 0。     

Separation and spectroscopic characterization of new metal chelates of 8-arylazo-6-formyl-7-hydroxy-5-methoxy-2-methyl chromones

Transition metal chelates of the title compounds have been prepared and characterized by elemental analyses, i.r., 1H-n.m.r., electronic spectra, thermogravimetric analysis, conductometric and magnetic measurements. Chelates of general formulae MLjX · nH2O for 1:1 (M:L), where X=OH– or Cl–, j=1 or 2, n=1– 4 and M=VO2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+ ions or ML2 for 1:2 (M:L) Ni-(1a), ML2·2H2O where M=Co2+, Ni2+ and Cu2+ or M2LjX·nH2O for 2:1 (M:L) Cr3+, Fe2+, Ni2+ and Cu2+, L=Ligand, have been prepared. I.r. and 1H-n.m.r. spectra indicate that the aldehydic group in position six and the hydroxylic group in position seven are involved in chelation in the 1:1 and 1:2 (M:L) chelates, whereas for 2:1 (M:L) chelates with (1c), the interaction of the metal ion takes place through CHO, OH, CO2H and NN groups. Tetrahedral, octahedral and square planar geometries are proposed for the chelates based on their electronic spectra and magnetic moments.     

水杨醛-4-甲氧基苯甲酰腙识别锌离子的研究

设计合成了荧光传感分子水杨醛-4-甲氧基苯甲酰腙(SAMB),通过IR、1HNMR和元素分析确证了其结构,利用紫外-可见吸收光谱和荧光光谱考察了其对不同阳离子的识别作用。结果表明,SAMB的荧光发射对锌离子表现出高选择性响应,且形成1∶1型配合物。乙醇中锌离子的加入导致SAMB的荧光增强328倍,而其他过渡金属离子只引起SAMB的荧光的略微增强。初步探讨了受体分子与锌离子的结合模式与荧光增强机理。     

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.     

吡咯并[2,1,5-cd]中氮茚酰腙衍生物的合成及Cu2+荧光探针行为

设计合成了吡咯并[2,1,5-cd]中氮茚酰腙衍生物6. 测试了其紫外光谱和荧光光谱, 研究了其对铜离子的选择性识别作用. 结果表明, 化合物6作为铜离子荧光探针, 受常见离子干扰较小, 对于铜离子有着较高的选择性和较低的检出限.     

A copper(II) ion-selective on-off-type fluoroionophore based on zinc porphyrin-dipyridylamino

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2'-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties: the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an "on-off"-type fluoroionophoric switching property. The detection limit is found to be 3.3 x 10(-7) M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of fluorescent sensors for metal ions.