基于苯并噻唑Zn2+荧光探针及其细胞造影应用

设计合成基于苯并噻唑Zn²⁺荧光增强型探针BHP,在HEPES缓冲液中测其对Zn²⁺识别性能。实验结果表明,BHP对Zn²⁺有较高的选择性,对其他金属离子如Cd²⁺,Fe²⁺,Ni²⁺,Pb²⁺,Hg²⁺,Al³⁺,Mn²⁺,Ag⁺,Cu²⁺,Co²⁺,Na⁺,K⁺,Mg²⁺和Ca²⁺无明显荧光增强响应。BHP与Zn²⁺按1：1计量比配位,在生理条件下荧光强度不受pH值影响。在HeLa细胞中对Zn²⁺的造影表明BHP可用于生物体Zn²⁺检测。     

锌离子选择性化学传感器的设计与合成

设计合成了带有羟基取代的希夫碱配体化合物1，并研究了它与Zn²⁺的识别。结果发现：在乙腈溶剂中化合物1与Zn²⁺络合后有强的荧光发射，而化合物1除了与Mg²⁺络合后有弱的荧光发射被检测到外，与其他离子(Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Ca²⁺, Ba²⁺, Sr²⁺)络合后未检测到荧光发射。研究结果还表明：化合物1能在多组分混合离子中对Zn²⁺进行选择性检测而不受其他离子的干扰。为了弄清配体化合物1与Zn²⁺络合的反应机理，本论文还设计合成了其他三个带羟基取代的希夫碱配体化合物2-4，并分别研究了它们与Zn²⁺的识别。     

CdS/MS(M=Ag,Pb,Cu,Zn)半导体纳米复合结构的制备

利用金属硫化物在水溶液中溶度积的差异和通过水热及超声波等辅助方式,利用离子置换法与共沉淀法,对CdS纳米棒上金属离子(Cd²⁺)的部分置换而对纳米微粒进行侵蚀或包覆,形成镶嵌式点缀结构或完全包覆层的异质核-壳结构CdS/MS(M=Ag⁺,Cu²⁺,Pb²⁺,Zn²⁺)。使用XRD和TEM对所得样品进行了表征。     

三种水杨醛席夫碱荧光探针的合成及对Zn2+的识别

设计、合成了3种新型席夫碱Zn²⁺荧光探针：水杨醛缩三羟甲基氨基甲烷(L1)、5-氯水杨醛缩三羟甲基氨基甲烷(L2)和4-甲氧基水杨醛缩三羟甲基氨基甲烷(L3),并用¹H NMR、¹³C NMR、元素分析和HRMS进行了表征。光谱分析实验结果表明,相比于探针L1和L3,探针L2对Zn²⁺具有更好的选择性和灵敏度,检出限为11.96 nmol·L^-1,远低于国标GB5749—2006规定的饮水中Zn²⁺的限量值1.0 mg·L^-1(约15 μmol·L^-1)。在0~10 μmol·L^-1范围内,探针L2的荧光强度与Zn²⁺浓度可呈良好的线性关系。同时,配合物[Zn (C₁₁H₁₃ClNO₄)₂](L2-Zn²⁺)的单晶结构和Job曲线证实探针L2与Zn²⁺以物质的量之比2∶1配位。另外,探针L2能够对实际水样中的Zn²⁺进行有效检测。     

一例喹喔啉酰腙荧光探针对锌离子的选择性高灵敏识别及细胞成像应用

通过缩合反应制备了一例席夫碱荧光探针2-喹喔啉甲醛缩2-吡啶酰肼(1),使用核磁共振氢谱和碳谱及质谱等手段表征了探针的结构。荧光光谱分析表明,探针1自身无荧光,而Zn²⁺能够导致其在500 nm处出现强发射峰。该荧光增强能够在常见阳离子中选择性检测 Zn²⁺,检测限低至 0.16 μmol·L^-1。通过核磁、质谱和紫外等手段推测了探针 1与 Zn²⁺可能的配位模式。通过单晶X射线衍射解析了1-Zn²⁺配合物的晶体结构,进一步确认了探针的配位行为。1-Zn²⁺晶体中探针分别采取ONN和NN配位模式螯合2个Zn²⁺,并由桥联CH₃O^-和Cl^-连接形成一维链状结构。此外,该探针还可用于活细胞中Zn²⁺的检测。     

一种用于活细胞中检测Zn2+的萘酚席夫碱类荧光探针

设计合成了1种基于C=N异构化和螯合荧光增强机理（CHEF）的Zn²⁺荧光探针BMO和NBMO,其结构经¹H NMR,¹³C NMR,¹H-¹H COSY,HSQC,IR和HRMS进行了表征。光谱分析实验结果显示,探针对Zn²⁺均具有较好的选择性和灵敏度,检出限分别为30和21 nmol·L^-1。在0~20 μmol·L^-1浓度的范围内,BMO和NBMO的荧光强度与Zn²⁺浓度可呈良好的线性关系。NBMO-Zn²⁺配合物单晶结构和Job曲线证实该探针与Zn²⁺以1：1配位。NBMO被成功应用于活细胞中Zn²⁺的检测。     

一种基于硫杂杯[4]芳烃的高效银离子载体

合成了基于下缘含有酰肼基团的硫杂杯芳烃衍生物的银离子载体1,其核磁研究证实硫杂杯芳烃以1,3-交替构象存在,并且通过非竞争萃取实验和竞争萃取实验研究了它对碱金属和过渡金属离子（Li⁺, Na⁺, K⁺, Cs⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Ag⁺）的键合能力和选择性。实验结果表明：将酰肼基团引入1,3-交替构象的硫杂杯芳烃骨架的下缘可以提高其对Ag⁺的键合能力和选择性,同时,对Cu²⁺的萃取能力较弱,对碱金属离子和其它的重金属离子几乎没有萃取能力。进一步的核磁滴定和电喷雾质谱实验显示化合物1与银离子形成配合物的配合计量比为1：1,由此推断主要由“N-Ag⁺”配位键以及硫杂杯芳烃骨架的协同作用构成了化合物1与银离子的配合模式。     

一种基于DPA识别基团的可视化检测锌离子的荧光增强型探针

以N,N-二（2-吡啶甲基）胺（DPA）为识别基团,设计合成了一种用于检测Zn²⁺的荧光增强型探针WN,在CH₃CH₂OH/Tris-HCl（1：9,V/V,pH=7.4）缓冲溶液中研究了它对Zn²⁺的识别特性。实验结果表明,WN对Zn²⁺有较高的选择性和灵敏度,它们之间的结合比为1：1,对Zn²⁺的检出限为1.14×10^-8mol·L^-1。WN能够快速地可视化检测Zn²⁺,在HeLa活细胞中对Zn²⁺的荧光显微成像表明WN可应用于生物体的检测。     

1,8-萘酰亚胺为发色团的Zn2+荧光探针的合成及性能研究

合成了以1,8-萘酰亚胺为发色团,以联吡啶为离子受体的Zn²⁺荧光探针,并进行了表征及离子识别性能的研究。研究表明该化合物对Zn²⁺具有良好的识别性能,同时相对于Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Ni²⁺, Pb²⁺等金属离子具有良好的选择性。     

基于席夫碱的四种Zn2+荧光探针的合成及其性能

以乙二胺与水杨醛及其衍生物为原料,构建了4种席夫碱Zn²⁺荧光探针,其结构均由¹H NMR、¹³C NMR和IR进行了表征。光谱分析实验结果表明,相比于其他探针,探针L2对Zn²⁺具有更好的选择性和灵敏度,检出限为92.15 nmol·L^-1。在0~30μmol·L^-1的浓度范围内,探针L2的荧光强度与Zn²⁺浓度可呈良好的线性关系,在紫外灯下可用肉眼观察到明显颜色变化。通过Job曲线、核磁滴定实验、密度泛函理论计算和L2-Zn²⁺配合物单晶结构对识别机理进行了研究,结果表明探针L2与Zn²⁺以物质的量之比1∶1配位。此外,探针L2还可用于检测实际水样中的Zn²⁺。     

Thiazole sulfonamide based ratiometric fluorescent chemosensor with a large spectral shift for zinc sensing

A new thiazole sulfonamide (TTP, 1) based Zn²⁺ selective intrinsic chemosensor has been synthesized and investigated. The chemosensor shows a selective fluorescence enhancement (3.0 fold) with Zn²⁺ over biologically relevant cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺) and biologically non-relevant cations (Cd²⁺) in an aqueous ethanol system. It produces an increase in the quantum yield and a longer emission wavelength shift (64 nm) on Zn²⁺ binding with the potential of a ratiometric assay.     

A New Fluorescent Chemosensor for Metal Ions Based upon 1,8‐Naphthalimide and 8‐Hydroxyquinoline

A new fluorescent chemosensor based upon 1,8‐naphthalimide and 8‐hydroxyquinoline was synthesized, and its fluorescent properties in the presence of different metal cations (Hg²⁺, Ag⁺, Zn²⁺, Fe²⁺, Cd²⁺, Pb²⁺, Ca²⁺, Cu²⁺, Mg²⁺, and Ba²⁺) were investigated. It displayed fluorescence quenching with some heavy and transition metal (HTM) ions, and the quenching strongly depended on the nature of HTM ions.     

A Highly Selective and Sensitive Fluorescent Chemosensor for Detection of Al3+ in Totally Aqueous Media

A fluorescent chemosensor ( 1 ) based on 2‐hydroxy‐1‐naphthaldehyde Schiff‐base was developed for the detection of Al³⁺ in 100% aqueous solution. Upon addition of Al³⁺, a significant fluorescence enhancement was observed, which was not affected by other metal ions including Na⁺, K⁺, Ca²⁺, Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cr³⁺, Ag⁺, Pb²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Fe²⁺ and Fe³⁺ under weak acid conditions. Moreover, the specific response to Al³⁺ was visible under natural light. The binding mode between 1 and Al³⁺ was clarified by ESI‐MS and ¹H NMR.     

Ratiometric and turn-on monitoring for heavy and transition metal ions in aqueous solution with a fluorescent peptide sensor

A novel fluorescent peptide sensor containing tryptophan (donor) and dansyl fluorophore (acceptor) was synthesized for monitoring heavy and transition metal (HTM) ions on the basis of metal ion binding motif (Cys-X-X-X-Cys). The peptide probe successfully exhibited a turn on and ratiometric response for several heavy metal ions such as Hg²⁺, Cd²⁺, Pb²⁺, Zn²⁺, and Ag⁺ in aqueous solution. The enhancements of emission intensity were achieved in the presence of the HTM ions by fluorescent resonance energy transfer (FRET) and chelation enhanced fluorescence (CHEF) effects. The detection limits of the sensor for Cd²⁺, Pb²⁺, Zn²⁺, and Ag⁺ were lower than the EPA's drinking water maximum contaminant levels (MCL). We described the fluorescent enhancement, binding affinity, and detection limit of the peptide probe for HTM ions.     

Highly selective fluorescent recognition of Zn2+ based on naphthalene macrocyclic derivative

A new macrocyclic chemosensor containing two naphthalene fluorophores has been synthesized. The fluorescent properties of this receptor has been studied in the presence of various metal ions such as Na⁺, Ag⁺, Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Pb²⁺. When increasing concentrations of Zn²⁺ ions were introduced, the emission of L was drastically increased (EFE = 4.34). This special change was not observed when other metal ions were used; such highly selective fluorescent response indicates that this receptor can easily discriminate Zn²⁺ ions from other similar species. Model calculations at DFT level further suggest the possible interaction mode, and relatively steric position between the host and guest also influence the optical response.     

Synthesis and selective recognition toward zinc ion of chiral poly(imine‐triazole)

A novel AB type of clickable monomer, (S)‐2‐[(2‐azido‐1‐phenylethylimino)methyl]‐5‐propargyloxyphenol (AMPP) was designed and polymerized to yield a class of main‐chain chiral poly(imine‐triazole)s through the metal‐free click reaction. With the thermally induced polymerization, the desired polytriazoles can be easily prepared in high yields by a stepwise heating‐up process and have the number‐average molecular masses ranging from 5.1 × 10³ to 58.1 × 10³ (polydispersity indices = 1.38?1.68). The polymers were characterized by Fourier Transform Infrared spectroscopy (FTIR), ¹H Nuclear Magnetic Resonance (NMR), and gel permeation chromatography, and their optical properties were studied by fluorescence and circular dichroism (CD) spectroscopies. As a chemosensor, these polymers exhibited a selective “turn‐on” fluorescence enhancement response toward Zn²⁺ ion over other cations such as Na⁺, K⁺, Mg²⁺, Ca²⁺, Ag⁺, Pb²⁺, Cd²⁺, Hg²⁺, Mn²⁺, and Ni²⁺ in dimethyl sulfoxide. However, the Zn²⁺‐induced fluorescence signal was subject to serious interference by Al³⁺, Cu²⁺, Cr³⁺, and Fe³⁺ ions. Interestingly, the chiral polymer showed distinctive changes in the CD spectra on complexation with Zn²⁺, which allowed for the discrimination of this ion in the presence of other species tested including those interfering ions observed in the fluorescent detection. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2248–2257     

A highly selective ratiometric fluorescent chemosensor for Zn2+ ion based on a polyimine macrocycle

A new ratiometric fluorescent chemosensor based on a polyimine macrocycle ligand 1 has been synthesized. The chemosensor can exhibit a pronounced fluorescence response and high selectivity to Zn²⁺ ion over other 15 metal ions, including Cd²⁺. Sensor 1 appears an emission peak at 370 nm. Upon the addition of Zn²⁺ ion, the typical emission peak for 1 at 370 nm is obviously quenched, but a new emission peak at around 470 nm appears and shows a large enhancement due to the formation of a 1:1 Zn²⁺-1 complex. In addition, there is a good linear relationship between the fluorescence ratio I_470nm/I_370nm and the concentration of Zn²⁺, which makes a ratiometric assay of Zn²⁺ ion possible.     

Preparation of a fluorescent sensor based on BODIPY-functionalized hydroxyapatite nanoparticles and spectroscopic study of the Cd2+ and Zn2+ complex formation

A new fluorescent chemosensor 1, which based on hydroxyapatite (HA) nanoparticles covalently functionalized with a difluoroboron dipyrromethene, has been prepared by nucleophilic substitution of the fluorescent dye 3-chloro-4,4-difluoro-8-(4-tolyl)-5-[bis(pyridine2-ylmethyl)amino]-4-bora-3a,4a-diaza-s-indacene (2) with surface-modified HA nanoparticles. The HA particles were prepared by using SiO₂ as templates (THA) with 3-(aminopropyl)triethoxysilane (THA-APTES). Substitution of the electron-withdrawing chlorine in 2 by an electron-donating amino group of HA changes the properties of the nanoparticles 1 and the corresponding fluorescent dye 2. Absorption and emission maxima of 1 in ethanol are red-shifted by 75 and 30?nm, respectively, in comparison with those of 2. In contrast to no selectivity of dye 2 for Cd²⁺ or Zn²⁺ in EtOH/H₂O (95/5?V/V) solutions, the nanofluorescent probe 1 forms 1?:?1 complexes with Cd²⁺ or Zn²⁺, producing an instant color change along with large hypsochromic shifts in the absorption and fluorescence spectra by 70 and 35?nm, respectively, and large cation-induced fluorescence amplifications.