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。     

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。     

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⁺。     

Sb掺杂ZTO透明导电薄膜的结构和性能

采用溶胶凝胶法和旋涂法制备Sb掺杂钙钛矿结构ZTO（ZnSnO₃）透明电薄膜,并借助XRD、SEM、XPS、UV-Vis和Hall效应测试等手段研究了其结构和性能。比较了Sb离子单独置换ZnSnO₃晶体中的Zn²⁺或Sn⁴⁺,以及同时置换Zn²⁺和Sn⁴⁺等3种置换方式所得薄膜的结晶状态,分析了不同置换方式形成的薄膜中Sb离子实际占有的晶格位置,以及Sb⁵⁺与Sb³⁺的比例变化。探讨了不同置换方式晶体中氧空位（V_O^..）、锌间隙（Zn_i^..）和锡离子变价（Sn_Sn"）等结构缺陷相应的含量变化,并研究Sb离子掺杂浓度对薄膜晶体结构、结构缺陷和电阻率的影响。研究表明,3种置换方式的Sb掺杂ZTO薄膜均保持单一ZnSnO₃晶相,并且Sb离子均按设计的方案进入了相应的晶格位置,但不同置换方式的薄膜中,Sb⁵⁺与Sb³⁺的比例不同,并且会随Sb离子浓度增大而逐渐减小。研究证明Sb离子置换方式以及掺杂浓度均会显著影响薄膜中载流子的浓度和迁移率,从而影响其电性能。在所制备的薄膜中,Sb离子单独置换Zn²⁺且组成为Sb_0.15Zn_0.35Sn_0.5O_1.5的薄膜电阻率最低,为0.423 Ω·cm。此外,所有Sb掺杂ZTO薄膜在360~800 nm波长范围内透过率均在78%以上。     

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。     

Fe（C5H4-CH2-Trp-OMe）2的合成、晶体结构及金属离子识别性能

摘要： 以优化的两步一锅反应法合成了生物金属有机化合物Fe（C₅H₄-CH₂-Trp-OMe）₂（FcL）,通过NMR、HRMS及IR等对其结构进行了表征,利用X射线单晶衍射测定了分子结构。循环伏安法研究表明FcL在0.00~0.90 V电位范围内,给出一稳定的、形态良好的氧化还原峰,这归于化合物中Fc/Fc⁺电对的氧化还原过程。电化学金属离子识别研究显示FcL在过渡金属离子Zn²⁺和Cu²⁺的存在下,导致了配体Fc/Fc⁺式量电位的显著阳极移动,其△E^0''对Zn²⁺和Cu²⁺分别为342和335 mV,表明了FcL对Zn²⁺和Cu²⁺具有良好的识别能力。     

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。     

掺杂和取代对红色荧光材料SrAl12O19:Mn4+发光性能的影响

SrAl₁₂O₁₉:Mn⁴⁺是一种用于高显色性白光发光二极管的候选红色荧光材料。本论文研究了Mg²⁺、Zn²⁺和Ge⁴⁺离子的掺杂效应以及Ge³⁺、Ca²⁺和Ba²⁺离子的取代效应SrAl₁₂O₁₉:Mn⁴⁺荧光材料性能的影响。样品通过高温固相反应制备,焙烧温度在1 250~ 1 500℃之间。利用X射线衍射技术表征了材料的相纯度,用荧光激发光谱和发射光谱表征了材料的荧光性能。研究结果指出,与未进行Mg²⁺或Zn²⁺掺杂的样品相比,Mg²⁺或Zn²⁺离子对Al³⁺格位的掺杂可以使材料的发光强度提高~60%,其原因被认为是掺杂促进了激活剂Mn⁴⁺离子进入晶格,其过程可以表示为:MO+MnO₂=M_Al''+Mn_Al^·+3O_O^×(M=Mg,Zn),电子顺磁共振谱支持这一结果。Ge⁴⁺离子的掺杂使材料的发光性能明显下降。Ge³⁺离子可以取代Al³⁺离子形成全范围的固溶体,其中少量Ge³⁺离子的掺杂可以使材料的荧光发射强度提高~13%,而掺杂量进一步提高使材料的荧光性能下降。Ca²⁺和Ba²⁺对Sr²⁺的取代仅形成有限范围的固溶体。Ca²⁺的取代使材料的发光性能提高;而 Ba²⁺的取代使材料的发光强度下降。     

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。     

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.     

Simple imine linked colorimetric and fluorescent receptor for sensing Zn ions in aqueous medium based on inhibition of ESIPT mechanism

Herein, we report the highly selective binding of Zn²⁺ ion by the salicylaldimine based Schiff base chromogenic receptor 1 [(N,N′-bis (salicylidine)-o-phenylenediamine]. Receptor 1 senses Zn²⁺ ion in aqueous medium by colorimetric and fluorescent response in the presence of other metal ions like Pb²⁺, Hg²⁺, Sn²⁺, Cd²⁺. Receptor 1 on binding with Zn²⁺ ion exhibits fluorescence enhancement which is due to the inhibition of the (ESIPT) mechanism.     

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。     

A new acridine derivative as a fluorescent chemosensor for zinc ions in an 100% aqueous solution: a comparison of binding property with anthracene derivative

A new acridine derivative was synthesized as a fluorescent chemosensor for Zn²⁺ in an 100% aqueous solution. Compound 1 displayed a selective CHEF (chelation enhanced fluorescence) effect with Zn²⁺, on the other hand, a similar anthracene derivative 2 did not display any significant change with the metal ions examined.     

Novel highly selective fluorescent chemosensors for Zn(II)

Two novel fluorescent Zn²⁺ chemosensors were synthesized in four steps from inexpensive starting materials. They exhibited very strong fluorescence responses to Zn²⁺ and had remarkably high selectivity to Zn²⁺ than other metal ions including Mg²⁺, Ca²⁺, Ni²⁺, Cu²⁺, and Cd²⁺. These two new molecules could be used as low-priced yet high-quality Zn²⁺ chemosensors.     

Exploring fluorescent covalent organic frameworks for selective sensing of Fe<Superscript>3+</Superscript>

Covalent organic frameworks (COFs) have been widely applied in gas capture and separation, but the fluorescent property of COFs with large π-conjugated system tends to be underexplored. Here we report the fluorescent properties of several COFs including TaTa, DhaTab, TRITER-1 and TzDa and the effect of metal ions of Na⁺, Mg²⁺, K⁺, Ca²⁺, Cu²⁺, Zn²⁺, Pb²⁺, Ag⁺, Cd²⁺ and Fe³⁺ on the fluorescence of these COFs. The results show that only Fe³⁺ significantly quenched the fluorescence of the studied COFs. The possibility of the four COFs for selective sensing of Fe³⁺ was demonstrated. The possible mechanism of the effect of Fe³⁺ on the fluorescence of the COFs was based on the absorption competition quenching.     

Actual aspects of the chemistry of dipyrrin dyes and prospects for their application in molecular sensorics

The results of research on the correlation between molecular structure and spectral luminescent and photophysical properties for a new class of dyes and luminophores based on dipyrrins, bis(dipyrrins), and their coordination compounds in different media are summarized. The new perspective applications of dipyrrin dyes and luminophores as fluorescent sensors for measuring the polarity, viscosity, and temperature of the medium and highly sensitive and selective fluorescent “off-on” chemosensors for detecting Zn²⁺, Cd²⁺, and Hg²⁺ cations in weakly polar and nonpolar organic solvents and biological systems are discussed.     

Imidazo-benzo-15-crown-5 ethers bearing arylthienyl and bithienyl moieties as novel fluorescent chemosensors for Pd and Cu

Novel fluorescent ionophores bearing imidazo-arylthienyl or imidazo-bithienyl π-conjugated bridges functionalized with one or two fused benzo-15-crown-5 ethers as receptor units are reported. The sensing ability of the compounds in the presence of metallic cations (Li⁺, Na⁺, K⁺, Ca²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Pd²⁺, and Hg²⁺) and fluoride ion was studied in MeCN/DMSO solutions by absorption and emission spectroscopy. The experimental results indicate that all compounds could act as selective fluorimetric sensors for Cu²⁺ and Pd²⁺ and also for the fluoride ion, in the case of the bis-substituted crown ether derivatives.     

Two‐Photon Probes for Zn2+ Ions with Various Dissociation Constants. Detection of Zn2+ Ions in Live Cells and Tissues by Two‐Photon Microscopy

A series of Zn²⁺‐selective two‐photon fluorescent probes (AZnM1−AZnN) that had a wide range of dissociation constants (K_d^TP=8 nm‐ 12 μM ) were synthesized. These probes showed appreciable water solubility (>3 μM ), cell permeability, high photostability, pH insensitivity at pH>7, significant two‐photon action cross‐sections (86–110 GM) upon complexation with Zn²⁺, and can detect the Zn²⁺ ions in HeLa cells and in living tissue slices of rat hippocampal at a depth of >80 μm without mistargeting and photobleaching problems. These probes can potentially find application in the detection of various amounts of Zn²⁺ ions in live cells and intact tissues.