Azomethine-H as a Highly Selective Fluorescent Probe for Fe3+ Detection in 100％ Aqueous Solution and Its Application in Living Cell Imaging

A simple assay for the detection of Fe³⁺ in water by means of fluorescence spectroscopy was developed based on a commercially available reagent, Azomethine-H(A-H), allowing sensing trace levels of Fe³⁺ with high selectivity over other cations. A significant fluorescence quenching of A-H at 424 nm was found after its binding with Fe³⁺ in 100% aqueous solution at pH=7.0, while other physiologically relevant metal ions posed little interference. The fluorescence responses can be well described by the modified Stern-Volmer equation. A good linear relationship(R²=0.9904) was observed up to 1.6×10^-5 mol/L Fe³⁺ ions. The detection limit, calculated via the 3σ IUPAC(international union of pure and applied chemistry) criteria, was 1.95×10^-7 mol/L. Moreover, the colorimetric and fluorescent response of A-H to Fe³⁺ can be conveniently detected by the naked eye, providing a facile method for visual detection of Fe³⁺. The proposed method was used to determine Fe³⁺ in water samples. Moreover, inverted fluorescence microscopy imaging using human umbilical vein endothelial cells shows that A-H can be used as an effective fluorescent probe for detecting Fe³⁺ in living cells.     

A Novel Coumarin-based Fluorescence Chemosensor for Fe^3＋

A novel coumarin derivative[7-diethylamino-2-oxo-2H-chromene-3-carboxylic acid（6-amino-pyridin2-yl）-amide,CFe1] has been synthesized and its potential application as a chemosensor for the detection of metal ions has been further investigated.The responses of CFe1 to Fe^3＋ were studied by fluorescence emission spectrometry in the presence of other metal ions such as Al^3＋,Ba^2＋,Ca^2＋,Co^3＋,Cr^3＋,Cu^2＋,Fe^2＋,Hg^2＋,Mg^2＋,Mn^2＋,Na^＋,Ni^＋,Pb^2＋,Zn^2＋,K^＋,and Ag^＋.CFe1 showed a good selectivity for Fe^3＋ with fast response,a wide pH span of 3.3-9.18,and a large Stocks shift.CFe1 in the presence of Fe^3＋ and ethylene diamine tetraacetic acid（EDTA） makes the blue solution fade to colorless,which is due to the formation of CFe1-Fe^3＋ complex instead of any catalytic action of Fe^3＋.Furthermore,the imaging of Fe^3＋ in cultured single mice microglia cells was realized with the aid of CFe1,indicating that CFe1 has a great potential to be used as promising models for the future design of novel and robust chemosensor for metal ion detection in the field of biomedical and environmental analyses.     

含蒽双三联吡啶化合物的合成及其对金属离子的荧光识别性能

以蒽,醋酸,溴化氢,1,3,5-三聚甲醛,N,N,N-三甲基-1-十四烷基溴化铵,双(2-吡啶基甲基)胺,三乙胺等为原料,合成了含蒽的双三联吡啶化合物,其结构经¹H NMR、 ¹³C NMR和HR-MS表征。目标产物中含有双三联吡啶结构,可以与金属离子之间具有较强的螯合作用,从而改变原来目标化合物的光学性质,尤其是其荧光性能。实验结果表明：体系中随着Zn²⁺、Ag⁺和Mn²⁺浓度不断增大,含蒽双三联化合物荧光强度不断增强;Cu²⁺、Co²⁺、Hg²⁺、Pb²⁺、Na⁺、Fe³⁺、Ni²⁺均随着浓度的增大,含蒽双三联化合物荧光强度不断减弱。在此基础上,运用荧光光谱法能高灵敏度的检测痕量金属离子。      

11-Mercaptoundecanoic acid functionalized gold nanoclusters as fluorescent probes for the sensitive detection of Cu2+ and Fe3+ ions

Metal ions are physiologically essential,but excessive metal ions may cause severe risk to plants and animals.Here,we prepared gold nanoclusters(Au NCs) protected by 11-mercaptoundecanoic acid(11-MUA),which have excellent fluorescence properties for the detection of metal ions.The results showed that the copper ions(Cu~(2+)) and iron ions(Fe~(3+)) in the solution have obvious quenching effect on the fluorescence intensity of Au NCs.The detection range of Fe~(3+) was 0.8–4.5 mmol/L(R~2= 0.992) and 4.5–11.0 mmol/L(R~2= 0.997).And Cu~(2+) has a lower linear range(0.1–1.0 mmol/L,R2= 0.993).When EDTA was added into the reaction system,it was observed that the quenching effect of Cu~(2+) and Fe~(3+)on Au NCs showed different phenomenon.Then,the effect of metal ions on the fluorescence of Au NCs was investigated.The selective detection of Cu~(2+) was achieved by EDTA masking of Fe~(3+).In addition,we realized the metal ions detection application of Au NCs in the serum     

Novel Fluorescent Chemosensors Based on Tryptophan Unit for Cu2+ and Fe3+ in Aqueous Solution

We reported four fluorescent chemosensors containing tryptophan units. The fluorescence spectrum titration experiments suggest that chemosensors 1, 2, 3 and 4 are highly selective for Cu²⁺ and Fe³⁺ over Li⁺, Na⁺, K⁺, Co²⁺, Zn²⁺, Ni²⁺, Hg²⁺ and Cr³⁺ via forming complexes with Cu²⁺ or Fe³⁺, which is confirmed by dramatical quench of fluoreseence in aqueous solution at pH 7.4, thus making all the chemosensors suitable for Cu²⁺ and Fe³⁺ fluorescent sensors.     

Rational Design of Ratiometric Fe3+ Fluorescent Probes Based on FRET Mechanism

As the most abundant transition metal element in mammals, iron(Fe) plays a vital role in life activities. It is of great significance to study the variation of Fe³⁺ level in living organisms. In virtue of the advantages of high sensitivity, good selectivity and low damage to living systems, the fluorescence detection of Fe³⁺ has attracted much attention. Compared with the intensity-based fluorescent probe, the ratiometric fluorescent probe has less interference of environmental and can realize quantitative detection. In this study, four ratiometric Fe³⁺ fluorescent probes, R1, R2, R3 and R4_, were designed and synthesized using fluorescence resonance energy transfer(FRET) mechanism to achieve quantitative detection of Fe³⁺. In the FRET systems, 1,8-naphthalimide fluorophore derivatives were adopted as donors while rhodamine B derivatives were selected as receptors. The connection sites of the donor and acceptor in R3 and R4 are different from those in R1 and R2. All the four probes showed good response and selectivity to Fe³⁺. The energy transfer efficiencies of R3 and R4 were obviously higher than those of R1 and R2. This work provided a promising strategy for the development of fluorescent ratiometic Fe³⁺sensors.     

A New Tetrasubstituted Imidazole Based Difunctional Probe for UV-spectrophotometric and Fluorometric Detecting of Fe3+ Ion in Aqueous Solution

Two new compounds,4-(2-bromophenxl-4,5-diphenyl-imidazol-1-yl)ani 1 ine(probe 1)and 4-[2,4,5-tris(4-bromopheny1)-1H-imidazol-1-y1]aniline(probe 2),were synthesized via a soft and high-efficiency one-pot microwave-assisted method under solvent-free conditions.Their sensing to different metal ions was detected by UV spectrophotometry and fluorescence spectrometry.Probe 2 revealed highly selective and sensitive UV and fluorescence response to Fe^3+ion.Upon the addition of Fe^3+ion,probe 2 showed obvious color change of the solution,conspicuous absorbance enhancement and relatively quick fluorescence quenching.The detection limit for Fe^3+ion was respectively calculated to be 0.72μmol/L(fluorescent detection)and 0.48μmol/L(UV-spectnim detection).Also,probe 2 was bound by Fe^3+ion to tonn a 1:1 complex.Moreover,preliminary application of probe 2 tor detecting Fe^3+ion in aqueous solution was attempted,and satisfying results were obtained.     

Metal-organic framework as a multi-component sensor for detection of Fe3+, ascorbic acid and acid phosphatase

In this research,a hydroxyl group functionalized metal-organic framework(MOF),UiO-66-(OH)₂,was synthesized as a "on-off-on" fluore scent switching nanoprobe for highly sensitive and selective detection of Fe³⁺,ascorbic acid(AA) and acid phosphatase(ACP).UiO-66-(OH)₂ emits yellow-green light under ultraviolet light,when Fe³⁺ was added,Fe³⁺ was chelated with hydroxyl group,the electrons in the excited state S_1 of the MOF transferred to the half-filled 3 d orbits of Fe³⁺,resulting in fluorescence quenching because of the nonradiative electron/hole recombination annihilation.AA could reduce Fe³⁺ to Fe²⁺,which can destroy the electron transfer between UiO-66-(OH)₂ and Fe³⁺ after AA adding,resulted in nonoccurrence of the nonradiative electron transfer,leading to the recovery of UiO-66-(OH)₂ fluorescence intensity.The probe can also be used to detect ACP based on the enzymolysis of 2-phospho-L-ascorbic acid(AAP) to produce AA.Benefitting from the hydroxyl group and the characteristics of UiO-66,including the high porosity and large surface area,the developed UiO-66-(OH)₂ showed extensive advantages as a fluorescent probe for detection of multi-component,such as high sensitivity and selectivity,colorimetric detection,fast response kinetics and easy to operate,economical and secure.This is the first time to use active group functionalized MOFs as a multicomponent sensor for these three substances detection.     

由蚕砂制备的碳量子点在不同激发、pH、金属离子、温度及极性环境下的荧光性质研究

碳量子点作为一种新兴的荧光纳米材料,具有粒径分布均匀、光稳定性好、激发-发射波长可调控、表面可修饰等优良的性质,兼具低毒性、生物相容性好等优点,在分析检测和生物成像等领域展现出广阔的应用前景。而蚕砂是家蚕的干燥粪便,简单易得。利用蚕砂作为碳量子点制备原料,采用微波合成的方法制备得到了一种平均水合粒径为4.86 nm,含氮、硫修饰的碳量子点材料,可作为针对激发波长、pH、金属离子浓度、温度及溶剂极性的变化有着显著响应特性的碳量子点型荧光探针。该探针的荧光最大发射波长随激发波长或pH的增加而红移;荧光强度随温度或pH的降低而增加;随着金属离子,特别是铜离子的加入而逐渐降低,并随着EDTA络离子的加入而逐渐回复。在多种溶剂中该探针均具有较好的溶解度,当换用不同极性的溶剂时,随着溶剂极性的增加荧光发射波长逐渐红移。荧光性质随多重环境参数变化为该碳量子点在未来的生物检测和成像领域提供了广阔的应用前景。     

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.     

A highly selective chemosensor for copper ion based on ICT fluorescence

Simple structural compounds 1 to 3 were synthesized.The presence of Cu²⁺ resulted in the fluorescence and absorption spectra change of 1 and 2,which indicated that 1 and 2 showed a highly selective response to Cu²⁺ over other metal ions.However,3 showed no selectivity for metal ions,which means that the compound could bind with several metal ions,such as,Ni²⁺,Zn²⁺,Cd²⁺.Hg²⁺, Pb²⁺,Fe³⁺,Mg²⁺,Ca²⁺,and Co²⁺,except Cu²⁺ and Ag⁺.The different spectral responses were attributed to the difference in binding sites for 1 and 3.     

喹啉取代的氟硼二吡咯染料类三价铁离子荧光探针的合成与性能

设计合成了喹啉取代的氟硼二吡咯荧光探针(BHQ),并用核磁共振波谱仪(NMR)和高分辨质谱仪(HRMS)等技术手段对合成的化合物进行了表征。 结果表明,在水溶液中,探针BHQ在Fe³⁺存在下具有良好的荧光增强识别效果,对 Fe³⁺ 具有响应快、较好的灵敏度和选择性特点,而其它金属离子的存在不干扰 Fe³⁺ 的检测。 探针BHQ与Fe³⁺以摩尔比1:1的方式进行配位。 该探针在Fe³⁺的检测方面具有潜在的应用价值。     

可区别铁离子荧光探针异构体的合成及其水样分析

分别以2-（2-氨基苯基）菲并咪唑和2-（3-氨基苯基）菲并咪唑为原料,与5-硝基水杨醛反应合成了两个菲并咪唑-苯酚异构体衍生物（PI?o?OH和PI?m?OH）。在水相体系中（V（DMF）∶V（HEPES） = 1∶1,pH = 7.4）,两个异构体发射中等强度的荧光。Fe³⁺存在下,两个异构体的荧光强度分别淬灭为原来的1/3和1/6,淬灭常数为4.8×10³和4.6×10³ L/mol,且淬灭效果不受其它干扰离子和pH值变化的影响。间位异构体PI?m?OH与Fe³⁺的荧光识别在2 min之内完成,配合速度明显优于邻位基异构体,且配合稳定性高于邻位异构体,配合常数为3.82×10⁴ L/mol。通过高分辨质谱和Job's曲线,确定了两个异构体与Fe³⁺识别配合比为1∶1,并建议了PI?m?OH-Fe³⁺ and PI?o?OH-Fe³⁺两个配合物的结构。两个异构体均可实现实际水样中Fe³⁺的定量检测,表明它们在实际水样的Fe³⁺分析中具有一定的应用价值。     

以9-蒽醛为荧光基团的吡唑啉衍生物荧光探针对Fe3+和Cu2+的检测

以9-蒽醛为荧光基团,吗啉环和吡唑环为识别基团,合成了一种新型荧光探针1,5-二苯基-3-(10-(吗啉甲基)蒽-2-基)吡唑啉(PMAP),利用1H NMR、13C NMR和单晶衍射表征其结构,通过荧光发射光谱和紫外可见吸收光谱研究其离子识别性能。结果表明,探针PMAP对Fe³⁺、Cu²⁺具有良好的识别效果,荧光量子产率分别从0.14降到0.05和0.04,溶液颜色从淡黄色变为蓝色。PMAP与Fe³⁺/Cu²⁺以1∶1的化学计量比形成配合物,检测限约为1μmol·L^-1。同时,干扰实验表明PMAP具有良好的抗干扰性能。在实际样品中的应用表明,PMAP传感器能有效地检测实际水样中的Cu²⁺和Fe³⁺。另外,根据Fe³⁺、Cu²⁺和H+不同组合时PMAP的量子产率构建了分子水平上的三输入NOR逻辑门电路。     

Determination of labile Cu(2+) in fresh waters by chemiluminescence: interference by iron and other cations

Analysis of labile Cu²⁺ in fresh waters using the Cu²⁺-catalysed oxidation of 1,10-phenanthroline by superoxide anion radical has been investigated. It was found that certain metal ions, notably Fe³⁺, Fe²⁺ and Pb²⁺ enhance the chemiluminescence (CL) intensity of this reaction by up to an order of magnitude when present in the μM concentration range. This enhancement is considered to arise through coordination of the metal ion to 1,10-phenanthroline, which prevents free rotation of the benzene rings in the excited state intermediate thought to be responsible for light emission. This introduces a potential interference when analyzing fresh waters, which usually contain Fe³⁺ concentrations of this magnitude. However, the enhancement effect saturates at about 4 μM Fe³⁺, so that reliable results can be obtained if the water sample is supplemented with Fe³⁺ to reach this level. Application of the enhanced technique to a river water, and a reservoir to which CuSO₄ had been added to control algal growth, are described. In both cases, only a small fraction of total dissolved Cu²⁺ is labile with respect to the chemiluminesence method.     

N,N-二甲基吡啶苯甲醛缩对二甲氨基苯甲酰腙的合成及对Cu2+的选择性识别

设计合成了可用于识别铜离子的化合物N,N-二甲基吡啶苯甲醛缩对二甲氨基苯甲酰腙(1), 通过¹H NMR, ¹³C NMR和MS等对其结构进行了表征; 采用荧光光谱和吸收光谱法研究了化合物1与金属离子间的相互作用. 结果表明, 化合物1对Cu²⁺ 呈现良好的选择性, Cu²⁺ 的加入使化合物1的荧光强度增强12.5倍, 加入其它金属离子如Fe³⁺, Zn²⁺, Pb²⁺, Hg²⁺, Cd²⁺, Co²⁺, Ni²⁺, Li⁺, K⁺, Ca²⁺, Mg²⁺ 和 Ag⁺, 仅引起化合物1荧光强度的微降. 采用双倒数线性回归拟合法计算可知, 化合物1与Cu²⁺ 形成了1: 1型强发光配合物, 结合常数为2.0×10⁷ L/mol.     

含磷酰杂菲侧基的苯乙烯衍生物聚集诱导发光特性及其在过渡金属离子检测中的应用

以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基)-1,4-二羟基苯(ODOPB) 为中心结构单元, 通过两步酯化反应, 在两侧分别引入4-戊氧基苯甲酰基和4-乙烯基苯甲酰基, 得到苯乙烯衍生物(MED).由于磷酰杂菲基团的大π共轭结构和极性共同作用, 使得形成聚集体后分子内转动受到限制, 降低了非辐射去活效率, 使 MED在达到一定聚集程度时, 荧光强度成倍增加, 呈现出聚集诱导发光增强(AIEE) 特性. 同时, Pt²⁺, Ru³⁺, Fe³⁺的加入对MED有显著的猝灭效果; 而Fe²⁺只是在形成聚集体过程中才有猝灭效果.     

金属离子对彩色成像过程的影响

通过测量和计算彩色单层片中成色剂的照相活性、偶合效率以及漂白前银密度等参数,研究了在分散四当量成色剂青(Ⅰ)时掺入金属离子Mg²⁺、Zn²⁺、Fe³⁺和Cu²⁺对彩色青单层片的成像过程中各个化学反应的影响。本实验的结果表明,成色剂中加入的金属离子Cu²⁺和Fe³⁺对成像过程的初始反应中的Ag影像形成产生不利的影响,但它们能促进偶合过程中青(Ⅰ)与显影剂氧化产物作用所生成的隐色体转变成染料的速率。Mg²⁺和Zn²⁺的加入主要是对偶合过程中青(Ⅰ)的偶合效率产生不利的影响。上述原因的综合影响,最终降低了彩色单层片的感光度。     

Synthesis of some new o-thioazo ligands and evaluation of their metallochromic properties

The synthesis of several new o-thioazo derivatives of p-cresol and 2-naphthol is reported, as well as their spectral properties, acid dissociation constants, and potential as metallochromic reagents. All the ligands form complexes with CU²⁺ and Ni²⁺. o-Mercaptoazo complexes of Fe³⁺ and Cu²⁺ with molar absorptivities of 3.83 × 10⁴ and 3.58 × 10⁴ l.mole⁻¹ cm⁻¹, respectively, are described.     

Multi-functional Photoelectric Sensor Based on a Three-fold Interpenetrated Cd(II) Coordination Polymer for Sensitively Detecting Different Ions

Athree-fold interpenetrated cadmium coordination polymer[Cd₃(BTC)₂(H₂O)₉]·2H₂O(CP 1)(H₃BTC=1,3,5-benzenetricar-boxylic acid) was selected and synthesized to investigate its photoelectric properties. CP 1 showed excellent sensitivity for Cr₂O₇^2- and Fe³⁺, low limit of detection(LOD:0.39 µmol/L for Cr₂O₇^2- and 1.72 µmol/L for Fe³⁺) and stability as electrochemical sensor. More importantly, fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe³⁺, Fe²⁺, and MnO₄^- with good cyclic stability and selectivity. Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.