基于激发态分子内质子转移(ESIPT)和聚集诱导发光(AIE)活性的菲并咪唑Fe~(3+)荧光探针及细胞成像研究

设计合成具有激发态分子内质子转移(ESIPT)和聚集诱导发光(AIE)特征的酚羟基菲并咪唑Fe~(3+)荧光探针PIP-o-OH,对其结构进行了表征和确认,并通过单晶结构确认了探针PIP-o-OH中的O—H与咪唑N的分子内氢键.紫外和荧光光谱分析表明,探针PIP-o-OH与Fe~(3+)形成络合物后实现Fe~(3+)的选择性识别,并通过质谱和离散傅立叶变换(DFT)计算确定了探针PIP-o-OH与Fe~(3+)的配位方式.探针PIP-o-OH与Fe~(3+)络合前后的荧光变化成功应用于HeLa细胞和实际水样中Fe~(3+)的检测.     

新型Fe~(3+)荧光探针及其生物成像研究（英文）

以罗丹明为基础合成、表征了一种"turn-on"型荧光探针.该探针对Fe~(3+)表现出很高的选择性和灵敏性.将Fe~(3+)加入到探针中,溶液的紫外吸收值和荧光强度都有很明显的变化,同时伴随着肉眼可见的溶液颜色改变.研究发现,探针与Fe~(3+)按照1∶1进行络合,引起了探针内酰胺环的打开,进而吸收值和荧光强度值发生变化.研究表明,在有其他共存离子存在下,该探针仍然可以有效检测Fe~(3+).细胞实验发现,探针可以穿过细胞膜,在细胞内与Fe~(3+)作用,同时也可检测小鼠体内Fe~(3+),呈现出很好的荧光成像效果.     

在纯水体系和活细胞中高选择检测Fe3+的香豆素荧光探针

设计、合成了一种香豆素类荧光探针CF470,该探针通过引入高水溶性且选择性与Fe~(3+)配位的多羟基基团实现了纯水体系中Fe~(3+)的检测。当在探针体系中加入Fe~(3+)后,其强烈的蓝色荧光在2 min内就可被完全猝灭。探针不仅对Fe~(3+)快速、高选择响应,而且由于引入了亲水的多羟基基团具有良好的水溶性。更重要的是,探针对活细胞低毒、生物相容性好,被成功应用于活细胞中Fe~(3+)的成像。     

一种基于香豆素衍生物的铁离子水溶性荧光探针的合成及其应用

设计合成了一种基于香豆素衍生物的水溶性荧光探针7-二乙氨基-3-甲醛香豆素,并通过~1HNMR,~(13)CNMR和MS确认其结构。探针具有良好的荧光发射性能,荧光最大发射峰位于471 nm;向其中加入Fe~(3+)后,荧光强度随着Fe~(3+)浓度的增加而逐渐减弱。探针L的荧光发射强度与Fe~(3+)的浓度在0.02~60.00μmol/L范围内呈良好的线性关系,可对Fe~(3+)进行定性与定量检测,检出限为22 nmol/L(S/N=3),对Fe~(3+)的选择性良好,不受其它常见金属离子的干扰。此外,探针对Fe~(3+)的检测具有可逆性。本探针具有很好的水溶性,在生理p H环境中检测效果较好成功用于人体淋巴肿瘤细胞Ramos中Fe~(3+)荧光成像。     

含蒽硫杂杯[4]芳烃荧光探针的合成及其对Fe~(3+)的识别

合成含蒽硫杂杯[4]芳烃荧光探针A,通过~1H NMR和~(13)C NMR对其结构进行了表征,考察了探针的光谱性能及其对常见离子的选择性识别,并进行了实际水样的加标回收检测。结果表明,在四氢呋喃/Tris-HCl缓冲溶液(4:1,V:V,pH 7.0)中,该探针可选择性识别Fe~(3+),且受常见金属阳离子和阴离子的干扰较小; Fe~(3+)的浓度在0.05～0.50 mmol/L范围内,荧光探针A的荧光强度与Fe~(3+)的浓度呈现较好的线性关系,相关系数(R~2)为0.99696,检出限(LOD)为0.75μmol/L;荧光探针A的荧光强度受pH的影响很小,在较宽的pH范围内,仍可有效地检测Fe~(3+)。该荧光探针A用于实际样品中Fe~(3+)检测,回收率和相对标准偏差(RSDs)均达到要求,有望用于水环境和生命体系中Fe~(3+)的选择性检测。     

罗丹明类Schiff碱荧光探针对Fe~(3+)的特异性识别研究

基于罗丹明结构设计合成了一种新型Schiff碱类荧光探针。随着Fe~(3+)的加入,探针溶液表现出明显的荧光增强,该现象表明探针和Fe~(3+)络合能力较强,避免了因Fe~(3+)自身磁性引起的荧光猝灭。探针在识别Fe~(3+)时,表现出很好的选择性,并且识别过程不受其他常见干扰离子的影响。进一步,通过job’s曲线和高斯理论计算对探针的识别机理进行了较深入的探究,得到探针与Fe~(3+)按照1∶1络合的结论,并提出了可能的络合位点和识别过程。     

一种罗丹明衍生物的合成及其对三价金属离子(Fe~(3+)、Cr~(3+)和Al~(3+))的识别

三价金属离子(Cr~(3+)、Fe~(3+)和Al~(3+))与人体健康密切相关。目前,检测Cr~(3+)、Fe~(3+)和Al~(3+)需要采用不同的荧光探针,增加了检测成本和检测时间。发展能够同时检测Cr~(3+)、Fe~(3+)和Al~(3+)的高灵敏度和强抗干扰能力的荧光探针具有非常重要的意义。本文以罗丹明B为原料,合成和表征了一种罗丹明类荧光增强型探针(P),并研究了其光谱性质。研究表明,在V(甲醇)∶V(水)=9∶1体系中对三价金属离子Fe~(3+)、Cr~(3+)和Al~(3+)具有较高的选择性,不受其它二价金属离子及一价金属离子的影响,抗干扰能力强。同时,探针P对三价金属离子具有较高的灵敏度,对Cr~(3+)、Al~(3+)和Fe~(3+)的检测限分别为3.0×10~(-4)、2.7×10~(-4)和1.0×10~(-4)mol/L,表明其可用于Cr~(3+)、Al~(3+)和Fe~(3+)的检测。     

亚铁离子荧光探针的研究进展

铁作为生命系统中最丰富的过渡金属元素,在许多生理和病理过程中发挥着无可替代的作用.铁平衡失调不仅会导致诸如癌症、心血管疾病、神经退行性疾病等的发生和发展,而且还会造成细胞铁死亡.尽管细胞中的铁有Fe~(2+)和Fe~(3+)两种形式,但细胞还原性微环境使其主要以Fe~(2+)形式存在.因此,开发一种对Fe~(2+)的特异性检测技术有助于深入了解Fe~(2+)与人类健康和疾病的关系.随着荧光成像技术的发展,近年来特异性检测Fe~(2+)的荧光探针引起学者们的极大关注.对近10年来报道的Fe~(2+)荧光探针,根据探针的设计思路、与Fe~(2+)的作用机理、光学特性以及其生物应用等方面进行了总结,并对Fe~(2+)荧光探针的发展前景进行了展望.     

一种螯合型Fe2+探针的构筑及性质

铁是人体的必需过渡金属元素,体内铁离子平衡的紊乱与多种疾病相关。发展铁离子探针,实现细胞和生命体中铁离子时空分布的跟踪与成像,对铁离子生理功能的研究具有重要价值。我们将BODIPY荧光团与三联吡啶通过乙烯基偶联,构建了新型Fe~(2+)螯合型探针BTPY,通过比色法与荧光法结合,实现了Fe~(2+)的特异性检测。探针最大激发波长582 nm在可见光区,荧光发射波长678 nm在近红外区,满足活体近红外成像的初步要求。BTPY与Fe~(2+)/Fe~(3+)结合导致吸收波长由573 nm红移至607nm,溶液颜色由红色到蓝色。其他金属离子的结合不发生明显吸收峰和颜色变化。同时,Fe~(2+)引起BTPY荧光猝灭而Fe~(3+)对BTPY荧光不造成明显影响,实现了Fe~(2+)与Fe~(3+)的区分。     

一种基于AIE机理识别Fe2+的荧光探针研究

合成了一种基于苯并噻唑衍生物的Fe~(2+)荧光探针YBTM。YBTM具有聚集诱导发光(AIE)性质,考察了YBTM在DMF/H_2O混合溶液中的荧光性质。在DMF/H_2O(1/9,v/v,HEPES 10 m M,p H=7.4)溶液中,探针YBTM对Fe~(2+)具有良好的选择性,Fe~(2+)可引起荧光猝灭,探针对Fe~(2+)响应快速,检测限为2.46×10~(-6)M。以酒石酸二铵作为掩蔽剂消除Fe~(3+)的潜在干扰。此外,探针YBTM可用于MCF-7细胞中Fe~(2+)的荧光成像。     

新型吡啶-杯[4]芳烃荧光探针的合成及其对Fe3+的检测性能

合成了一种新型的高选择性检测Fe3+的上沿功能化吡啶-杯[4]芳烃荧光探针,其结构经1H NMR, 13C NMR和HR-MS表征。离子检测实验结果表明,该吡啶-杯[4]芳烃探针的最大吸收峰出现在295 nm处,并在371 nm处显示出一个强的荧光发射带。与其他金属离子相比,新型探针对Fe3+表现出高选择性和强抗干扰能力的荧光淬灭响应。通过荧光滴定法和Job曲线图研究了探针与Fe3+的结合性。结果表明,探针与Fe3+形成2:1的配合物,缔合常数为3.26×107 M-1,检出限为7.9×10-7 M。     

A simple,water-soluble,Fe3+-selective fluorescent probe and its application in bioimaging

A simple,water-soluble,Fe³⁺-selective fluorescent probe,derived from rhodamine B,was synthesized and characterized.The probe exhibits a fluorescence response toward Fe³⁺ with acceptable sensitivity and selectivity and even facilitates visual or naked-eye detection of Fe³⁺.The experiment results show that the response of the probe to Fe³⁺ is pH-independent over a wide range of 4.0-10.0.In addition,fluorescence microscopic imaging experiments have proven that the probe is cell permeable and can be used for monitoring intracellular Fe³⁺ in living cells.     

A turn-on fluorescent probe for Au3+ based on rodamine derivative and its bioimaging application

A new fluorescent probe RY was synthesized for the detection of Au³⁺ ions based on a rhodamine B derivative. The fluorescent probe showed good selectivity and sensitivity to Au³⁺ ions. Obvious color and fluorescence changes could be observed with the naked eye while the fluorescent probe reacted with the Au³⁺ ions. The detection limit of the probe was determined to be 36 ppb by the fluorescence titration; the excellent linear relationship suggests that the probe is potentially useful for quantitative detection of Au³⁺ in vitro. We also demonstrated its bioimaging application in both living cells and mice; this was the first time that a fluorescent probe was successfully applied to imaging Au³⁺ in living animals.     

A highly sensitive naphthalimide-based fluorescent probe for detection of Cu2+ via selective hydrolysis reaction and its application in practical samples

A novel fluorescent probe CN3, containing 1,8-naphthalimide and picolinate units, was synthesized, and its structure was characterized by ¹H nuclear magnetic resonance spectroscopy (H NMR), ¹³C nuclear magnetic resonance spectroscopy (C NMR), and mass spectroscopy techniques. The detection property of CN3 toward copper ions (Cu²⁺) has been investigated in ethanol–HEPES buffer (v/v = 1/1, pH = 7.40) solution by UV–Vis absorption and fluorescence emission spectra. The results showed that CN3 had a highly selective and sensitive fluorescence quenching response to Cu²⁺, which was attributed to the generation of weak fluorescent N-ethyl-4-hydroxyphenyl-1,8- naphthalimide (compound 2) in polar ethanol–HEPES buffer (v/v = 1/1, pH = 7.40) via selective hydrolysis reaction. The detection of CN3 for Cu²⁺ was not influenced in the presence of other competing metal ions, and the limit of detection was as low as 50.0 nM. Therefore, the color of CN3 changed from colorless to yellowish when the Cu²⁺ was added. Furthermore, the fluorescent probe CN3 was utilized to detect Cu²⁺ in real water samples with fine performance.     

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.     

Selective sensing of Fe3+ based on fluorescence quenching by 2,6-bis(benzoxazolyl)pyridine with beta-cyclodextrin in neutral aqueous solution

A selective and sensitive fluorescent chemosensor (BBOZP-CD) for Fe(3+) was composed of water-soluble beta-cyclodextrins and 2,6-bis(benzoxazolyl)pyridine which was synthesized through the reaction of 2,6-pyridinedicarboxylic acid and o-aminophenol catalyzed by polyphosphoric acid under microwave irradiation. The chemosensor BBOZP-CD for metal ions were carefully investigated by fluorescent quenching in present of metal ions. The result showed BBOZP-CD chemosensor was remarkable fluorescence quenching and a highly selectivity and sensitivity for Fe(3+) in neutral aqueous solution, and the other common metal ions did not notably disturb the detection of Fe(3+). Additionally, the effect of pH to the chemosensor for Fe(3+) was also studied. The result indicated the respond signals of BBOZP-CD to Fe(3+) was stable and hardly influenced while the pH value was greater than 3.6.     

A squaraine based fluorescent probe for mercury ion via coordination induced deaggregation signaling

Due to the high affinity between dithiocarbamate(DTC) and Hg2+,a fluorescent probe based on squaraine chromophore with DTC side arm for Hg2+via coordination induced deaggregation signaling has been designed and synthesized.Squaraine has a high tendency to aggregate in aqueous solution,and such self-aggregation usually results in a dramatic absorption spectral broadening with fluorescence emission quenching.The combination of the DTC side arm of the probe with Hg2+induces steric hindrance,leading to the deaggregation of the dye complex,companying with a fluorescence emission restoration.In EtOH–H2O(20:80,v/v) solution,this ‘‘turn on' fluorescent probe has high selectivity and sensitivity toward Hg2+over other metal ions,and the limit of detection for Hg2+was estimated as2.19 ? 10à8mol/L by 3s/k.     

Synthesis of Highly Sensitive Fluorescent Probe Based on Tetrasubstituted Imidazole and Its Application for Selective Detection of Ag+ Ion in Aqueous Media

A small molecule fluorescent probe, 4-[2-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-1-yl]aniline(L) for detecting Ag⁺ ion was gently synthesized via one-pot multi-component reaction catalyzed by H₃[PW₁₂O₄₀] under solvent-free microwave irradiation. When the concentration of Ag⁺ ion changed from 0 to 8.0×10⁻⁶ mol/L in the solution of H₂O/CH₃OH(19:1, volume ratio), the fluorescence emission spectrum was blue-shifted and accompanied by a gradual increase in fluorescence intensity with a low detection limit of 3.0×10⁻¹¹ mol/L. Moreover, UV-Vis absorption titration experiment demonstrated a 1:1 stoichiometric ratio and an association constant of (9.95±0.44)×10⁵ L/mol between probe L and Ag⁺ ion, and thus their complexation mechanism was also proposed and verified. More importantly, this fluorescent probe was remarkably specific for Ag⁺ ion under the interference of other metal ions and exhibited a wide pH application range of 4.0-8.0. Additionally, preliminary application of this probe was also carried out and satisfactory results were shown.     

Highly selective chromogenic and fluorogenic probe based on benzothiazole-thiosemicarbazone Schiff base for detection of copper (II) in real samples

Copper is the third most abundant essential transition metal ion in the human body. It's responsible for important activities in many living things, but excessive intake of Cu²⁺ can lead to a range of diseases. A colorimetric and turn-off fluorescent probe (E)-2-(5-(benzothiazol-2-yl)-2-(diethylamino)-4-hydroxybenzylidene)-N-phenylhydrazine-1-carbothioamide ( ZTR ) was designed and synthesized by thiosemicarbazone Schiff base as a specific complexes site strategy to achieve highly specific Cu²⁺ detection. The fluorescence of the probe ZTR solution fell dramatically when Cu²⁺ was added, and its appearance changed from dazzling blue to nearly colorless. The simple structure and readily available fluorescent probe provide a novel approach for the quantitative detection of Cu²⁺ in the linear range from 0 to 0.12 μM, with a detection limit down to 16 nM, and with high selectivity for Cu²⁺ over 15 other metal ions. Job’s plot analysis showed that probe ZTR and Cu²⁺ formed a 1:1 coordination complex. In addition, because of its low detection limits and fast response time, the created fluorescent molecule was effectively used to study the target ions on test paper strips and in water samples.))     

溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe3+检测中的应用

利用溶剂热法, 基于氢氧化钾的插层作用制备了荧光氮化碳量子点(g-C₃N₄ QDs). 所获得的氮化碳量子点具有良好的水溶性和荧光稳定性. 透射电子显微镜(TEM)照片显示, 氮化碳量子点的粒径约为2.3 nm; X射线光电子能谱(XPS)和红外光谱(FTIR)结果表明, 氮化碳量子点表面存在大量的亲水基团; 荧光发射光谱(PL)结果表明, 氮化碳量子点具有激发波长依赖性. 基于三价铁离子(Fe³⁺)对荧光氮化碳量子点荧光的猝灭现象, 构建了一种用于检测Fe³⁺的荧光传感器, 在Fe³⁺浓度为5~100 μmol/L范围内, 检测体系表现出良好的线性关系, 检出限约为0.5 μmol/L, 实现了对Fe³⁺的高效、 灵敏、 选择性检测.