官能化罗丹明基金属阳离子荧光探针

重金属离子对环境和生物体具有极强的生理毒性,故高选择性和高灵敏度的离子检测荧光探针的研究有着重要意义。荧光分子探针在表达分子间识别行为以及复杂的环境、生命体系的内状态信息方面具有优异的性能,已广泛深入的用于构建新型功能性探针分子。本文综述了近年来基于罗丹明的金属阳离子如Hg₂₊、Cu₂₊、Fe₃₊等荧光分子探针的研究进展,包括探针的结构特征、检测机理、检测水平,更重要的是其在环境检测、生物成像、分子器件等方面的新应用,并对荧光探针所面临的问题和发展前景做了分析。     

Highly selective chromogenic and redox or fluorescent sensors of Hg2+ in aqueous environment based on 1,4-disubstituted azines

Two new chemosensors that exhibit high affinity and high selectivity for Hg2+ in aqueous environment which operate through two different channels, optic/redox and optic/fluorescent, are reported. The optical change in sensing can be used even for a "naked-eye" detection of Hg2+ ions, whereas the fluorescent response can be modulated by varying the solvent polarity.     

A general strategy to convert the MerR family proteins into highly sensitive and selective fluorescent biosensors for metal ions

The MerR family metal-regulatory proteins are converted into fluorescent biosensors that can detect different metal ions with high sensitivity and selectivity.     

Selective and Sensitive Fluorescent Chemosensors for Cu2+ Ion Based upon Bis‐1,8‐naphthalimide Dyads

A series of new fluorescent chemosensors 5a – 5e , composed of two aminonaphthalimide fluorophores and 2,6‐bis((N‐aminoalkyl)aminocarboxy)pyridines, were prepared, characterized, and their fluorescent properties towards heavy and transition metal (HTM) ions were investigated. Chemosensors 5c – 5e exhibited high selectivity and sensitivity for Cu²⁺ ion over other HTM ions with fluorescent quenching (green to colourless). It clearly demonstrated that the length of the linkers (diamines) between the aminonaphthalimides and 2,6‐dicarboxypyridine of 5a – 5e was very important for their sensitivity and selectivity for Cu²⁺ ion over other HTM ions.     

荧光法检测重金属铅离子的研究进展北大核心CSCD

铅作为一种重金属,广泛应用于工业生产,对环境和人体健康具有显著影响。因此,开发铅离子检测技术是一项具有重要意义的研究内容。荧光法与传统重金属离子检测方法相比,具有灵敏度高、选择性好等优点,故荧光法常用于水体等实际样品中重金属离子的定性或定量分析。本文围绕近几年报道的基于荧光法检测铅离子的研究现状进行介绍,包括荧光染料、荧光纳米材料、荧光生物材料包括荧光蛋白等3种检测材料,并在此基础上提出荧光法检测铅离子领域面临的主要挑战,对未来的研究趋势进行了展望。     

Rhodamine triazole-based fluorescent probe for the detection of Pt(2+)

A rhodamine triazole-based fluorescent chemosensor has been developed for the selective detection of platinum ions in aqueous solutions. The rhodamine 6G hydroxamate linked with a propargyl group is converted to the corresponding triazole by a "click" reaction. The dual binding unit composed of a hydroxamate and a triazole shows high selectivity and sensitivity toward Pt(2+) over a range of other metal ions in water. The fluorescent probe is applied to monitor cisplatin in aqueous solutions.     

Using fluorescence dyes as a tool for analyzing the MALDI process

In a recent paper (Setz, P. D.; Knochenmuss, R. Phys. Chem. A2005, 109, 4030-4037) energy-transfer from excited matrix molecules to fluorescent traps was used to study the role of pooling reactions for the ionization processes in matrix-assisted laser desorption ionization (MALDI) using 2,5-dihydroxybenzoic acid as matrix. Exciton trapping was shown to interfere with matrix ionization. These investigations were extended to analyze the influence of fluorescent traps on both matrix and analyte ions for alpha-cyano-4-hydroxycinnamic acid and further matrices. A strong influence of the fluorescent traps on both matrix and analyte ionization was revealed, depending on the matrix:trap ratio, and manifested itself differently for low and high mass analytes. The observations are rationalized by the intermediate formation of a "hot spot" due to an efficient conversion of electronic excitation energy to vibronic energy within the fluorescent traps. This process favors the desorption and ionization of small vaporizable analytes and compromises the cluster ablation process needed for larger analyte ions.     

Phenoxazine‐based Near‐infrared Fluorescent Probes for the Specific Detection of Copper (II) Ions in Living Cells

Abstract : It is well known that copper ions play a critical role in various physiological processes. However, a variety of human diseases are tightly correlated with copper overload. Although there are numerous fluorescent probes capable of detecting copper ions, most of them are “turn‐off” probes owing to copper (II) ions fluorescence quenching effect, resulting in poor sensitivity. Herein, a novel “turn‐on” near‐infrared (NIR) fluorescent probe PZ‐N based on phenoxazine was designed and synthesized for the selective detection of copper (II) ions (Cu²⁺). Upon the addition of Cu²⁺, the probe could quickly react with Cu²⁺ and emit strong fluorescence, along with colour change from colourless to obvious blue. Moreover, the probe PZ‐N showed good water solubility, high selectivity, and excellent sensitivity with low limit of detection (1.93 nM) towards copper (II) ions. More importantly, PZ‐N was capable of effectively detecting Cu²⁺ in living cells.     

Fluorescence turn-on chemodosimeter for rapid detection of mercury (II) ions in aqueous solution and blood from mice with toxicosis

The heavy metal mercury (Hg) is a threat to the health of people and wildlife in many environments. Among various chemical forms, Hg²⁺ salts are usually more toxic than their counterparts because of their greater solubility in water; thus, they are more readily absorbed from the gastrointestinal tract into circulation. Therefore, new chemical receptors for detecting Hg²⁺ ions in circulation are needed. In this study, we developed a rhodamine-based turn-on fluorescence probe to monitor Hg²⁺ in aqueous solution and in blood of mice with toxicosis. The chemodosimeter responds to Hg²⁺ ions stoichiometrically, rapidly, and irreversibly at room temperature as a result of a chemical reaction that produces strongly fluorescent oxadiazole. The new fluorescent probe shows good fluorescence response, with high sensitivity and selectivity, toward Hg²⁺ ions in aqueous solution and in blood from mice with toxicosis and facilitates the naked-eye detection of Hg²⁺ ions.     

钯离子荧光探针的研究进展

钯是一种重要的贵金属,在制药、燃料电池、电子电气和珠宝等行业得到广泛的应用。 然而,它的大量使用不可避免会造成其在环境中的残留,产生毒害,因此对钯的检测与识别具有重要的意义。 荧光探针具有较高的选择性、较高灵敏度、对设备依赖小、操作简单、检测限低等优点。 本文综述了近年应用于低浓度检测钯离子荧光分子探针的设计方法及作用机制。 按照荧光探针检测钯离子的响应模式,主要分为淬灭型、增强型、比率型3种方式进行评述。 尽管钯离子探针的研究在分子设计上取得了重要进展,但荧光染料与钯离子的响应时间尚且不能人为控制,尤其对于复杂体系中钯离子的检测效果尚待进一步改进。 因此,开发钯离子响应时间短、灵敏度高、专一识别性高并能应用于复杂体系的荧光探针,可能是今后主要发展方向。     

具有重要生物学意义的重金属及过渡金属离子荧光分子探针

过渡金属及重金属广泛地存在于自然界中,其中的一些元素（如铜、锌等）在生命过程中具有非常重要的功能,而另外一些元素（如铅、汞、镉等）则在很低浓度时就对生物体具有极强的毒性。本文简要介绍了金属离子荧光探针的设计原理,并综述了近5年来具有重要生物学意义的重金属及过渡金属离子Pb²⁺、Hg²⁺、Cd²⁺、Cu²⁺、Cu⁺、Zn²⁺荧光分子探针的设计合成、性能及其在活细胞中应用研究的最新进展。     

Development of Fluorescent Film Sensors Based on Electropolymerization for Iron(III) Ion Detection

Two electroactive materials, M1 and M2 , are synthesized and their fluorescent electropolymerized (EP) films are prepared and used to detect metal ions. From the tested metal ions, M1 and M2 are demonstrated to be sensitive and selective for Fe³⁺ ions. In particular, M2 exhibits higher sensitivity towards Fe³⁺ ions. The fluorescent detection ranges from 10^?5 M to 4×10^?4 M . The excellent performance of the EP fluorescent films is mainly due to the strong metal‐chelated properties of M2 and the intrinsic porous cross‐linked‐network microstructure of the EP films. This study, thus, provides a promising Fe³⁺ sensing candidate and a potential preparation method for fluorescent sensing films.     

A fluorescent probe for zinc ions based on N-methyltetraphenylporphine with high selectivity

N-methyl-alpha,beta,gamma,delta-tetraphenylporphine (NMTPPH) has been used to detect trace amount of zinc ions in ethanol-water solution by fluorescence spectroscopy. The fluorescent probe undergoes a fluorescent emission intensity enhancement upon binding to zinc ions in EtOH/H(2)O (1:1, v/v) solution. The fluorescence enhancement of NMTPPH is attributed to the 1:1 complex formation between NMTPPH and Zn(II) which has been utilized as the basis for the selective detection of Zn(II). The linear response range covers a concentration range of Zn(II) from 5.0x10(-7) to 1.0x10(-5)mol/L and the detection limit is 1.5x10(-7)mol/L. The fluorescent probe exhibits high selectivity over other common metal ions except for Cu(II).     

A Selective and Sensitive "Turn-on" Fluorescent Chemosensor for Recognition of Hg(2+) Ions in Water

Based upon highly selective and irreversible Hg(2+) -promoted deprotection of the dithioacetal reaction, a new water-soluble "turn-on" fluorescent chemosensor (1) was prepared and exhibited high selectivity and sensitivity towards the Hg(2+) ion over other heavy and transition-metal ions in pure water by transforming a weakly fluorescent precursor (colorless) to a highly fluorescent aldehyde (yellow-green; see figure) with a 155-fold increase in fluorescent intensity.     

一个高度灵敏和高选择性铝离子比率探针的合成及应用

本文构建了一种基于3-苯丙噻唑基-2-羟基-5-甲基苯甲醛的荧光探针用于检测铝离子。该荧光探针能够灵敏、高选择性地检测铝离子,并显示出颜色和强烈的荧光变化双重响应。研究结果表明,该探针对铝离子表现出非常好的荧光增强效果,检测过程中其它金属离子不会对检测结果产生明显的干扰。其比率荧光强度(I490/I567)与铝离子的浓度(0~20μmol/L)之间具有良好的线性关系,检测限低至0.5μmol/L。由于具有高效的选择性,该探针可以用于检测污染河水中的铝离子含量。     

Rhodamine-based highly sensitive colorimetric off-on fluorescent chemosensor for Hg2+ in aqueous solution and for live cell imaging

A novel rhodamine-based highly sensitive and selective colorimetric off-on fluorescent chemosensor for Hg(2+) ions is designed and prepared by using the well-known thiospirolactam rhodamine chromophore and furfural hydrazone as signal-reporting groups. The photophysical characterization and Hg(2+)-binding properties of sensor RS1 in neutral N, N-dimethylformamide (DMF) aqueous solution are also investigated. The signal change of the chemosensor is based on a specific metal ion induced reversible ring-opening mechanism of the rhodamine spirolactam. The response of the chemosensor for Hg(2+) ions is instantaneous and reversible. And it successfully exhibits a remarkably "turn on" response toward Hg(2+) over other metal ions (even those that exist in high concentration). Moreover, this sensor is applied for in vivo imaging in Rat Schwann cells to confirm that RS1 can be used as a fluorescent probe for monitoring Hg(2+) in living cells with satisfying results, which further demonstrates its value of practical applications in environmental and biological systems.     

A Single‐Wavelength‐Emitting Ratiometric Probe Based on Phototriggered Fluorescence Switching of Graphene Quantum Dots

Ratiometric fluorescent probes are of great importance in research, because a built‐in correction for environmental effects can be provided to reduce background interference. However, the traditional ratiometric fluorescent probes require two luminescent materials with different emission bands. Herein a novel ratiometric probe based on a single‐wavelength‐emitting material is reported. The probe works by regulating the luminescent property of graphene quantum dots with UV illumination as activator. The ratiometric sensor shows high sensitivity and specificity for iron ions. Moreover, the ratiometric sensor was successfully employed to monitor ferritin levels in Sprague Dawley rats with chemical‐induced acute liver damage. The proposed single‐wavelength ratiometric fluorescent probe may greatly broaden the applicability of ratiometric sensors in diagnostic devices, medical applications, and analytical chemistry.     

Highly fluorescent Ag nanoclusters: microwave-assisted green synthesis and Cr3+ sensing

Highly fluorescent Ag nanoclusters were prepared in aqueous solution via a rapid microwave-assisted green approach and used as a novel fluorescence probe for the determination of Cr(3+) ions with high sensitivity and excellent selectivity.     

激发态分子内质子转移荧光探针的研究进展

荧光探针凭借其选择性好、灵敏度高、响应时间快、易于操作和检测限低等优点得到了广泛的关注。 激发态分子内质子转移(ESIPT)化合物具有特殊的激发态光物理过程,其显著的光物理性质是有较高的荧光量子产率及大的斯托克斯位移。 对于荧光分子而言,较大的斯托克斯位移可以减少自吸收和由内滤效应产生的干扰,增强分子的耐光性,有利于荧光的发射。 本文对ESIPT荧光探针检测离子(包括金属阳离子和阴离子)、中性小分子和生物大分子的研究进展进行阐述,并对ESIPT荧光分子的存在问题和应用前景进行评述。     

Highly Selective Ratiometric Fluorescent Sensor for La(III) Ion Based on a New Schiff's Base

Abstract

A new fluorescent sensor containing (1-[({2-[2-(2-hydroxy-1-naphtyl)-3-(2-{[(E)-1-(2-hydroxy-1-naphtyl)methylidene]amino}ethyl)-1-imidazolidinyl]ethyl}imino)methyl]-2-naphthol) (L) was synthesized for detecting La(III) ratiometrically. Complexation between compound L and La(III) with high selectivity gives rise to a great red shift from 430 to 522 nm in the emission spectra. In acetonitrile, the red shift of fluorescent emission upon lanthanium binding is due to the formation of a 1:1 metal–ligand complex. The fluorescent probe exhibits high selectivity over other common metal ions and mono-, di-, and trivalent cations, which indicates good selectivity for La(III) ions over a large number of interfering cations.