A fluorescent probe for Hg2+sensing in solutions and living cells with a wide working pH range简

In this paper, 2-carboxybenzaldehyde rhodamine B thiohydrazine(1) was synthesized and developed as a fluorescent probe to recognize Hg2+in DMF/H2 O(1:9, v/v) solution with high selectivity. The probe can be applied to the quanti?cation of Hg2+with a linear concentration range covering from 1.0×10-7mol/L to 1.0×10-5mol/L(R2= 0.9985) and a detection limit of 4.2×10-8mol/L. The experiment results show that the response of probe 1 to Hg2+is pH-independent in a wide range from 4.0 to 9.0. Moreover, the probe 1 exhibits excellent selectivity toward Hg2+over other common metal cations. Most importantly, the probe can be employed to monitor Hg2+in living cells using fluorescent imaging technique with satisfied results.     

Quantum dot-based "turn-on" fluorescent probe for detection of zinc and cadmium ions in aqueous media

Health or environmental issue caused by abnormal level of metal ions like Zn²⁺ or Cd²⁺ is a worldwide concern. Developing an inexpensive and facile detection method for Zn²⁺ and Cd²⁺ is in urgent demand. Due to their super optical properties, fluorescent quantum dots (QDs) have been developed as a promising alternative for organic dyes in fluorescence analysis. In this study, a CdTe QDs-based sensitive and selective probe for Zn²⁺ and Cd²⁺ in aqueous media was reported. The proposed probe worked in fluorescence “turn-on” mode. The initial bright fluorescence of CdTe QDs was effectively quenched by sulfur anions (S²⁻). The presence of Zn²⁺ (or Cd²⁺) can “turn-on” the weak fluorescence of QDs quenched by S²⁻ due to the formation of ZnS (or CdS) passivation shell. Under optimal conditions, a good linear relationship between the fluorescence response and concentration of Zn²⁺ (or Cd²⁺) could be obtained in the range from 1.6 to 35 μM (1.3–25 μM for Cd²⁺). The limit of detection (LOD) for Zn²⁺ and Cd²⁺ were found to be 1.2 and 0.5 μM, respectively. Furthermore, the present probe exhibited a high selectivity for Zn²⁺ and Cd²⁺ over other metal ions and was successfully used in the detection of Zn²⁺ or Cd²⁺ in real water samples.     

罗丹明类测定三聚氰胺的荧光探针的合成及应用研究

报道了罗丹明乙二醛酰腙的合成及与三聚氰胺的反应。在pH 3.0的缓冲溶液中三聚氰胺对罗丹明乙二醛酰腙的荧光强度有增强作用,其增强程度与三聚氰胺的浓度成正比,据此建立了一种新的测定三聚氰胺含量的荧光分析法。该方法线性范围为0.5~10.0 mg/L,r=0.994,检出限为0.15 mg/L,样品测定的RSD为1.7%(n=7)。     

Highly selective fluorescent probe based on a rhodamine B and furan-2-carbonyl chloride conjugate for detection of Fe3+ in cells

A furan-2-carbonyl chloride modified rhodamine B derivative (RBFC) has been designed and synthesized. The probe RBFC exhibited excellent sensitivity and selectivity for detection of Fe³⁺ with a 1:1 stoichiometry over other tested metal ions in a MeOH/H₂O (1:1, v/v, pH 7.36, HEPES buffer, 1.3?mM) solution. The association constant and the detection limit were calculated to be 7.28?×?10³?M^?1 and 0.437?μM based on fluorescence titration analysis. Furthermore, the probe RBFC was successfully applied in living cells, and the results indicated that the probe could monitor intracellular Fe³⁺ in MCF-7 cells.     

A highly sensitive and selective fluorescent probe for trivalent aluminum ion based on rhodamine derivative in living cells

A rhodamine spirolactam derivative (1) is developed as a colormetric and fluorescent probe for trivalent aluminum ions (Al³⁺). It exhibits a highly sensitive “turn-on” fluorescent response toward Al³⁺ with a 70-fold fluorescence intensity enhancement under 2 equiv. of Al³⁺ added. The probe can be applied to the quantification of Al³⁺ with a linear range covering from 5.0 × 10⁻⁷ to 2.0 × 10⁻⁵ M and a detection limit of 4.0 × 10⁻⁸ M. Most importantly, the fluorescence changes of the probe are remarkably specific for Al³⁺ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the experiment results show that the response behavior of 1 towards Al³⁺ is pH independent in neutral condition (pH 6.0–8.0) and the response of the probe is fast (response time less than 3 min). In addition, the proposed probe has been used to detect Al³⁺ in water samples and image Al³⁺ in living cells with satisfying results.     

A highly selective turn-on fluorescent probe for hypochlorous acid based on hypochlorous acid-induced oxidative intramolecular cyclization of boron dipyrromethene-hydrazone

A BODIPY-based fluorescent probe, HBP, was developed for the detection of hypochlorous acid based on the specific hypochlorous acid-promoted oxidative intramolecular cyclization of heterocyclic hydrazone in response to the amount of HOCl. The reaction is accompanied by a 41-fold increase in the fluorescent quantum yield (from 0.004 to 0.164). The fluorescence intensity of the reaction between HOCl and HBP is linear in the HOCl concentration range of 1–8 μM with a detection limit of 2.4 nM (S/N = 3). Confocal fluorescence microscopy imaging using RAW264.7 cells showed that the new probe HBP could be used as an effective fluorescent probe for detecting HOCl in living cells.     

罗丹明型荧光探针的合成及对Hg2+的识别

本文以罗丹明B-酰肼和2-氯-3-喹啉醛经缩合反应得到新型的罗丹明B衍生物3,其结构经1H NMR,MS,元素分析表征.通过荧光光谱法研究了目标物3在CH3CN-H2O溶液中与金属离子的识别特性.结果表明:目标物3可作为荧光探针选择性识别Hg2+,识别过程是不可逆的.     

A highly sensitive and selective fluorescent probe for Fe3+ containing two rhodamine B and thiocarbonyl moieties and its application to live cell imaging

A novel turn-on rhodamine B-based fluorescent chemosensor (RBCS) was designed and synthesized by reacting N-(rhodamine B)lactam-1,2-ethylenediamine and carbon disulfide. Upon addition of Fe³⁺ in EtOH/H₂O solution (2:1, v/v, HEPES buffer, 0.6?mM, pH 7.20), the RBCS displayed a significant fluorescence enhancement at 582?nm and a dramatic color change from colorless to pink, which can be detected by the naked eye. Significantly, the RBCS exhibited a highly selective and sensitive ability toward Fe³⁺. The detection limit of the probe was 2.05?×?10^?7?M. Job's plot indicated the formation of 1:1 complex between the RBCS and Fe³⁺. Moreover, the practical use of the RBCS is demonstrated by its application in the detection of Fe³⁺ in HeLa cells.     

A highly selective pyrene based fluorescent sensor toward Hg detection

A new pyrene-containing fluorescent sensor has been synthesized from 2,3,3-trimethylindolenine. Spectroscopic and photophysical properties of sensor are presented. The large change in fluorescence intensity (I/I₀ = 0.13) at 381 nm and affinity to Hg²⁺ over other cations such as K⁺, Na⁺, Ca²⁺, Mg²⁺, Pb²⁺, and Cu²⁺ make this compound a useful chemosensor for Hg²⁺ detection in hydrophilic media. The sensor (6.0 × 10⁻⁶ M) displays significant fluorescence quenching upon addition of Hg²⁺ in pH 7.4 HEPES buffer without excimer formation. Job’s plot analysis shows the binding stoichiometry to be 2:1 (host/guest).     

Characterization of rhodamine B hydroxylamide as a highly selective and sensitive fluorescence probe for copper(II)

Rhodamine B hydroxylamide (1) is characterized as a highly selective and sensitive fluorescence probe for Cu²⁺. Under the optimized conditions, the probe exhibits specific absorbance-on and fluorescence-on responses to Cu²⁺ only. This remarkable property may allow Cu²⁺ to be detected directly in the presence of the other transition metal ions, and such an application has been demonstrated to human serum. The reaction mechanism is also investigated and proposed as that the hydroxylamide group of 1 binds Cu²⁺, and the subsequent complexation of Cu²⁺ displays a high catalytic activity for the hydrolytic cleavage of the amide bond, causing the release of fluorophore (rhodamine B) and thereby the retrievement of absorbance and fluorescence. The recovered fluorescence intensity is proportional to the concentration of Cu²⁺ in the range 1-20 μM. The detection limit for Cu²⁺ is 33 nM (k = 3). The reaction mechanism described here may be useful for developing excellent spectroscopic probes with cleavable active bonds for other analytes.     

A far-red fluorescent probe for selective G-quadruplex DNA targeting

The development of rapid and simple approaches for detection of G-quadruplex DNA structures has attracted significant attention to disclose their diverse physiological and pathological functions. Thiazole orange (TO) is a common fluorescence probe used for the detection of G-quadruplexes. However, it still suffers from some common problems like non-selective for G-quadruplex and emission in the lower wavelength region of spectrum, thus hampering its further applications. Probes with turn-on fluorescence in the far-red region are highly sought-after due to minimal auto-fluorescence and cellular damage. In this paper, we described a far-red fluorescent probe (L-1) by introducing an amine group into styrylquinolinium scaffold. The experimental results indicated that L-1 exhibited significant fluorescence enhancement when treated with G-quadruplexes but retained weak fluorescence in the presence of duplex DNAs. In addition, this probe also displayed higher binding affinity for parallel G-quadruplexes. The characteristics of L-1 were further investigated with UV–vis spectrophotometry, fluorescence, circular dichroism, KI quenching, FID assay and molecular docking to validate optical photophysical properties, as well as the selectivity, sensitivity and detailed binding mode toward G-quadruplex DNAs.     

Quinoline-based highly selective and sensitive fluorescent probe specific for Cd2+ detection in mixed aqueous media

Quinoline-based fluorescent probe as a recognition unit was designed and synthesized in this study. The probe R1 displayed excellent selectivity and sensitivity for cadmium ions (Cd²⁺) over a wide range of metal ions in acetonitrile-water (MeCN-H₂O) mixed solution. In order to better understand the recognition mechanism between probe and Cd²⁺, the density functional theory calculations were performed. Finally, the colorimetric experiment result was observed and conveniently monitored by the naked eye, and a visual detection limit of 4 × 10^?6 mol L^?1 was achieved. These experimental results indicated the promising potential of the probe to detect Cd²⁺ in biological system. Furthermore, the probe R1 was successfully used for the highly sensitive detection of Cd²⁺ in living cells.     

A coumarin-based fluorescent probe for selective detection of Cu2+ in water

Fluorescent Red GK, a commercially available coumarin-based dye, was developed as a “turn-off” fluorescent probe for detection of Cu²⁺ in aqueous solution. It exhibited high selectivity and sensitivity at room temperature. Upon addition of Cu²⁺, the strong fluorescence of Fluorescent Red GK was severely quenched and its color changed from orange to colorless under illumination with a UV lamp; the color of the solution also changed from pink to colorless. So, it can be used as a specific colorimetric and fluorescent probe for Cu²⁺ with a detection limit as low as 0.0634?μM.     

An ultrasensitive rapid-response fluorescent probe for highly selective detection of HSA

A fluorescent probe HCAB based on twisted intramolecular charge transfer (TICT) mechanism has been designed and synthesized by introducing benzoyl moiety to 4-dimethylamino-2′-hydroxychalcone. HCAB showed excellent selectivity towards human serum albumin (HSA) among different proteins with a remarkable 160-fold fluorescence enhancement and a wider linear range 0–100?mg/L of HSA. Job’s Plot analysis suggested that the formation of HCAB-HSA complex followed a 1:1 stoichiometry. Molecular docking and the displacement assay demonstrated the binding site of HCAB was subdomain IIA and IB of HSA. We also tested HSA levels in human plasma for practical application, the results obtained from HCAB method were similar to those obtained from the standard clinical method.     

荧光探针在氰化物分析中的研究进展

氰化物极易与细胞色素氧化酶键合,抑制电子转移、导致组织缺氧,从而显示较强的毒性。荧光化学传感器作为简易、灵敏且可视化的方法广泛应用于氰化物的检测。本文对荧光探针在氰化物检测中的应用进行综述,概述了氰化物的毒性机制和荧光探针对氰化物的响应机理。同时,本文总结了荧光探针在水体、食品和生物组织中对氰化物的检测及生物成像中的应用,并对荧光探针在结构设计中如何提高生物兼容性和靶向性等进行了展望,以期为光化学探针分子的设计及应用提供理论与研究依据。     

Dual-site fluorescent probe for highly selective and sensitive detection of sulfite and biothiols

A dual-site fluorescent probe that could discriminatively respond to Cys and HSO^3- through two emission channels was reported, and it could further applied in imaging biothiols in living cells.     

A proximity-induced covalent fluorescent probe for selective detection of bromodomain 4

Through proximity-induced conjugation reaction, a peptide-based fluorescent probe was designed and synthesized for selective detection of bromodomain 4.     

Determination of Er3+ using a highly selective and easy-to-synthesize fluorescent probe based on Rhodamine 6G

A inducible fluorescent ligand 2-(2-(2-amino-ethylamino) ethyl)-3′,6′- bis (ethylamino)-2′, 7′-dimethy-lspiro[isoindoline-1,9′-xanthen]-3-one was synthesized and used as a fluorescent probe to detect Er³⁺. Er³⁺ could induce the structural transformation of the fluorescent ligand, resulting in a sharp fluorescence emission in a buffered solution. The fluorescence intensity of the fluorescent ligand was enhanced quantitatively with an increase in the concentration of erbium ion. The detection limit of Er³⁺ was 3.0 × 10^?10 mol L^?1 (50 ng L^?1) under optimized conditions. The method applied for the determination of Er³⁺ in four alloy samples had achieved satisfactory results.     

Toward a highly sensitive and selective indole-rhodamine-based light-up probe for Hg2+ and its application in living cells

We herein designed and synthesized a light-up fluorescent probe L1 for Hg²⁺ species, which is based on indole derivative and Rhodamine fluorophore. The new probe can show a linear response to Hg²⁺ with high sensitivity and selectivity. As the Hg²⁺ concentration changed from 0 to 450 μM, the fluorescence intensity of L1 at 575 nm changed from 50 to 6181 (～120-fold). The detection limit of the probe was 5.0 × 10^?8 M. Besides, we have successfully applied L1 to monitor Hg²⁺ species in living MCF-7 cells by way of fluorescence imaging.     

A new ESIPT-based fluorescent probe for highly selective and sensitive detection of HClO in aqueous solution

A new ESIPT-based fluorescent probe, PHC2, for the detection of hypochlorous acid has been rationally designed and developed. Endowed by the specific reaction between hypochlorous acid and phenyl azo group, PHC2 features high degree of selectivity and sensitivity for HClO with a low detection limit (13.2 nM) under physiological conditions in neutral aqueous solution.