A benzocoumarin-based fluorescent probe for ultra-sensitive and fast detection of endogenous/exogenous hypochlorous acid and its applications.

Hypochlorous acid (HOCl) is widely used in daily production and life because of its green and strongly oxidizing properties. Additionally, as a vital reactive oxygen species (ROS), it is an innate immune system weapon and performs a critical function in many pathophysiology processes. In this paper, a novel water-soluble fluorescent probe, BMH, with excellent performance is designed and synthesized by simple condensation of benzocoumarin and 2-mercaptoethanol. BMH has specific selectivity, excellent sensitivity, ultra-fast response (<3 s), and a wide pH detection range. The fluorescence intensity of BMH has an excellent linear correlation with the concentration of HOCl in the scope of 0-10 µM, and the calculated detection limit (DL) is 2.45 nM. The intramolecular charge transfer (ICT) sensing mechanism of BL has been verified by fluorescence, UV, and MS studies as well as density functional theory (DFT) calculations. Furthermore, BMH can be incorporated into a solid-state visual sensor to detect HOCl conveniently. BMH was applied to detect HOCl-spiked actual water samples and achieved satisfying recovery rates. Also, the low-toxicity BMH can be successfully used to track changes in endogenous/exogenous HOCl in living cells. In short, BL provides a robust and reliable monitoring tool to reveal the biological functions of HOCl and ensure its safe use.

Two similar Schiff-base receptor based quinoline derivate: Highly selective fluorescent probe for Zn(II).

As is known, Zn2+ plays a vital role in a variety of biological processes but excessive exposure of Zn2+ to human beings can cause toxicity, inducing a series of overt poisoning symptoms and neurodegenerative disorders. Thus, we designed and synthesized two quinoline-derived Schiff-bases HL1 and HL2, and investigated the fluorescence emission responses of these two Schiff-bases to various metal ions. A significant enhancement in fluorescence emission band centered at 450 nm was observed in the ethanolic solution of HL1 with addition of Zn2+, while remarkably lower fluorescence emission enhancement was obtained in the case of HL2 in which one methyl group was introduced to the azomethine carbon. In addition, HL1 showed good selectivity and high sensitivity towards Zn2+ in the existence of other various interfering metal ions, and the reversibility and regeneration of HL1 were also perfect for extending its applications in environmental and biological systems. Therefore, HL1 could be identified as a fluorescent probe for sensing Zn2+ environmentally and biologically.

Study on synthesis and fluorescence property of rhodamine-naphthalene conjugate.

In this study, a novel ligand (HL) consisting of 2-methyl quinoline-4-carboxylic acid, rhodamine and naphthalene moiety, was designed and synthesized, it could be developed a ratiometric fluorescent sensor for selective detection of Al3+ via fluorescence resonance energy transfer (FRET) from naphthalimide moiety to rhodamine moiety. The addition of Al3+ trigger the significant fluorescence enhancement of HL at 550 nm at the expense of the fluorescent emission of HL centered at 524 nm.

A Schiff-base receptor based chromone derivate: Highly selective fluorescent and colorimetric probe for Al(III).

Upon excitation of the visible light, probes show colorimetric and fluorescent responses to the specific metal ion, which can be easily detected by the naked eye. Owing to the excitation of the visible light at 423 nm, a novel and simple Schiff-base receptor based chromone derivative called 7-methoxychromone-3-carbaldehyde-(indole-3-formyl) hydrazone (MCIH2) had been investigated as a selective and sensitive probe for Al3+ with colorimetric and fluorescent responses. Upon addition of Al3+ to compound MCIH2 solution, compound MCIH2 could respond to Al3+ with a good selective colorimetric signal, which was easily observed from colorless to yellow-green by the naked eye. Furthermore, a remarkable fluorescence emission enhancement with an "OFF-ON" signal by over 700-fold was triggered, but other various metal ions had no such significant effects on the fluorescence emission. In addition, the detection limit of compound MCIH2 for recognizing Al3+ was evaluated to be as low as 1 × 10-7 M level, which was sufficiently low for sensing Al3+ widely distributed in various environmental and biological systems.

A novel chromone and rhodamine derivative as fluorescent probe for the detection of Zn(II) and Al(III) based on two different mechanisms.

In this study, a novel fluorescent probe, 6­hydroxychromone­3­carbaldehyde­(rhodamine B carbonyl) hydrazine (L), for Zn2+ and Al3+ was designed and synthesized. Initially, this probe L exhibited inferior fluorescence emission peak centered at 488 nm in EtOH/HEPES solution (3/1, 10.0 µM HEPES, pH 7.4) when excited at 421 nm. After the addition of Zn2+, this probe L displayed excellent selectivity towards Zn2+ with obvious fluorescence color change from colorless to yellow, which might be attributed to the formation of a 1:1 ligand-metal complex resulting in the inhibition of photo-induced electron transfer phenomenon. Whereas, the prepared Zn2+ complex of L could be used as a ratiometric fluorescent probe to detect Al3+ on the basis of fluorescence resonance energy transfer mechanism. This ligand-metal complex of Zn2+ (LZn) showed high selectivity towards Al3+ with obvious enhancement in fluorescence emission intensity at 580 nm and remarkable decrease in fluorescence emission intensity at 488 nm, and the fluorescence color also changed from yellow to pink. Furthermore, the detection limit of the probe L, LZn towards Zn2+, Al3+ were 1.25 × 10-7 M and 3.179 × 10-6 M, respectively. Additionally, the complexation properties of L towards Zn2+ and LZn towards Al3+ were studied in detail.

Luminescent magnetic nanoparticles encapsulated in MOFs for highly selective and sensitive detection of ClO-/SCN- and anti-counterfeiting.

It is well-known that ClO- and SCN- can cause adverse effects on the environment and organisms; therefore, development of new strategies for detecting ClO- and SCN-, especially in water, are highly desirable. Here, we present luminous Eu(iii) complex-functionalized Fe3O4 nanoparticles encapsulated into zeolitic imidazolate framework materials (nano-ZIF-8) and successfully employ this nano-MOF as a fluorescence probe for selective and sensitive detection of ClO- and SCN-. The introduction of ClO- into nano-ZIF-8 solution induced a significant decrease in the characteristic fluorescence emission of Eu3+ at 613 nm. However, strong fluorescence emission was again observed when SCN- was successively injected into the prepared nano-ZIF-8-ClO-. Thus, a novel fluorescence system for simultaneous detection of free ClO- and SCN- was established. On the basis of the superior adsorption performance of nano-MOF materials, free residual ClO- and SCN- in water was rapidly, sensitively and selectively detected with a detection limit of 0.133 nM and 0.204 nM, respectively. Moreover, nano-ZIF-8 was successfully used for monitoring the concentration levels of ClO- and SCN- in specimens of tap water and Yellow River water. Furthermore, the reversibility and regeneration of nano-ZIF-8 in sensing ClO- and SCN- is advantageous for applications of nano-ZIF-8 in solid-state sensing and anti-counterfeiting. As far as we know, this is the first time that nano-MOFs have been used as a selective fluorescence probe for ClO-/SCN- detection and anti-counterfeiting.

A highly selective and sensitive fluorescent chemosensor and its application for rapid on-site detection of Al3.

In this paper, a simple naphthalene-based derivative (HL) has been designed and synthesized as a Al3+-selective fluorescent chemosensor based on the PET mechanism. HL exhibited high selectivity and sensitivity towards Al3+ over other commonly coexisting metal ions in ethanol with a detection limit of 2.72nM. The 1:1 binding stoichiometry of the complex (HL-Al3+) was determined from the Job's plot based on fluorescence titrations and the ESI-MS spectrum data. Moreover, the binding site of HL with Al3+ was assured by the 1H NMR titration experiment. The binding constant (Ka) of the complex (HL-Al3+) was calculated to be 5.06×104M-1 according to the Benesi-Hildebrand equation. In addition, the recognizing process of HL towards Al3+ was chemically reversible by adding Na2EDTA. Importantly, HL could directly and rapidly detect aluminum ion through the filter paper without resorting to additional instrumental analysis.

Development of a coumarin-furan conjugate as Zn2+ ratiometric fluorescent probe in ethanol-water system.

In this study, a novel coumarin-derived compound bearing the furan moiety called 7-diethylamino-3-formylcoumarin (2'-furan formyl) hydrazone (1) has been designed, synthesized and evaluated as a Zn2+ ratiometric fluorescent probe in ethanol-water system. This probe 1 showed good selectivity and high sensitivity towards Zn2+ over other metal ions investigated, and a decrease in fluorescence emission intensity at 511nm accompanied by an enhancement in fluorescence emission intensity at 520nm of this probe 1 was observed in the presence of Zn2+ in ethanol-water (V : V=9 : 1) solution, which provided ratiometric fluorescence detection of Zn2+. Additionally, the ratiometric fluorescence response of 1 to Zn2+ was nearly completed within 0.5min, which suggested that this probe 1 could be utilized for sensing and monitoring Zn2+ in environmental and biological systems for real-time detection.

A Novel Chromone Schiff-Base Fluorescent Chemosensor for Cd(II) Based on C=N Isomerization.

A new chromone Schiff-base fluorescent probe 7'-methoxychromone-3'-methylidene-1,2,4-triazole-3-imine (L) was designed and synthesized for selective recognition Cd(2+). With the fluorescence titration and the ESI-MS data, we reach the conclusion that the binding mode of the ligand-metal (L-Cd (2+) ) complex is 1:1. The sensor showed a strong fluorescence enhancement in ethanol system of Cd(2+) (excitation 409 nm and emission 462 nm) and the sensing mechanism based on the fact that C=N isomerization can be used to explain this phenomenon.

Interface coassembly of mesoporous MoS2 based-frameworks for enhanced near-infrared light driven photocatalysis.

The three-dimensional porous Fe3O4@Cu2-xS-MoS2 framework is reported for the first time. The as-prepared 3D framework exhibits good structural stability, high surface area, enhanced adsorption capacity to substrates, and strong absorption in the NIR range. As a result, such hybrid frameworks exhibit excellent NIR-light photocatalytic activity and stable cycling for the direct arylation of heteroaromatics at room temperature.

A Chromone-Derived Schiff-Base Ligand as Al(3+) "Turn on" Fluorescent Sensor: Synthesis and Spectroscopic Properties.

In this study, a novel chromone-derived Schiff-base ligand called 6-Hydroxy-3-formylchromone (2'-furan formyl) hydrazone (HCFH) has been designed and synthesized as a "turn on" fluorescent sensor for Al(3+). This sensor HCFH showed high selectivity and sensitivity towards Al(3+) over other metal ions investigated, and most metal ions had nearly no influences on the fluorescence response of HCFH to Al(3+). Additionally, the significant enhancement by about 171-fold in fluorescence emission intensity at 502 nm was observed in the presence of Al(3+) in ethanol, and it was due to the chelation-enhanced fluorescence (CHEF) effect upon complexation of HCFH with Al(3+) which inhibited the photoinduced electron transfer (PET) phenomenon from the Schiff-base nitrogen atom to chromone group. Moreover, this sensor formed a 1 : 1 complex with Al(3+) and the fluorescence response of HCFH to Al(3+) was nearly completed within 1 min. Thus, this sensor HCFH could be used to detect and recognize Al(3+) for real-time detection.

Two Schiff-base fluorescent sensors for selective sensing of aluminum (III): Experimental and computational studies.

Two Schiff-base fluorescent sensors have been synthesized, which both can act as fluorescent probes for Al(3+), upon addition of Al(3+), they exhibit a large fluorescence enhancement which might be attributed to the formation of 1:1 ligand-Al complexes which inhibit photoinduced electron transfer (PET) progress, and that the proposed binding modes of the sensors and Al(3+) are identified by theoretical calculations.

Design of a novel coumarin-based multifunctional fluorescent probe for Zn²âº/Cu²âº/S²â» in aqueous solution.

A multifunctional fluorescent chemosensor 7-(diethylamino)-coumarin-3-carbaldehyde-(2'-methylquinoline-4'-formyl) hydrazone (HL) has been designed and synthesized. The sensor shows significant fluorescence enhancement in the presence of Zn(2+), which might be mainly due to the restricted -CN isomerization process. In contrast, the fluorescence of the sensor is quenched by Cu(2+) attributed to the inherent paramagnetic species. More interestingly, the 'in situ' prepared L-Cu exhibits a selective response to S(2-) based on reversible formation-separation of complex L-Cu and CuS.

Triple-Emitting Dumbbell Fluorescent Nanoprobe for Multicolor Detection and Imaging Applications.

The combination of different fluorescent species into one nanostructure to develop fluorescent nanoparticles with multiple emission signatures by a single wavelength excitation has become a very popular research area in the field of multiplex bioanalysis, diagnostics, and multicolor imaging. However, these novel hybrids must be elaborately designed to ensure that the unique properties of each component are conveyed, i.e., fluorescent species and nanoparticles, and are maximized without serious interactions with each other. Herein, a first triple-fluorescence dumbbell nanoprobe with large Stokes shift based on incorporating fluorescein isothiocyanate (FITC) and lanthanide complexes onto Au-Fe3O4 NPs was synthesized. This hybrid displays well-resolved triple fluorescence emission, with FITC at 515 nm, Tb(III) complex at 545 nm, and Eu(III) complex at 616 nm under a single-excitation wavelength and is used for highly selective and sensitive colorimetric detection of Cu(2+) with a detection limit of 30 nM. Under different Cu(2+) concentrations, this hybrid exhibited distinguishable multiple colors under UV light, and the color could change in the presence of different concentrations of Cu(2+). This sensor for ratio/multianalyte microscopic imaging of Cu(2+) in HeLa cells and BHK cells was also demonstrated. Target molecules, such as folic acid, can be covalently attached to the fluorescent nanoparticle surface to serve as an effective probe for simultaneous multicolor imaging folate receptor-overexpressing HeLa cell lines in vitro.

A highly selective fluorescent probe for Al(3+) based on quinoline derivative.

A novel Schiff base fluorescent probe, 1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldehyde (2'-methylquinoline-4'-formyl) hydrazone (PMHCH), for selective detection of Al(3+) has been designed and synthesized. Upon addition of various metal ions, the receptor only shows 286-fold enhancement of fluorescence intensity which might be attributed to a 1:1 stoichiometry between PMHCH and Al(3+) and the photo-induced electron transfer progress in the present of Al(3+) at 505n m. More importantly, the detection limit of PMHCH for Al(3+) could reach at 10(-7) M level.

Highly efficient degradation of organic dyes by palladium nanoparticles decorated on 2D magnetic reduced graphene oxide nanosheets.

The application of nanohybrids in water treatment by the catalytic degradation of various pollutants has attracted much attention from researchers. Here, the Pd/Fe3O4-PEI-RGO nanohybrids (1d) with high shape selectivity and high specific surface area have been synthesized by the dispersion of Pd NPs and Fe3O4 NPs on PEI modified graphene oxide sheets. These nanohybrids show superior catalytic activity toward methylene blue with a high degradation efficiency above 99% in the presence of NaBH4 in aqueous solution, which is attributed to the effects of the Pd NPs supported on reduced graphene oxide nanosheets. Meanwhile, the 1d catalyst can be easily separated from the reaction mixture by applying an external magnetic field. The catalyst was recycled nine times without showing any significant loss in its activity. Such features enable this catalyst for promising application in catalysis, environment, and new energy fields.

A strongly coupled Au/Fe3O4/GO hybrid material with enhanced nanozyme activity for highly sensitive colorimetric detection, and rapid and efficient removal of Hg(2+) in aqueous solutions.

We have developed an efficient strategy for synthesizing a strongly coupled Au/Fe3O4/GO hybrid material to improve the catalytic activity, stability, and separation capability of Au nanoparticles (NPs) and Hg(2+). The hybrid material can be synthesized by the direct anchoring of Au and Fe3O4 NPs on the functional groups of GO. This approach affords strong chemical attachments between the NPs and GO, allowing this hybrid material to ultrasensitively detect Hg(2+) in aqueous solutions with a detection limit as low as 0.15 nM. In addition, the deposition of Hg(0) on the surface of Au/Fe3O4/GO could be quickly (within 30 min) and efficiently (>99% elimination efficiency) removed by the simple application of an external magnetic field and then Au/Fe3O4/GO could be subsequently reused at least 15 times, with the elimination efficiency remaining high (>96%).

ß-Hydroxy-α-naphthaldehyde [2-(quinolin-8'-yloxy) acetyl] hydrazone as an efficient fluorescent chemosensor for Mg2+.

An efficient fluorescent sensor based on ß-hydroxy-α-naphthaldehyde [2-(quinolin-8'-yloxy) acetyl] hydrazone (HL) for Mg2+ has been designed and synthesized. The receptor showed "off-on" fluorescent responses toward Mg2+ in acetonitrile. The reasons for this phenomenon is that the addition of Mg2+ to the solution of HL induce the formation of a 1:1 ligand-metal complex which inhibit excited-state intramolecular proton transfer (ESIPT).

Europium(III) complex-functionalized magnetic nanoparticle as a chemosensor for ultrasensitive detection and removal of copper(II) from aqueous solution.

Ultrasensitive, accurate detection and separation of heavy metal ions is very important in environmental monitoring and biological detection. In this paper, a highly sensitive and specific detection method for Cu(2+) based on the fluorescence quenching of a europium(III) hybrid magnetic nanoprobe is presented. This nanoprobe can detect Cu(2+) over a wide pH range (5.0-10.0) with a detection limit as low as 0.1 nM and it can be used for detecting Cu(2+) in living cells. After the magnetic separation, the Cu(2+) concentration decreased to 1.18 ppm, which is less than the US EPA drinking water standard (1.3 ppm), and more than 70% Cu(2+) could be removed when the amount of nanocomposite 1 reached 1 mg.

Palladium nanoparticles bonded to two-dimensional iron oxide graphene nanosheets: a synergistic and highly reusable catalyst for the Tsuji-Trost reaction in water and air.

Low cost, high activity and selectivity, convenient separation, and increased reusability are the main requirements for noble-metal-nanocatalyst-catalyzed reactions. Despite tremendous efforts, developing noble-metal nanocatalysts to meet the above requirements remains a significant challenge. Here we present a general strategy for the preparation of strongly coupled Fe(3)O(4) and palladium nanoparticles (PdNPs) to graphene sheets by employing polyethyleneimine as the coupling linker. Transmission electron microscopic images show that Pd and Fe(3)O(4) nanoparticles are highly dispersed on the graphene surface, and the mean particle size of Pd is around 3 nm. This nanocatalyst exhibits synergistic catalysis by Pd nanoparticles supported on reduced graphene oxide (rGO) and a tertiary amine of polyethyleneimine (Pd/Fe(3)O(4)/PEI/rGO) for the Tsuji-Trost reaction in water and air. For example, the reaction of ethyl acetoacetate with allyl ethyl carbonate afforded the allylated product in more than 99 % isolated yield, and the turnover frequency reached 2200 h(-1). The yield of allylated products was 66 % for Pd/rGO without polyethyleneimine. The catalyst could be readily recycled by a magnet and reused more than 30 times without appreciable loss of activity. In addition, only about 7.5 % of Pd species leached off after 20 cycles, thus rendering this catalyst safer for the environment.