Preparation, characterization and evaluation of water-soluble l-cysteine-capped-CdS nanoparticles as fluorescence probe for detection of Hg(II) in aqueous solution

Water-soluble l-cysteine-capped-CdS nanoparticles were prepared in aqueous solution at room temperature through a straightforward one-pot process by using safe and low-cost inorganic salts as precursors, and characterized by transmission electron microscopy, X-ray diffraction spectrometry, Fourier transform infrared spectrometry, spectrofluorometry and ultraviolet-visible spectrometry. The prepared l-cysteine-capped-CdS nanoparticles were evaluated as fluorescence probe for Hg(II) detection. The fluorescence quenching of the l-cysteine-capped-CdS nanoparticles depended on the concentration and pH of Hg(II) solution. Maximum fluorescence quenching was observed at pH 7.4 with the excitation and emission wavelengths of 360 nm and 495 nm, respectively. Quenching of its fluorescence due to Hg(II) at the 20 nmol l⁻¹level was unaffected by the presence of 5 × 10⁶-fold excesses of Na(I) and K(I), 5 × 10⁵-fold excesses of Mg(II), 5 × 10⁴-fold excesses of Ca(II), 500-fold excesses of Al(III), 91-fold excesses of Mn(II), 23.5-fold excesses of Pb(II), 25-fold excesses of Fe(III), 25-fold excesses of Ag(I), 8.5-fold excesses of Ni(II) and 5-fold excesses of Cu(II). Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 16 nmol l⁻¹ to 112 nmol l⁻¹. The limit of detection for Hg(II) was 2.4 nmol l⁻¹. The developed method was applied to the detection of trace Hg(II) in aqueous solutions.     

基于喹啉衍生物的汞离子选择性荧光传感分子的合成与应用

合成一种新型开-关(ON-OFF)型汞离子荧光传感分子triquinolin-8-yl benzene-1,3,5-tri-carboxylate（TQBTC）。 采用FT-IR、元素分析、¹H NMR测试技术对其结构进行了表征。 在对其荧光性质的研究中发现,TQBTC的乙腈-水溶液在253.0 nm波长辐射激发下于616.0 nm处发射强荧光,且对汞离子络合有较好的选择性。 TQBTC与Hg(Ⅱ)可形成1∶3型络合物,同时使荧光线性猝灭,TQBTC可作为Hg(Ⅱ)的荧光传感分子。 建立了一种测定Hg(Ⅱ)的灵敏分析方法。 Hg(Ⅱ)浓度在0~30 μmol/L的范围内与TQBTC的荧光猝灭呈线性关系,方法检出限为0.838 μmol/L。 方法应用于实际样品中Hg(Ⅱ)的检测,获得满意结果。     

A fluorescent chemical sensor for Hg(II) based on a corrole derivative in a PVC matrix

A fluorescent chemical sensor for Hg(II) using 5,10,15-tris(pentafluorophenyl)corrole (H₃(tpfc)) as fluorophore is described in this paper. The response of the sensor is based on the fluorescence quenching of H₃(tpfc) by coordination with Hg(II). H₃(tpfc) based sensor shows a linear response towards Hg(II) in the concentration range from 1.2 × 10⁻⁷ to 1.0 × 10⁻⁴ M, with a working pH range from 5.0 to 8.0. The response time for Hg(II) concentration ≤1.0 × 10⁻⁵ M is less than 5 min. The sensor shows good selectivity for Hg(II) over alkali, and alkaline earth, and most of transition metal cations. The effect of the composition of the sensor membrane has been studied and the experimental conditions optimized. The corrole based sensor membrane can be easily regenerated just by washing with blank buffer solution after each measurement. The sensor has been used for determination of Hg(II) in water samples with satisfactory results.     

A colorimetric and fluorescent turn-on chemosensor for Zn based on an azobenzene-containing compound

This paper presents a new colorimetric reversible fluorescent turn-on chemosensor molecule for zinc ion based on an azobenzene derivative. The basal fluorescence intensity of the chemosensor molecule is little affected under physiological pH 5-9, whilst the excitation (507 nm) and emission (610 nm) wavelength of the molecular probe for zinc ion is in the visible range.     

A functionalized gold nanoparticles and Rhodamine 6G based fluorescent sensor for high sensitive and selective detection of mercury(II) in environmental water samples

A gold-nanoparticles (Au NPs)-Rhodamine 6G (Rh6G) based fluorescent sensor for detecting Hg (II) in aqueous solution has been developed. Water-soluble and monodisperse gold nanoparticles (Au NPs) has been prepared facilely and further modified with thioglycolic acid (TGA). Free Rh6G dye was strongly fluorescent in bulk solution. The sensor system composing of Rh6G and Au NPs fluoresce weakly as result of fluorescence resonance energy transfer (FRET) and collision. The fluorescence of Rh6G and Au NPs based sensor was gradually recovered due to Rh6G units departed from the surface of functionalized Au NPs in the presence of Hg(II). Based on the modulation of fluorescence quenching efficiency of Rh6G-Au NPs by Hg(II) at pH 9.0 of teraborate buffer solution, a simple, rapid, reliable and specific turn-on fluorescent assay for Hg(II) was proposed. Under the optimum conditions, the fluorescence intensity of sensor is proportional to the concentration of Hg(II). The calibration graphs are linear over the range of 5.0 × 10⁻¹⁰ to 3.55 × 10⁻⁸ mol L⁻¹, and the corresponding limit of detection (LOD) is low as 6.0 × 10⁻¹¹ mol L⁻¹. The relative standard deviation of 10 replicate measurements is 1.5% for 2.0 × 10⁻⁹ mol L⁻¹ Hg(II). In comparison with conventional fluorimetric methods for detection of mercury ion, the present nanosensor endowed with higher sensitivity and selectivity for Hg(II) in aqueous solution. Mercury(II) of real environmental water samples was determined by our proposed method with satisfactory results that were obtained by atomic absorption spectroscopy (AAS).     

Specific mercury(II) adsorption by thymine-based sorbent

A new kind of polymer sorbent based on the specific interaction of Hg(II) with nucleic acid base, thymine, is described for the selective adsorption of Hg(II) from aqueous solution. Two types of sorbents immobilized with thymine were prepared by one-step swelling and polymerization and graft polymerization, respectively. The maximum static adsorption capacity of the new polymer sorbents for Hg(II) is proportional to the density of thymine on their surface, up to 200 mg/g. Moreover, the new kind polymer sorbent shows excellent selectivity for Hg(II) over other interfering ions, such as Cu(II), Cd(II), Zn(II), Co(II), Ca(II) and Mg(II), exhibits very fast kinetics for Hg(II) adsorption from aqueous solution, and can be easily regenerated by 1.0 M HCl. It also has been successfully used for the selective adsorption of spiked Hg(II) from real tap water samples. This new thymine polymer sorbent holds a great promise in laboratory and industrial applications such as separation, on-line enrichment, solid-phase extraction, and removal of Hg(II) from pharmaceutical, food and environmental samples.     

A near IR di-styryl BODIPY-based ratiometric fluorescent chemosensor for Hg(II)

A novel BODIPY-based near-IR emitting probe as a selective and sensitive fluorophore for Hg(II) is synthesized. This versatile BODIPY fluorophore is functionalized for long wavelength emission at the 3 and 5 positions via a condensation reaction in which two dithiodioxomonoaza-based crown-containing phenyl units are conjugated to the BODIPY core as a chelating unit. This designed fluorophore, employing an ICT sensor can be used effectively to detect Hg(II) cations by way of a hypsochromic shift (∼90 nm) in both the absorption and emission spectra.     

Selective sensing of Zn(II) ion by a simple anthracene-based tripodal chemosensor

A new and an easy-to-make simple tripodal shaped chemosensor 1, comprising an anthracene moiety as a fluorophore and amide, alcohol functionalities as ligating groups has been designed and synthesized for Zn(II). In CH₃CN containing 0.1% DMSO, upon excitation at 370 nm, the chemosensor 1 exhibited an emission at 412 nm, which increased to a large extent upon complexation of Zn(II). Among the other metal ions examined in the study, Cd²⁺ moderately perturbed the emission of 1 under similar conditions.     

Solid-phase extraction and preconcentration of cadmium(II) in aqueous solution with Cd(II)-imprinted resin (poly-Cd(II)-DAAB-VP) packed columns

A novel chelating resin (poly-Cd(II)-DAAB-VP) was prepared by metal ion imprinted polymer (MIIP) technique. The resin was obtained by one pot reaction of Cd(II)-diazoaminobenzene-vinylpyridine with cross-linker ethyleneglycoldimethacrylate (EGDMA). Comparing with non-imprinted resin, the poly-Cd(II)-DAAB-VP has higher adsorption capacity and selectivity for Cd(II). The distribution ratio (D) values for the Cd(II)-imprinted resin show increase for Cd(II) with respect to both D values of Zn(II), Cu(II), Hg(II) and non-imprinted resin. The relatively selective factor (α_r) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II), are 51.2, 45.6, and 85.4, which are greater than 1. poly-Cd(II)-DAAB-VP can be used at least 20 times without considerable loss of adsorption capacity. Based on poly-Cd(II)-DAAB-VP packed columns, a highly selective solid-phase extraction (SPE) and preconcentration method for Cd(II) from aqueous solution was developed. The MIIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 30 μg l⁻¹. The detection limit and quantification limit were 0.093 and 0.21 μg l⁻¹ (3σ) for flame atomic absorption spectrometry (FAAS). The relative standard deviation of the eleven replicate determinations was 3.7% for the determination of 10 μg of Cd(II) in 100 ml water sample. Determination of Cd(II) in certified river sediment sample (GBW 08301) demonstrated that the interfering matrix had been almost removed during preconcentration. The column was good enough for Cd(II) determination in matrixes containing components with similar chemical property such as Cu(II), Zn(II) and Hg(II).     

Aminoquinoline based highly sensitive fluorescent sensor for lead(II) and aluminum(III) and its application in live cell imaging

We have synthesized a new probe 5-((anthracen-9-ylmethylene) amino)quinolin-10-ol (ANQ) based on anthracene platform. The probe was tested for its sensing behavior toward heavy metal ions Hg²⁺, Pb²⁺, light metal Al³⁺ ion, alkali, alkaline earth, and transition metal ions by UV–visible and fluorescent techniques in ACN/H₂O mixture buffered with HEPES (pH 7.4). It shows high selectivity toward sensing Pb²⁺/Al³⁺ metal ions. Importantly, 10-fold and 5- fold fluorescence enhancement at 429 nm was observed for probe upon complexation with Pb²⁺ and Al³⁺ ions, respectively. This fluorescence enhancement is attributable to the prevention of photoinduced electron transfer. The photonic studies indicate that the probe can be adopted as a sensitive fluorescent chemosensor for Pb²⁺ and Al³⁺ ions.     

Fluorometric determination of cadmium(II) and mercury(II) using nanoclusters consisting of a gold-nickel alloy

A one-pot route has been developed for the preparation of bovine serum albumin-templated nickel-doped bimetallic gold-nickel nanoclusters (BSA-Au-Ni NCs) at a 10:1 M ratio of the precursor salts in a BSA matrix under alkaline conditions. The metal ions are reduced to the metal alloys by BSA. The resulting NCs display strong fluorescence and dual emission with peaks at 405 and 640 nm, respectively, under excitation at 340 nm. Fluorescence is strongly enhanced on addition of Cd(II) ions, but quenched on addition of Hg(II) ions. The findings have been exploited to design a fluorometric method for the separate determination of Cd(II) and Hg(II), respectively. The optimized analytical nanosystem displays relatively good dynamics between enhancement and quenching. Cd(II) and Hg(II) can be quantified in the 0 to 200 and 0 nM to 24 μM, respectively. The limits of detection are ~1.8 nM in both cases, which indicates the highest sensitivity to Cd(II) and Hg(II) ions for a fluorescent probe. This new kind of nanocrystal probe is hardly interfered by a range of commonly encountered metal ions. Its advantages were demonstrated by determining Cd(II) and Hg(II) ions in spiked serum samples.

Dually emitting nanoclusters composed of gold-nickel alloys are shown to act as very sensitive fluorescent probes for the detection of Cd(II) and Hg(II) ions.

     

Developing a genetically encoded green fluorescent protein mutant for sensitive light-up fluorescent sensing and cellular imaging of Hg(II)

Hg(II) is well-known for quenching fluorescence in a distance dependent manner. Nevertheless, when we exposed the fluorophore of a green fluorescent protein (GFP) toward Hg(II), through H148C mutation, the GFP fluorescence could be “lighted up” by Hg(II) down to sub-nM level. The detection linear range is 0.5–3.0 nM for protein solutions at 8.0 nM. The GFPH148C protein displayed a promising selectivity toward Hg(II) and also the cellular imaging capacity. Spectra measurements suggested that the ground-state redistribution of protein contributed to the fluorescence enhancement, which was found not limited to Hg(II), and thus presented an opening for building a pool of GFP-based chemosensors toward other heavy metal ions.     

On-line determination of mercury(II) by membrane separation flow injection analysis

A rapid and inexpensive gas-diffusion (GD) flow injection method for the on-line determination of Hg(II) in aqueous samples is described. The analytical procedure involves the injection of a Hg(II) sample into a 1.5 M H₂SO₄ carrier stream which is merged with a reagent stream containing 0.6% SnCl₂ and 1.5 M H₂SO₄. Under these conditions Hg(II) is reduced to metallic mercury which partially evaporates through a Teflon membrane into an acceptor stream containing 1.75×10⁻⁴ M KMnO₄ in 0.3 M H₂SO₄. The decrease in the absorbance of the acceptor stream at 528 nm corresponding to the absorption maximum of the permanganate anion can be related to the original concentration of Hg(II) in the sample. The method is characterized by a detection limit of 4 μg l⁻¹ and a sampling frequency of 8 h⁻¹. The flow system was successfully applied to the analysis of river samples spiked with Hg(II).     

A selective, sensitive probe for mercury(II) ions based on oxazine-thione

A selective, sensitive probe for Hg(II) ions, 7-(diethylamino)-3-methyl-2H-benzo[b][1,4] oxazine-2-thione (1), is developed. Compound 1 behaves as a ratiometric probe, exhibiting a large blue shift of 100 nm in its absorption spectra upon exposure to Hg(II) ions. The dramatic color change of the solution made ‘naked-eye’ detection of Hg(II) ions possible. Emission spectra of 1 displayed a selective enhancement in intensity in the presence of Hg(II) ions. ESI⁺-MS analysis indicated that Hg²⁺-induced desulfurization caused the large absorption response.     

3-(Aryl)-2-sulfanylpropenoates of mercury(II) and phenylmercury(II)

Compounds [HQ]₂[Hg(L)₂] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (¹H, ¹³C) spectroscopy. The crystal structures of the [HQ]₂[Hg(L)₂] compounds show the presence of diisopropylammonium cations and [Hg(L)₂]²⁻ anions. In each anion the Hg atom is in an HgO₂S₂ environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]⁻ anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L²⁻ determined by X-ray diffractometry in the solid remains in solution.     

Hg(II) immobilized MWCNT graphite electrode for the anodic stripping voltammetric determination of lead and cadmium

The preparation of Hg(II)-modified multi walled carbon nanotube (MWCNT) by reaction of oxidized MWCNT with aqueous HgCl₂ was carried out. The Hg(II)-modified multi walled carbon nanotube (Hg(II)/MWCNT) dispersed in Nafion solution was used to coat the polished graphite electrode surface. The Hg(II)/MWCNT modified graphite electrode was held at a cathodic potential (−1.0 V) to reduce the coordinated Hg(II) to Hg forming nanodroplets of Hg. The modified electrode was characterized by FESEM/EDAX which provided useful insights on the morphology of the electrode. The SEM images showed droplets of Hg in the size of around 260 nm uniformly distributed on the MWCNT. Differential pulse anodic stripping voltammetry (DPASV) and electrochemical impedance spectroscopy were used to study the Hg(II) binding with MWCNT. Differential pulse anodic stripping voltammetry of ppb levels of cadmium and lead using the modified electrode yielded well-defined peaks with low background current under a short deposition time. Detection limit of 0.94 and 1.8 ng L⁻¹ were obtained following a 3 min deposition for Pb(II) and Cd(II), respectively. Various experimental parameters were characterized and optimized. High reproducibility was observed from the RSD values for 20 repetitive measurements of Pb(II) and Cd(II) (1.7 and 1.9%, respectively). The determination of Pb(II) and Cd(II) in tap water and Pb(II) in human hair samples was carried out. The above method of fabrication of Hg(II)/MWCNT modified graphite electrode clearly suggests a safe route for preparing Hg immobilized electrode for stripping analysis.     

Unfolding with mercury: anthracene-oxyquinoline dyad as a fluorescent indicator for Hg(II)

An anthracene-oxyquinoline dyad (HQ-AN) is synthesized which acts as a selective fluorescent reporter for Hg(II) with a detection limit of 3.2 × 10⁻⁶ M in acetonitrile-water system. The phenomenon of unfolding of HQ-AN from its initial folded conformation in acetonitrile-water system, selectively in the presence of Hg(II) is indicated from spectrofluorometric studies. The sensing event is monitored by the marked change in fluorescence emission occurring due to quenching of the excimer and retaining of the monomer emission of the two anthracene units in HQ-AN.     

A colormetric and fluorescent chemosensor for adenosine-5′-triphosphate based on rhodamine derivative

A rhodamine spirolactam derivative (1) was developed as a colormetric and fluorescent chemosensor for adenosine-5′-triphosphate (ATP) via hydrogen bonds interaction. As far as we know, this is the first case to explore ATP-induced ring-opening of spirolactam in rhodamine derivatives. It exhibited a highly sensitive “turn-on” fluorescent response toward ATP with a 47-fold fluorescence intensity enhancement under 20 equiv. of ATP added. The chemosensor can be applied to the quantification of ATP with a linear range covering from 1.0 × 10⁻⁷ to 2.0 × 10⁻⁴ M and a detection limit of 2.5 × 10⁻⁸ M. The experiment results show that the response behavior of 1 toward ATP is pH independent in medium condition (pH 6.0–8.0). Most importantly, the novel chemosensor has well solved the problem of serious interferences from other nucleoside polyphosphates such as ADP and AMP generally met by previously reported typical fluorescent chemosensors for ATP. Moreover, the response of the chemosensor toward ATP is fast (response time less than 3 min). In addition, the chemosensor can be used for the fluorescence assay for protein kinase activity with satisfactory results. The chemosensor for ATP based on hydrogen bonds interaction provided a novel strategy for the design of colormetric and ratiometric fluorescent probes for other target anions with high sensitivity and selectivity.     

Spectrophotometric flow-injection analysis of mercury(II) in pharmaceuticals with p-nitrobenzoxosulfamate

A new, simple and rapid spectrophotometric FI method for the accurate and precise determination of Hg(II) in pharmaceutical preparations has been developed. The method is based on the measuring the decrease of absorbance intensity of p-nitrobenzoxosulfamate (NBS) due to the complexation with Hg(II). The absorption peak of the NBS, which is decreased linearly by addition of Hg(II), occurs at 430 nm in 2×10⁻⁴ mol l⁻¹ HNO₃ as a carrier solution. Optimization of chemical and FI variables has been made. A micro column consisting of several packing materials applied instead of reaction coil was also investigated. A background level of Fe(III) maintained in reagent carrier solution with NBS was found useful for sensitivity and selectivity. Under the optimized conditions, the sampling rate was over 100 h⁻¹, the calibration curve obtained were linear over the range 1-10 μg ml⁻¹, the detection limit was lower than 0.2 μg ml⁻¹ for a 20 μl injection volume, and the precision [S_r=1% at 2 μg ml⁻¹ Hg(II) (n=10)] was found quite satisfactory. Application of the method to the analysis of Hg(II) in pharmaceutical preparations resulted a good agreement between the expected and found values.     

Colorimetric and fluorescent chemosensor for citrate based on a rhodamine and Pb complex in aqueous solution

In this paper we unveil a novel rhodamine compound based fluorescent chemosensor (1-Pb²⁺) for colormetric and fluorescent detection of citrate in aqueous solution. This is the first fluorescent chemosensor for citrate based on rhodamine compound. The comparison of this method with some other fluorescence methods for citrate indicates that the method can detect citrate in aqueous solution by both color changes and fluorescent changes with long emission wavelength. In the new developed sensing system, 1-Pb²⁺ is fluorescent due to Pb²⁺-induced fluorescence enhancement of 1. However, the addition of citrate may release 1 into the solution with quenching of fluorescence. The chemosensor can be applied to the quantification of citrate with a linear range covering from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁵ M and a detection limit of 2.5 × 10⁻⁸ M. The experiment results show that the response behavior of 1-Pb²⁺ towards citrate is pH independent in medium condition (pH 6.0–8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for citrate in the presence of other anions (even those that exist in high concentration), which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward citrate is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of citrate in urine samples with satisfactory results.