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1.
A novel ratiometric fluorescence sensing system for the ultrasensitive detection of Hg2+ was developed. It used aminofunctionalized silicon nanoparticles and rhodamine B, which exhibit two distinct fluorescence emission peaks at 449 and 581?nm, respectively, under a single excitation wavelength (350?nm). The fluorescence of the amino-functionalized silicon nanoparticles was selectively quenched by Hg2+, while that of rhodamine B was insensitive to Hg2+. The ratio of fluorescence intensities at 449–581?nm linearly decreased with increasing concentrations of Hg2+ from 0.005–0.1 and 0.1–7?µM within 0.5?min, and a detection limit as low as 3.3?nM was achieved. Moreover, the ratiometric fluorescence sensing system exhibited good selectivity toward Hg2+ over other metal ions with relatively low background interference, even in a complex matrix such as lake water. Most importantly, the practical use of this sensing system for Hg2+ detection in real water samples was also demonstrated.  相似文献   

2.
Yulong Gao  Tao Wang  Fengyu Liu 《中国化学》2016,34(12):1297-1303
The electrochemiluminescence (ECL) of the Ru(phen)32+/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg2+ in tap water. The ECL intensity of Ru(phen)32+ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)32+/T system rapidly decreased with the addition of Hg2+ because of the formation of a T‐Hg2+‐T complex. A linear response (R2=0.9914) was obtained over a Hg2+ concentration range of 1.0×10?9 mol/L to 1.0×10?5 mol/L with a detection limit of 3.4×10?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg2+ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg2+.  相似文献   

3.
Polycationic Hg–As Frameworks with Trapped Anions. II Synthesis, Crystal Structure, and Magnetism of (Hg6As4)[MoCl6]Cl, (Hg6As4)[TiCl6]Cl, and (Hg6As4)[TiBr6]Br (Hg6As4)[MoCl6]Cl is obtained by reaction of Hg2Cl2, Hg, As, and MoCl4 in closed, evacuated glass ampoules in a temperature gradient 450 → 400 °C in form of dark red cubelike crystals. (Hg6As4)[TiCl6]Cl and (Hg6As4)[TiBr6]Br are also formed in closed, evacuated ampoules from Hg2X2 (X = Cl, Br), Hg, As, and Ti metal at 275 °C and 245 °C in form of dark green and black crystals, respectively. All three compounds are air and light sensitive. They crystallize isotypically (cubic, Pa 3, a = 1207.8(4) pm for (Hg6As4)[MoCl6]Cl, a = 1209.4(3) pm for (Hg6As4)[TiCl6]Cl, a = 1230.9(3) pm for (Hg6As4)[TiBr6]Br, Z = 4). The structures consist of a three‐dimensionally connected Hg–As framework which is made up of As2 groups (As–As distance averaged 242 pm) each connected via six Hg atoms to six neighbouring As2 groups. There are two cavities of different size in the polycationic framework. The bigger cavity is filled with [MoCl6]3–, [TiCl6]3–, and [TiBr6]3– ions of nearly ideal octahedral shape, the smaller cavity with discrete halide ions. The magnetic properties of the two Ti containing compounds are in accordance with a d1 paramagnetism. The temperature dependence and the magnitude of the magnetic moment can be interpreted with consideration of the spin‐orbit coupling. The so far known representatives of this structure type can be characterised by the ionic formula (Hg6Y4)4+[MX6]3–X (Y = As, Sb; M = Sb3+, Bi3+, Mo3+, Ti3+; X = Cl, Br).  相似文献   

4.
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.  相似文献   

5.
Mercury is one of the major toxic pollutants and has many adverse effects on human health. The main mercury species in the environment or in living organisms are inorganic mercuric ion (Hg2+) and organic methylmercury (CH3Hg+). Detection of the two mercury ions is a particularly active topic in the molecular sensing field during the past decade. However, efficient sensors that can sensitively detect and discriminate the two species are rare. In this work, we adopt the concept of restriction of intramolecular rotations which is the basis of aggregation induced emission, and design a molecular probe with pyridyl group as the chelating unit and 1,8-naphthalimide as the fluorescent unit for the detection of both Hg2+ and CH3Hg+. When the probe is free in solution, it exhibits weak fluorescence because free intramolecular rotations of the 1,8-naphthalimide moieties non-radiatively annihilate its excited state. However, upon coordination with Hg2+ or CH3Hg+, the rotation of 1,8-naphthalimide moieties would be restricted due to the chelation between 1,8-naphthalimide and Hg2+ or CH3Hg+, leading to significantly enhanced fluorescent emission. The response induced by Hg2+ is much stronger than CH3Hg+; but for specific detection of CH3Hg+, we introduced a T-rich DNA fragment which could completely mask Hg2+ in solution. Furthermore, we have employed the sensor for confocal imaging of Hg2+ and CH3Hg+in immobilized cells. We expect the probe design tactics can be generally useful for sensing many other analytes.  相似文献   

6.
Lin YW  Liu CW  Chang HT 《Talanta》2011,84(2):324-329
We have developed a fluorescence technique for the detection of Hg2+ and Pb2+ ions using polythymine (T33)/benzothiazolium-4-quinolinium dimer derivative (TOTO-3) and polyguanine (G33)/terbium ions (Tb3+) conjugates, respectively. Hg2+ ions induce T33 to form folded structures, leading to increased fluorescence of the T33/TOTO-3 conjugates. Because Pb2+ ions compete with Tb3+ ions to form complexes with G33, the extent of formation of the G33-Tb3+ complexes decreases upon increasing the Pb2+ concentration, leading to decreased fluorescence at 545 nm when excited at 290 nm. To minimize interference from Hg2+ ions during the detection of Pb2+ ions, we conducted two-step fluorescence measurements; prior to addition of the G33/Tb3+ probe, we recorded the fluorescence of a mixture of the T33/TOTO-3 conjugates and Hg2+ ions. The fluorescence signal obtained was linear with respect to the Hg2+ concentration over the range 25.0-500 nM (R2 = 0.99); for Pb2+ ions, it was linear over the range 3.0-50 nM (R2 = 0.98). The limits of detection (at a signal-to-noise ratio of 3) for Hg2+ and Pb2+ ions were 10.0 and 1.0 nM, respectively. Relative to other techniques for the detection of Hg2+ and Pb2+ ions in soil and water samples, our present approach is simpler, faster, and more cost-effective.  相似文献   

7.
A new type of fluorescent probe capable of detecting Ag+ and Hg2+ in two independent channels was developed in the present work. Specifically, in CH3CN–MOPS mixed solvents with CH3CN/MOPS ratio (v/v) of 15/85, this type of probe fluoresced weakly, and the addition of Ag+ remarkably induced fluorescence enhancement of the probe. In CH3CN–MOPS mixed solvents with the percentage of CH3CN increased up to 65%, the probe was highly fluorescent and addition of Hg2+ dramatically induced the fluorescence quenching. Thus, using such single-fluorophore-based probe and tuning the polarity of the mixed solvent, Ag+, and Hg2+ can be detected in independent channels with high selectivity and sensitivity. As a result, the mutual interference usually encountered in most cases of Ag+ and Hg2+ sensing owing to the similar fluorescence response that these two ions induced, can be effectively circumvented by using the probes developed herein.  相似文献   

8.
Shi L  Song W  Li Y  Li DW  Swanick KN  Ding Z  Long YT 《Talanta》2011,84(3):900-904
A new sensing molecule 8-hydroxyquinoline ferrocenoate (Fc-Q) which combines ferrocene and 8-hydroxyquinoline moieties was synthesized and applied as a multi-channel sensor for the detection of Hg2+ ion. Fc-Q can coordinate with Hg2+ to give colorimetric, fluorescent and electrochemical responses. Upon complexation with Hg2+ ion, the characteristic absorption peak is red-shifted (Δλ = 45 nm), the fluorescent intensity is quenched at 303 nm, and the oxidation peak is cathodic shifted (ΔE1/2 = −149 mV). Quantitatively analyzed Hg2+ ions at the range of ppb level could be achieved by electrochemical response. For the practical application of sensing Hg2+ in real world water, Fc-Q modified screen-printed carbon electrodes were obtained for facile, sensitive, and on-site analysis of Hg2+.  相似文献   

9.
The paper presents a novel method for the separation/enrichment of Hg2+ using microcrystalline thymolphthalein loaded with ternary association complex prior to the determination by spectrophotometry. The effects of different parameters, such as the dosages of KI and dodecyl trimethyl ammonium bromide (DTAB) and thymolphthalein, various salts and acidity etc. on the enrichment yield of Hg2+ have been investigated to select the experimental conditions. The results showed that in the presence of 1.0 g NaCl, when the dosage of 0.1 M KI solution was 1.50 mL and 5.0 × 10−3 M dodecyl trimethyl ammonium bromide (DTAB) solution was 1.50 mL respectively, the water‐insoluble ternary association complex of (DTAB)2(HgI4) which produced by Hg2+ and I, DTAB cation (DTAB+) was quantificationally absorbed on the surface of microcrystalline thymolphthalein Therefore, Hg2+ was separated completely from Zn2+, Mn2+, Ni2+, Co2+, Fe3+, Al3+, Pb2+, Bi3+ and Cr3+ etc. by contolling acidity. The possible enrichment mechanism of Hg2+ was deduced. The proposed method has been successfully applied to the determination of Hg2+ in the sample of industrial waster water, and the results agreed well with the dithizone method. The recoveries were 94.5%∼106.5%, and the RSD was 2.0%∼2.8%.  相似文献   

10.
段娜娜  王娜  杨薇  孔德明 《分析化学》2014,42(10):1414-1420
对鸟嘌呤碱基G重复序列之间连接环结构对G-四链体形成的影响进行了研究。发现在连接环较长,DNA链不易形成G-四链体的情况下,可以通过将环序列设计成双链结构的方式促进G-四链体的重新形成。这就为传感器的设计提供了一个新途径,即可以利用目标分子对环部双链的调节作用控制G-四链体DNA酶的活性。为证明这一点,在双链区域引入T-T碱基错配,破坏双链结构使DNA链不能形成G-四链体。Hg2+对T-T错配的稳定作用可以促进双链结构的形成,DNA链重新折叠成G-四链体,得到的G-四链体与氯化血红素(Hemin)结合后形成具有过氧化物酶活性的G-四链体DNA酶,据此构建了Hg2+传感器。利用此传感器可在10~700 nmol/L范围内实现Hg2+的定量检测,检出限为8.7 nmol/L。在此基础上,利用半胱氨酸可以将Hg2+从T-Hg2+-T碱基对上竞争下来的能力,设计了一种半胱氨酸的检测方法。此方法可以在20~600 nmol/L范围内实现半胱氨酸的定量检测,检出限为14 nmol/L。  相似文献   

11.
The Cu2+‐dependent ligation DNAzyme is implemented as a biocatalyst for the colorimetric or chemiluminescence detection of Cu2+ ions, Hg2+ ions, or cocaine. These sensing platforms are based on the structural tailoring of the sequence of the Cu2+‐dependent ligation DNAzyme for specific analytes. The tethering of a subunit of the hemin/G‐quadruplex DNAzyme to the ligation DNAzyme sequence, and the incorporation of an imidazole‐functionalized nucleic‐acid sequence, which acts as a co‐substrate for the ligation DNAzyme that is tethered to the complementary hemin/G‐quadruplex subunit. In the presence of different analytes, Cu2+ ions, Hg2+ ions, or cocaine, the pretailored Cu2+‐dependent ligation DNAzyme sequence stimulates the respective ligation process by combining the imidazole‐functionalized co‐substrate with the ligation DNAzyme sequence. These reactions lead to the self‐assembly of stable hemin/G‐quadruplex DNAzyme nanostructures that enable the colorimetric analysis of the substrate through the DNAzyme‐catalyzed oxidation of 2,2′‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonic acid), ABTS2?, by H2O2 into the colored product ABTS.?, or the chemiluminescence detection of the substrate through the DNAzyme‐catalyzed oxidation of luminol by H2O2. The detection limits for the sensing of Cu2+ ions, Hg2+ ions, and cocaine correspond to 1 nM , 10 nM and 2.5 μM , respectively. These different sensing platforms also reveal impressive selectivities.  相似文献   

12.
A series of novel (oligo)thienyl-imidazo-benzocrown ethers were synthesised through a simple method and evaluated as fluorimetric chemosensors for transition metal cations. Interaction with Ni2+, Pd2+, and Hg2+ in ACN/DMSO solution (99:1) was studied by absorption and emission spectroscopy. Chemoselectivity studies in the presence of Na+ were also carried out and a fluorescence enhancement upon chelation (CHEF) effect was observed following Hg2+ complexation. Considering that most systems using fluorescence spectroscopy for detecting Hg2+ are based on the complexation enhancement of the fluorescence quenching (CHEQ) effect, the present work represents one of the few examples for sensing of Hg2+ based on a CHEF effect.  相似文献   

13.
The tetrapeptide (Bz-ΔPhe(p-NPh2)-l-DOPA(protected)-l-Phe-l-Phe-OMe was designed to incorporate seven phenyl rings so that it’s conformation, self-assembly and application in Hg2+ ions sensing could be studied. Peptide molecules adopted an overlapping β-turn of type III/III conformation in crystals. The peptide showed a highly selective turn-on response towards mercuric ion over other metal ions with a 10-fold enhancement in fluorescence intensity. This intensity change coupled with the selectivity of the peptide towards mercury allowed us to demonstrate simple colorimetric dip sensing of Hg2+ ions. The technique provides a highly selective and effective way to detect Hg2+ ions. The peptide also self-assembled into nanospheres with diameter ranges from 100 to 500?nm. Mercuric ion coordination enabled these peptide nanospheres to aggregate into well-defined nanoparticles. The enhanced fluorescence upon Hg2+ addition demonstrates that peptide scaffolds can be exploited in the development of different selective sensors.  相似文献   

14.
Mercury(II) ions have emerged as a widespread environmental hazard in recent decades. Despite different kinds of detection methods reported to sense Hg2+, it still remains a challenging task to develop new sensing molecules to replenish the fluorescence‐based apparatus for Hg2+ detection. This communication demonstrates a novel fluorescent sensor using UiO‐66‐NH2 and a T‐rich FAM‐labeled ssDNA as a hybrid system to detect Hg2+ sensitively and selectively. To the best of our knowledge, it has rarely been reported that a MOF is utilized as the biosensing platform for Hg2+ assay.  相似文献   

15.
Despite several types of fluorescent sensing molecules have been proposed and examined to signal Hg2+ ion binding, the development of fluorescence‐based devices for in‐field Hg2+ detection and screening in environmental and industrial samples is still a challenging task. Herein, we report the synthesis and characterization of three new coumarin‐based fluorescent chemosensors featuring mixed thia/aza macrocyclic framework as receptors units, that is, ligands L1 – L3 . These probes revealed an OFF–ON selective response to the presence of Hg2+ ions in MeCN/H2O 4:1 (v/v), which allowed imaging of this metal ion in Cos‐7 cells in vitro. Once included in silica core–polyethylene glycol (PEG) shell nanoparticles or supported on polyvinyl chloride (PVC)‐based polymeric membranes, ligands L1 – L3 can also selectively sense Hg2+ ions in pure water. In particular we have developed an optical sensing array tacking advantage of the fluorescent properties of ligand L3 and based on the computer screen photo assisted technique (CSPT). In the device ligand L3 is dispersed into PVC membranes and it quantitatively responds to Hg2+ ions in natural water samples.  相似文献   

16.
We herein report two salicyaldehyde-quinoxaline ( HQS and HQSN ) conjugates and a benzaldehyde-quinoxaline ( QBN ) conjugate to fabricate selective chemosensors for F and Hg2+ in the micromolar range. This work demonstrates how sensing outcomes are affected by modulating proton acidity by introducing an electron donating group, −NEt2, in the probe backbone. Interestingly, the un-substituted probe HQS can selectively detect F, whereas HQSN and QBN are selective for Hg2+. In order to gain insights into the mechanism of sensing, geometry optimizations have been carried out on QS(−1) , QS(−1)⋅⋅⋅HF , QSN(−1) and QSN(−1)⋅⋅⋅HF and the experimental data are validated in terms of free energy and pKa values. Detailed DFT and TD-DFT analyses provide ample support towards the mechanism of sensing of the analytes.  相似文献   

17.
A sensitive and simple electrochemical method for norepinephrine (NE) determination was developed based on a poly(1,5‐diaminonaphthalene) film electrode (PDAN). Cathodically pretreated PDAN presents good selectivity, sensitivity, and reproducibility for NE. The polymer film can be easily electropolymerized onto a platinum electrode by cyclic voltammetry in 1.0 M HClO4. A cathodic pretreatment, consisting of the application of a potential of ?0.7 V for 3 s (vs. Ag/AgCl) to PDAN before each voltammetric measurement, enhanced the electrochemical activity of NE with no inference of ascorbic acid (AA). In optimized conditions, PDAN presents linear responses for NE in the range of 9.90 to 90.9 µM by differential pulse voltammetry (DPV) with a detection limit of 1.82 µM. A relative standard deviation of 3.0 % was obtained for 10 consecutive measurements of 40.0 µM NE solutions. The cathodically pretreated PDAN was successfully applied for NE determination in pharmaceutical formulation samples.  相似文献   

18.
Heavy metal ion pollution poses severe risks in human health and environmental pollutant, because of the likelihood of bioaccumulation and toxicity. Driven by the requirement to monitor trace-level mercury ion (Hg2+), herein we construct a new DNA-based sensor for sensitive electrochemical monitoring of Hg2+ by coupling target-induced formation of gold amalgamation on DNA-based sensing platform with gold amalgamation-catalyzed cycling signal amplification strategy. The sensor was simply prepared by covalent conjugation of aminated poly-T(25) oligonucleotide onto the glassy carbon electrode by typical carbodiimide coupling. Upon introduction of target analyte, Hg2+ ion was intercalated into the DNA polyion complex membrane based on T–Hg2+–T coordination chemistry. The chelated Hg2+ ion could induce the formation of gold amalgamation, which could catalyze the p-nitrophenol with the aid of NaBH4 and Ru(NH3)63+ for cycling signal amplification. Experimental results indicated that the electronic signal of our system increased with the increasing Hg2+ level in the sample, and has a detection limit of 0.02 nM with a dynamic range of up to 1000 nM Hg2+. The strategy afforded exquisite selectivity for Hg2+ against other environmentally related metal ions. In addition, the methodology was evaluated for the analysis of Hg2+ in spiked tap-water samples, and the recovery was 87.9–113.8%.  相似文献   

19.
The present study was aimed to use of N doped graphene quantum dots (N-GQDs) and N,K co-doped graphene quantum dots (N,K-GQDs) as a fluorescence quenching sensor to determine both mercury and copper in water sample, simultaneously using simple fluorescence protocol. Each of N-GQDs or N,K-GQDs was optimized separately with 1–5% (w/v) HNO3 or KNO3, respectively, and their quantum yields were determined and compared. It was found that N-GQDs, obtained from 3% (w/v) HNO3 doped resulted higher fluorescence intensity at the maximum excitation and emission wavelengths of 370 and 460 nm, respectively, with higher quantum yield (QY = 83.42%) compared with that of undoped GQDs (QY = 16.35%). While N,K-GQDs obtained from 5%(w/v) KNO3 gave somewhat different fluorescence spectrum, but still had the same maximum excitation and emission wavelengths with rather highest QY (94.07%). However, it is interesting that detection sensitivity expressed as slope of their calibration curve (y = 5.43x − 19.48; r2 = 0.9971) of the N-GQDs is rather higher than that (y = 1.29x + 17.66; r2 = 0.9977) of the N,K-GQDs for Hg2+ fluorescence quenching sensor, and the fluorescence intensity of N-GQDs had better selectively quenching effect only by both Hg2+ and Cu2+. Thus, their quenching effects were selected to develop the fluorescence turn-off sensor for trace level of both metal ions in real water samples. For method validation, the N-GQDs exhibited high sensitivity to detect both Hg2+ and Cu2+ with wide linear ranges of 20–100 μM and 100–500 μM, respectively. Limit of detection (LOD) and limit of quantitation (LOQ) were 0.42 μM & 1.41 μM for Hg2+ and 13.19 μM & 43.97 μM for Cu2+, respectively, with their precision expressed as an intra-day and an inter-day analysis of 6.98% & 11.35% for Hg2+ and 11.78% & 9.43% for Cu2+, respectively. Also the study of matrix analysis of the water samples (drinking water and tap water), was carried out using N-GQDs and N,K-GQDs resulted good percentage recoveries in comparison with those using undoped GQDs under the same optimum conditions.  相似文献   

20.
Developing novel photoresponsive oxidase mimics is highly useful for environmental pollution monitoring and biological sensing. Herein, long-life room-temperature phosphorescent nitrogen-doped carbon quantum dots (P-NCDs) were synthesized from triethylenetetramine hexaacetic acid via a simple one-step hydrothermal method. The P-NCDs showed high photoresponsive oxidase-like activity. On this basis, a P-NCD-based photostimulated colorimetric sensing system was developed and used to detect Hg2+ in environmental and biological samples. P-NCDs under 365 nm UV lamp irradiation converted dissolved oxygen, via triplet excited state (T1) exciton transfer, to singlet oxygen (1O2), which then oxidized 3,3′,5,5′-tetramethylbenzidine (TMB), leading to a color changing reaction. Cysteine can suppress the catalysis of P-NCDs, and its specific complexation with Hg2+ can recover the oxidation activity of P-NCDs. Hence, efficient colorimetric Hg2+ detection with a linear range of 0.01–14 μM and a detection limit of 3.1 nM was achieved by detecting the color change of TMB. The feasibility of this strategy was validated through real sample analysis. Our study broadens the application scope of phosphorescent nanomaterials into colorimetric sensing.  相似文献   

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