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1.
In this article, we describe the analysis of aptamers for Hg2+ ions through CE with LIF (CE‐LIF) detection using 2% poly(ethylene oxide) solutions containing OliGreen (fluorophore). In the presence of an EOF, DNA strands migrating against the EOF were detected at the cathode end. Four DNA strands – T33, T5C28, T5C5T23, and T15C5T13 – could not be separated through CE‐LIF in the absence of Hg2+. At 0.3 mM Hg2+, however, all four were partially separated within 20 min, with SDs of the migration times all being less than 2.5%. From the CE, fluorescence, and ellipticity data, we concluded that the conformations of these four DNA strands all changed from random‐coil to folded structures as a result of T–Hg2+–T bonding. In addition, we found that this CE approach provided different electropherograms patterns for T7, T15, and T33 in the absence and presence of Hg2+, indicating various interactions of the DNA strands with Hg2+. Using this simple, high‐resolution CE approach, we also demonstrated that adenosine triphosphate has a stronger interaction with the adenosine triphosphate aptamer than with either the platelet‐derived growth factor aptamer or T33. This CE approach holds great potential for screening aptamers for small solutes, studying the catalytic activity of DNAzymes, and evaluating the biological functions of microRNA.  相似文献   

2.
Several DNA templates with the sequence 5′‐T n TAACCCCTAACCCCT ‐3′ (n = 0, 15, 30, and 45) were used to prepare DNA template–silver nanoclusters (DNA –Ag NCs ). The T n sequence acts as a recognition element for Hg2+, while the rest of the sequence acts as a template for DNA –Ag NCs . At pH 3.0, the fluorescence intensity of DNA –Ag NCs is enhanced by ATP , and the enhanced fluorescence is quenched by Hg2+. The length of polyT shows a slight effect on the sensitivity for the detection of Hg2+ but almost no effect on the optical properties of DNA –Ag NCs . The fluorescence response of DNA –Ag NCs (T15‐DNA –Ag NCs ) vs. Hg2+ concentration shows two linear ranges over 10–100 and 100–1000 nM , mainly because of the fluorescence quenching due to DNA conformational changes through T–Hg2+–T coordination and the formation of an amalgam with Ag NCs , respectively. The sensitivity of the T15‐DNA –Ag NC probe was validated through the analysis of Hg2+ in spiked pond water. Based on the switch‐on and switch‐off fluorescence properties of T15‐DNA –Ag NCs , an IMPLICATION logic gate was fabricated using the concentrations of ATP and Hg2+ as inputs and the fluorescence intensity at 585 nm as output.  相似文献   

3.
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   

4.
In this research a Hg2+ ion biosensor was developed by combining Prussian blue (PB) with glucose oxidase (GOx) – an enzyme that can be inhibited by Hg2+ ions. An application of PB in the design of Hg2+ ion biosensor enabled detecting changes in hydrogen peroxide reduction current at low operational potential of 0.2 vs Ag|AgCl,KClsat. The described Hg2+ ion biosensor exhibited wide linear range from 27 μM to 247 μM of Hg2+ and higher maximal detectable concentration of Hg2+ than other GOx inhibition-based biosensors, making it convenient for the analysis of samples with high concentration of Hg2+ ions.  相似文献   

5.
The absorption and luminescence of bisbidentate complexes of aminomethylene derivatives of 5-pyrazolethione with Zn2+, Cd2+, Hg2+, and Pb2+ in dilute solutions in hydrocarbons and 95% ethanol are determined by the structure of the ligand in the complexes. In the Zn2+, Cd2+, and Hg2+ complexes, N···M coordination is realized, whereas in the Pb2+ complexes, S··· M. In the Zn-Cd-Hg series, a heavy-atom effect is revealed, which stimulates exclusively radiationless transitions involving the S 1 and T states.  相似文献   

6.
Lu J  He X  Zeng X  Wan Q  Zhang Z 《Talanta》2003,59(3):553-560
A novel calix[4]arene derivative containing benzothiazole group was coated on glassy carbon electrode (GCE) and then applied to the recognition of mercury ion. Cyclic and square wave voltammetric results showed that the modified electrode selectively recognizes Hg2+ ion in aqueous media. A new anodic stripping peak at −0.3 V (vs. Ag/Ag+) can be obtained by scanning the potential from −0.6 to 0.6 V, and the peak currents are proportional to the Hg2+ concentration. The modified electrode in a 0.1 M H2SO4+0.01 M NaCl solution shows linear voltammetric response in the range of 25-300 μg l−1 and detection limit of 5 μg l−1 (ca. 2.5×10−8 M). This modified GCE does not present any significant interference from alkali, alkaline and transition metal ions except for Pb2+, Ag+ and Cu2+ ions. Only 500, 50 and 100-fold molar excess of Pb2+, Ag+ and Cu2+ ions, respectively, can lead to voltammetric response comparable with that of Hg2+. The proposed method was successfully applied to determine mercury in natural water.  相似文献   

7.
In this study, a nanocomposite consisting of three-dimensional reduced graphene oxide (3D-rGO) and plasma-polymerized propargylamine (3D-rGO@PpPG) was prepared and used as a highly sensitive and selective DNA sensor for detecting Hg2+. Given the high density of amino groups in the resultant 3D-rGO@PpPG nanocomposite, thymine-rich and Hg2+-targeted DNA was preferentially immobilized on the fabricated sensor surface via the strong electrostatic interaction between DNA strands and the amino-functionalized nanocomposites, followed by detecting Hg2+ through T–Hg2+–T coordination chemistry between DNA and Hg2+. The results of electrochemical measurements revealed that the anchored amount of DNA strands anchored on the 3D-rGO@PpPG nanofilm surface affects the determination of Hg2+ in aqueous solution. It showed high sensitivity and selectivity toward Hg2+ within concentrations ranging from 0.1 to 200 nM and displayed a low detection limit of 0.02 nM. The new strategy proposed also provides high selectivity of Hg2+ against other interfering metal ions, good stability, and repeatability. The excellent applicability of the developed sensor confirms the potential use of plasma-modified nanofilms for the detection of heavy metal ions in real environmental samples and water.  相似文献   

8.
Two novel rhodamine-based fluorescence enhanced molecular probes (RA1 and RA2) were synthesized, which were both designed as comparative fluoroionophore and chromophore for the optical detection of Hg2+. The recognizing behaviors were investigated both experimentally and computationally. They exhibited high selectivity and sensitivity for Hg2+ over other commonly coexistent metal ions in CH3CN/H2O (1:1, V/V) solution. Test shows that hydroxy benzene of rich electron was beneficial to the chelate of Hg2+ with sensors. The detection limit was measured to be at least 0.14 μmol/L. After addition of Hg2+, the color changed from colourless to pink, which was easily detected by the naked eye in both solution and hydrogel sensor.  相似文献   

9.
A novel electrochemical sensor on ZIF-8 nanocomposites (Ag/ZnO/ZIF-8) was developed to analyze the mercury ions (Hg2+). The ZIF-8 materials are one of the 3-dimensional porous metal-organic frameworks with highly accessible pores and great surface area. The ZIF-8 nanocomposites were prepared through simple sol-gel methods and their physio-chemical properties were characterized via different analytical analyses. As a result of cyclic voltammetry, Ag/ZnO/ZIF-8 exhibited a better electrocatalytic behavior towards the detection of mercury ions (Hg2+). Furthermore, the composite modified electrode was then inspected as a sensor for DPV detection of mercury ions. The nanocomposite sensor performed a wide linear range from 0.5 μM to 140 μM with a low detection limit of 40 nM, and high sensitivity of 56.06 μA μM−1 cm−2. Moreover, the ZIF-8 composite sensor showed a higher selectivity toward the detection of mercury ions (Hg2+). The real-time applications of the ZIF-8 composites sensor were inspected in various samples with good sensitivity.  相似文献   

10.
Polythymine oligonucleotide (PTO)‐modified gold electrode (PTO/Au) was developed for selective and sensitive Hg2+ detection in aqueous solutions. This modified electrode was prepared by self‐assembly of thiolated polythymine oligonucleotide (5′‐SH‐T15‐3′) on the gold electrode via Au? S bonds, and then the surface was passivated with 1‐mercaptohexanol solution. The proposed electrode utilizes the specific binding interactions between Hg2+ and thymine to selectively capture Hg2+, thereby reducing the interference from coexistent ions. After exchanging the medium, electrochemical reduction at ?0.2 V for 60 s, voltammetric determination was performed by differential pulse voltammetry using 10 mM HEPES; pH 7.2, 1 M NaClO4 as supporting electrolyte. This electrode showed increasing voltammetric response in the range of 0.21 nM Hg2+, with a relative standard deviation of 5.32% and a practical detection limit of 60 pM. Compared with the conventional stripping approach, the modified electrode exhibits good sensitivity and selectivity, and is expected to be a new type of green electrode.  相似文献   

11.
In this study, we developed a fluorescence assay for the highly sensitive and selective detection of Hg2+ and Pb2+ ions using a gold nanoparticle (Au NP)-based probe. The Hg–Au and Pb–Au alloys that formed on the Au NP surfaces allowed the Au NPs to exhibit peroxidase-mimicking catalytic activity in the H2O2-mediated oxidation of Amplex UltraRed (AUR). The fluorescence of the AUR oxidation product increased upon increasing the concentration of either Hg2+ or Pb2+ ions. By controlling the pH values of 5 mM tris–acetate buffers at 7.0 and 9.0, this H2O2–AUR–Au NP probe detected Hg2+ and Pb2+ ions, respectively, both with limits of detection (signal-to-noise ratio: 3) of 4.0 nM. The fluorescence intensity of the AUR oxidation product was proportional to the concentrations of Hg2+ and Pb2+ ions over ranges 0.05–1 μM (R2 = 0.993) and 0.05–5 μM (R2 = 0.996), respectively. The H2O2–AUR–Au NP probe was highly selective for Hg2+ (>100-fold) and Pb2+ (>300-fold) ions in the presence of other tested metal ions. We validated the practicality of this simple, selective, and sensitive H2O2–AUR–Au NP probe through determination of the concentrations of Hg2+ and Pb2+ ions in a lake water sample and of Pb2+ ions in a blood sample. To the best of our knowledge, this system is the first example of Au NPs being used as enzyme-mimics for the fluorescence detection of Hg2+ and Pb2+ ions.  相似文献   

12.
The substoichiometric extraction of Hg2+ using diethyldithiocarbamic acid and 203Hg tracer was studied. Chloroform was employed to remove the complexes from the aqueous media which were 0.5M H2SO4 or 1 M HClO4 and 0 to 5 M NaCL. - Systems containing Cl? allowed extraction of Hg2+ for all DDC/Hg molar ratios, the extracted complexes being HgCl(DDC) and Hg(DDC)2. Their exchange constant was determined. - In the absence of Cl?, no extraction could be effected in either system if the DDC/Hg molar ratio was < 1; the H2SO4 system remained clear, whereas a precipitate of HgClO4(DDC) formed in the HClO4 system. For molar ratios > 1, the extraction of Hg2+ increased linearly with the addition of DDC, the extracted complex being Hg(DDC)2.  相似文献   

13.
Electrospray ionization mass (ESI-MS) spectrometry was used to investigate the nature of metal complexes of alachlor and their dissociations on activation. Ions of the first row transition metal series were employed to react with alachlor and the products were subjected to collision-induced dissociation (CID) for further structural characterization. The formation of diverse complex ions including doubly charged metal/alachlor complexes; [3L + M]2+ and [4L + M]2+ (L: alachlor and M: transition metal ions) were observed depending on the experimental conditions including the tube lens offset voltage (TLOV) and relative concentrations of alachlor and transition metal ions. It is clear that complexation with transition metal ions alters the reactive site of alachlor, promoting the loss of chlorine over the loss of CH3OH that is the major reaction pathway in uncomplexed system. Direct elimination of chlorine from alachlor molecule was confirmed by the use of MnBr2 instead of MnCl2. These evidences clearly illustrate the catalytic activities of the metal ions through insertion mechanism. The function of transition metal ions in complexation was emphasized comparing the fragmentation patterns with those of protonated molecule. A change in the oxidation state of copper from + 2 to + 1 during the dissociation of metal complex was observed in company with elimination of radicals which is specific for the copper complex ions.  相似文献   

14.
Stoichiometric reactions of 4,4'-diacetylcurcumin ( HL ) with series of transition metal ions, namely Fe3+, Co2+, Ni2+ and Zn2+, in methanol result in the corresponding homoleptic metal complexes. All the obtained complexes were characterized by elemental analysis, high resolution mass spectrometry, IR spectroscopy, magnetic moment and single-crystal X-ray diffraction. Structural analyses are unprecedentedly performed for the FeIII, CoII, and NiII complexes and reveal octahedral mononuclear complexes with the compositions [Fe(L)3] and [M(L)2(MeOH)2] (M = Co2+, Ni2+, Zn2+) for trivalent and divalent metal ions, respectively. In all complexes, the deprotonated ligands serve as monoanionic and bidentate ligands with (O,O)-chelating β-diketonate moieties. The free ligand HL exhibits considerable antiproliferative effects for the human MCF-7 breast and HepG2 liver cancer cells with IC50 values of 20.91 ± 2.16 μg · mL–1 and 12.85 ± 1.85 μg · mL–1, respectively. The CoII and ZnII complexes with IC50 values in the range of 14.53–20.80 μg · mL–1 for MCF-7 breast and 8.48–10.68 μg · mL–1 for HepG2 liver cancer cells show stronger antiproliferative effects than HL, the FeIII and NiII complexes cause weaker reductions of the growth of the two tested cancer cell lines.  相似文献   

15.
A new nitrobenzoxadiazole (NBD)-based chemosensor N′-(7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)thiophene-2-carbohydrazide ( NTCH) was synthesized for detecting Hg2+. NTCH could sense Hg2+ through a color change method from pale yellow to pink. Binding ratio of NTCH and Hg2+ was determined to be 1:1 with the analysis of electrospray ionization mass spectrometry and Job plot. Detection limit turned out to be 0.69 μM. In addition, NTCH could be successfully utilized for detecting Hg2+ in real water samples and visible color test strips. The probing mechanism of NTCH to Hg2+ was explained with 1H nuclear magnetic resonance (NMR) titration, Job plot, electrospray ionization mass spectrometry (ESI-MS), and theoretical calculations.  相似文献   

16.
There is widespread interest in non‐covalent bonding and weak interactions, such as electrostatic interactions, hydrogen bonding, solvophobic/hydrophobic interactions, metal–metal interactions, and π–π stacking, to tune the molecular assembly of planar π‐conjugated organic and inorganic molecules. Inspired by the roles of metal–aromatic interaction in biological systems, such as in ion channels and metalloproteins, herein, we report the first example of the use of Hg2+–aromatic interactions to selectively control the assembly and disassembly of zinc–salen complexes in aqueous media; moreover, this process exhibited significant “turn on” fluorescent properties. UV/Vis and fluorescence spectroscopic analysis of the titration of Hg2+ ions versus complex ZnL1 revealed that the higher binding affinity of Hg2+ ions (compared to 13 other metal ions) was ascribed to specific interactions between the Hg2+ ions and the phenyl rings of ZnL1 ; this result was also confirmed by 1H NMR spectroscopy and HRMS (ESI). Further evidence for this type of interaction was obtained from the reaction of small‐molecule analogue L1 with Hg2+ ions, which demonstrates the proximity of the N‐alkyl group to the aromatic protons during Hg2+‐ion binding, which led to the consequential H/D exchange reaction with D2O. DFT modeling of such interactions between the Hg2+ ions and the phenyl rings afforded calculated distances between the C and Hg atoms (2.29 Å) that were indicative of C? Hg bond‐formation, under the direction of the N atom of the morpholine ring. The unusual coordination of Hg2+ ions to the phenyl ring of the metallosalen complexes not only strengthened the binding ability but also increased the steric effect to promote the disassembly of ZnL1 in aqueous media.  相似文献   

17.
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   

18.
Novel 15-hydroxybenzomonothia-15-crown-5 containing the sulfur atom linked with the benzene ring and its S-oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15-hydroxybenzo-15-crown-5 with Na, Ca, AgI, Cd, HgII, and PbII perchlorates were determined by 1H NMR titration. In MeCN-d3, the benzothiacrown ether demonstrates a high selectivity towards the thio- and oxothiophilic Hg2+ (logK 1 = 7.1) and Pb2+ ions (logK 1 = 7.4). In MeCN-d3-D2O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the “soft” Ag+ and Hg2+ ions having low affinity for the “hard” oxygen atoms and, on the contrary, very high affinity for the “soft” SII atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds preferably the Hg2+ (logK 1 = 5.0) and Ag+ ions (logK 1 = 2.7). In MeCN-d3, the benzothiacrown-derived sulfoxide is a weak and non-selective complexing agent towards all the metal cations under study; the reference 15-hydroxybenzo-15-crown-5 forms more stable complexes with the oxophilic sodium, calcium, and lead(ii) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X-ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia-15-crown-5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high-selective and efficient complexing agents for the “soft” mercury(ii) and silver(i) cations in acetonitrile-water mixtures.  相似文献   

19.
The yeast cells, Saccharomyces cerevisiae, were exposed to Hg2+ ions (10–4M) and SeO2 (2·10–4–10–2M) or Se- methionine (2·10–4M). Instrumental neutron activation analysis (INAA) was used to analyze changes in the Hg, Zn, Fe and Co levels in these cells. When the yeast was incubated in a medium containing 10–3M and 10–2M SeO2, the Hg content of the yeast markedly increased. It was also found that the uptake of Se and Hg influenced the levels of Zn, Fe and Co found in the cells. While the presence of Se-methionine (Se-Met), SeO2 or Hg2+ ions caused increases in the intracellular Zn levels, the combined presence of Hg2+ and SeO2 and their assumed interaction, reduced the efficiency of Se for increasing the Zn content of yeast.  相似文献   

20.
The liquid-liquid extraction of ion-pair complexes of zinc(II), copper(II) and cadmium(II) is described. The macrocyclic ligands 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (4Me-cyclam-14) and rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (Tet b) are used with xanthene dyes as the counter ions. The apparent extraction constants (Dc) are reported. The sequences of extraction efficiency of both ligands are related to the structure of the complexes. The apparent molar absorptivity of the Cd(4Me-cyclam-14)—erythrosin A ion-associate is 1.1 × 105 l mol? cm?1. The calibration graph is linear over the range 0—10?5 M, which allows even 0.05 μg ml?1 cadmium to be determined in a 0.5 M sodium hydroxide medium. No interference was observed from Ni2+, Pb2+, Zn2+, Mg2+, Sn4+, Ga3+, Al3+ and Fe3+. Interferences were Cu2+, Hg2+, Ag+ and large anions.  相似文献   

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