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1.
An ultrasensitive surface‐enhanced Raman spectroscopy (SERS) sensor based on rolling‐circle amplification (RCA)‐increased “hot‐spot” was developed for the detection of thrombin. The sensor contains a SERS gold nanoparticle@Raman label@SiO2 core‐shell nanoparticle probe in which the Raman reporter molecules are sandwiched between a gold nanoparticle core and a thin silica shell by a layer‐by‐layer method. Thrombin aptamer sequences were immobilized onto the magnetic beads (MBs) through hybridization with their complementary strand. In the presence of thrombin, the aptamer sequence was released; this allowed the remaining single‐stranded DNA (ssDNA) to act as primer and initiate in situ RCA reaction to produce long ssDNAs. Then, a large number of SERS probes were attached on the long ssDNA templates, causing thousands of SERS probes to be involved in each biomolecular recognition event. This SERS method achieved the detection of thrombin in the range from 1.0×10?12 to 1.0×10?8 M and a detection limit of 4.2×10?13 M , and showed good performance in real serum samples.  相似文献   

2.
This work reports a new electrochemical monitoring platform for sensitive detection of Cu2+ coupling click chemistry with nanogold‐functionalized PAMAM dendrimer (AuNP‐PAMAM). The system involved an alkyne‐modified carbon electrode and an azide‐functionalized AuNP‐PAMAM. Initially, the added Cu2+ was reduced to Cu+ by the ascorbate, and then the azide‐modified AuNP‐PAMAM was covalently conjugated to the electrode via Cu+‐catalyzed azide‐alkyne click reaction. The carried AuNPs accompanying PAMAM dendrimer could be directly monitored by stripping voltammetry after acidic pretreatment. By introduction of high‐loading PAMAM dendrimer with gold nanoparticles, as low as 2.8 pM Cu2+ (ppt) could be detected, which was 125‐fold lower than that of gold nanoparticle‐based labeling strategy. The method exhibited high specificity toward target Cu2+ against other potentially interfering ions, and was applicable for monitoring Cu2+ in drinking water with satisfactory results.  相似文献   

3.
A highly substituted imidazole‐based colorimetric and fluorogenic chemosensor, 2‐methoxy‐4‐(4,5‐diphenyl‐1H‐imidazol‐2‐yl)phenol (L), for the detection of Cu2+ ion and subsequent colorimetric detection of an amino acid, cysteine, was investigated. L exhibited a distinct color change from colorless to red in the presence of Cu2+ in an aqueous medium. The L‐Cu2+ complex can also be used to detect cysteine by the naked eye over a series of amino acids. The receptor L behaves as a highly selective colorimetric and fluorescent sensor for Cu2+ ions at concentrations as low as 4.33 and 2.25 μM, respectively. These values are much less compared to the WHO recommended limit of 30 μM for Cu2+ in drinking water. From Job's plot and the ESI‐MS spectrum, a 1:1 stoichiometric complex between L and Cu2+ ions can readily be reckoned. This binding was also substantiated by the EPR spectrum and magnetic susceptibility measurements. Additionally, the binding of L with Cu2+ ions was also manifested in the detection of B16F10 cells. This was substantiated through fluorescence microscopy. The spectrum of the L‐Cu2+ entity was also attempted to reproduce theoretically. The probable structure of this was also propounded through Density Functional Theory.  相似文献   

4.
Abstract : It is well known that copper ions play a critical role in various physiological processes. However, a variety of human diseases are tightly correlated with copper overload. Although there are numerous fluorescent probes capable of detecting copper ions, most of them are “turn‐off” probes owing to copper (II) ions fluorescence quenching effect, resulting in poor sensitivity. Herein, a novel “turn‐on” near‐infrared (NIR) fluorescent probe PZ‐N based on phenoxazine was designed and synthesized for the selective detection of copper (II) ions (Cu2+). Upon the addition of Cu2+, the probe could quickly react with Cu2+ and emit strong fluorescence, along with colour change from colourless to obvious blue. Moreover, the probe PZ‐N showed good water solubility, high selectivity, and excellent sensitivity with low limit of detection (1.93 nM) towards copper (II) ions. More importantly, PZ‐N was capable of effectively detecting Cu2+ in living cells.  相似文献   

5.
Stable ultra‐thin Langmuir monolayers of calix[4]resorcinarene derivatives, namely: C‐dec‐9‐enylcalix[4]resorcinarene‐O‐(R+)‐α‐methylbenzylamine (Ionophore I ), and C‐dec‐9‐enylcalix[4]resorcinarene‐O‐(S‐)‐α‐methylbenzylamine (Ionophore II ), were prepared at the air‐water interface. Their interactions with a series of heavy metals (HM) ions (Cu2+, Pb2+, Hg2+ and Cd2+) present in the aqueous subphase were investigated by measuring surface pressure‐area isotherms, at different concentrations. The surface pressure‐area (Π‐A) isotherms were stable and demonstrated the HM amounts influence on the limiting area (Alim) values, therefore confirming the examined macrocycles capability to host the metallic toxicants. Additionally, a HM concentration dependence was realized and interpreted by a selective tendency of both ionophores towards Cu2+ and Cd2+ ions over Pb2+ and Hg2+, especially at high concentrations. The HM ions interactions with the applied calix[4]resorcinarene Langmuir ultra‐thin monolayers were interpreted based on the Gibbs‐Shishkovsky adsorption equation. Moreover, quartz crystal microbalance with impedance measurement (QCM‐I), was applied for the detection of HM ions in solutions. The QCM‐I results showed the effectiveness of the coated QCM‐I crystals in detecting the ions at different concentrations. The detection limit values were in the order of 0.16, 0.3, 0.65, 1.1 ppm (Ionophore I), as well 0.11, 0.45, 0.2, 0.89 (Ionophore II) for the Cu2+, Pb2+, Hg2+ and Cd2+ cations, respectively. Additionally, a selective tendency of both ionophores towards copper ions was shown.  相似文献   

6.
A sensitive voltammetric method for detection of trace heavy metal ions using chemically modified carbon nanotubes (CNTs) electrode surfaces is described. The CNTs were covalently modified with cysteine prior to casting on electrode surfaces. Cysteine is an amino acid with high affinities towards some heavy metals. In this assay, heavy metals ions accumulated on the cysteine‐modified CNT electrode surfaces prior to being subjected to differential pulse anodic stripping voltammetry analysis. The resulting peak currents were linearly related to the concentrations of the metal ions. The method was optimized with respect to accumulation time, reduction time and reduction potential. The detection limits were found to be 1 ppb and 15 ppb for Pb2+ and Cu2+ respectively. The technique was used for the detection of Pb2+ and Cu2+ in spiked lake water. The average recoveries of Pb2+ and Cu2+ were 96.2% and 94.5% with relative standard deviations of 8.43% and 7.53% respectively. The potential for simultaneous detection of heavy metal ions by the modified CNTs was also demonstrated.  相似文献   

7.
A water in soluble long‐chain crown ether alkyl (C18)‐benzo‐15‐crown‐5 was synthesized and applied as a coating material on quartz crystal membranes of a liquid flow piezo electric crystal sensor. The oscillating crown ether‐coated piezo electric (PZ) crystal with a home‐made computer inter face was prepared as a liquid chromato graphic (LC) detector for organic species and metal ions in aqueous solutions. The oscillating frequency of the quartz crystal decreased due to the adsorption of organic molecules or metal ions on crown ether molecules. Effects of functional group, molar mass, steric hindrance, and polarity of organic molecules on frequency responses of the crown ether coated PZ crystal detector were investigated. The frequency responses of the crown ether coated PZ crystal detector for various molecules were in the order: amines > carboxylic acids > alcohols > ketones. The crown ether PZ detector also exhibited good sensitivity for some heavy metal ions and the frequency shifts were in the order: Cr3+ » Pb2+ > Co2+ > Cd2+ > Ni2+ > Cu2+. The crown ether coated piezo electric crystal LC detector demonstrated low detection limits for various polar organic molecules, e.g., 6.0 × 10?5 M for propylamine, and metal ions, e.g., 2.9 × 10?5 M (1.8 ppm) for Cu2+; the crown ether PZ detector also gave good reproducibility when re used. A quite sensitive electrochemical quartz crystal microbalance (EQCM) detection system was also set‐up for detecting trace heavy metal ions in solutions. The variation in frequency of the PZ crystal and the diffusion current were observed simultaneously after the reduction in heavy metal ions such as Cu2+ and Ni2+. The EQCM detection system exhibited fairly good sensitivity, e.g., 112 Hz/ppm for Cu2+ and a good detection limit, e.g., 0.13 ppm for Cu2+ ions. Comparison between EQCM and PZ detection systems was made and discussed.  相似文献   

8.
We described a new ensemble‐approach‐based chemosensor, NCH‐Cu2+, for highly selective and reversible detection of histidine (His) in aqueous solution and live cells. The ligand NCH exhibited specific binding with Cu2+ ions over other metal ions, accompanied with a 92.2 % fluorescence quenching. The decomplexation of NCH‐Cu2+ ensemble by His led to the liberation of the fluorophore, NCH, and thus the fluorescence was recovered. The specific fluorescence enhancement of NCH‐Cu2+ towards His showed a good linearity with a detection of limit at 70 nm . Quantification of intracellular His at the single cell level was achieved by microscopy and flow cytometry. Besides the UV/Vis and emission titration, reversibility of the NCH‐Cu2+ towards His was further confirmed by imaging and cytometry analysis. In addition, microscopy studies revealed that NCH‐Cu2+ was distributed in the lysosome of live cells, where it could be employed as a fluorescent biosensor for imaging of His at subcellular level.  相似文献   

9.
Copper is an indispensable trace element for human health. Too much or too little intake of copper ion (Cu2+) can lead to its own adverse health conditions. Therefore, detection of Cu2+ is always of vital importance. In this work, a simple sensor was developed for rapid detection of trace Cu2+ in water, in which L‐cysteine (Cys) as a molecular probe was self‐assembled on a gold interdigital electrode to form a monolayer for specific capture of Cu2+. The interfacial capacitance of interdigital electrode was detected to indicate the target adsorption level under an AC signal working as the excitation to induce directed movement and enrichment of Cu2+ to the electrode surface. This sensor reached a limit of detection of 4.14 fM and a satisfactory selectivity against eight other ions (Zn2+, Hg2+, Pb2+, Cd2+, Mg2+, Fe2+, As3+, and As5+). Testing of spiked tap water was also performed, demonstrating the sensor's usability. This sensor as well as the detection method shows a great application potential in fields such as environmental monitoring and medical diagnosis.  相似文献   

10.
Carboxylated peptide‐functionalized gold nanoparticles (peptide‐GNPs) self‐assemble into two‐ and three‐dimensional nanostructures in the presence of various heavy metal ions (i.e. Pb2+, Cd2+, Cu2+, and Zn2+) in aqueous solution. The assembly process is monitored by following the changes in the surface plasmon resonance (SPR) band of gold nanoparticles in a UV/Vis spectrophotometer, which shows the development of a new SPR band in the higher‐wavelength region. The extent of assembly is dependent on the amount of metal ions present in the medium and also the time of assembly. TEM analysis clearly shows formation of two‐ and three‐dimensional nanostructures. The assembly process is completely reversible by addition of alkaline ethylenediaminetetraacetic acid (EDTA) solution. The driving force for the assembly of peptide‐GNPs is mainly metal ion/carboxylate coordination. The color and spectral changes due to this assembly can be used for detection of these heavy‐metal ions in solution.  相似文献   

11.
《中国化学会会志》2017,64(12):1432-1445
A new 1,8‐naphthalimide‐based fluorescence “turn off” chemosensor, N‐phenyl‐4‐(3,3′‐((2‐aminoethyl)azanediyl)dipropanoic acid)‐1,8‐naphthalimide ( MAST ), for the detection of Cu2+ was synthesized. Upon treatment with Cu2+, in coexistence with various competitive metal ions in HEPES‐buffered dimethylsulfoxide (DMSO) solution (v/v, 1:1; pH 7.4), MAST displayed a high selectivity toward Cu2+ with a fluorescence quenching of 83.67%. Additionally, a good linear response of MAST for the detection of Cu2+ was obtained in the concentration range of 10 × 10−6 to 50 × 10−6 M. A 1:1 stoichiometric interaction of MAST with Cu2+ was observed, and the association constant and detection limit were calculated to be 1.37 × 106 and 0.69 × 10−8 M, respectively. The sensing mechanism of the chemosensor toward Cu2+ was proposed due to the effect of the paramagnetic nature of Cu2+ and reverse‐photo‐induced electron transfer (PET) process. Ultimately, the proposed chemosensor was applied to quantify Cu2+ in real‐world water samples, with excellent recovery rates of 98.00–109.80% observed.  相似文献   

12.
In this study, quasi‐cubic and hexagonal bipyramid α‐Fe2O3 polyhedrons with high‐index facets exposed were controllably synthesized by applying metal ions Zn2+ or Cu2+ as structure‐directing agents. The growth of the α‐Fe2O3 nanostructures with high‐index facets were induced by metal ions without the addition of any other surfactants. The quasi‐cubic form controlled by Zn2+ looks like a cube but has an angle of approximately 86° bound by (012), (10‐2), and (1‐12) facets, whereas the hexagonal bipyramid form controlled by Cu2+ has a sixfold axis bound by {012} facets. Magnetic measurements confirm that these two kinds of nanocrystals display shape‐ and surface‐dependent magnetic behaviors. The hexagonal bipyramid iron oxide nanocrystals show a lower Morin transition temperature of 240 K and might be spin‐canted ferromagnetically controlled at room temperature, and the ferromagnetism disappears at low temperature. The quasi‐cubic nanocrystals have a splitting between FC curve and ZFC curve from the highest experimental temperature and no Morin transformation occurs; this indicates that they would be defect ferromagnetically controlled at low temperature. The reported metal‐ion‐directing technique could provide a universal method for shape‐ and surface‐controlled synthesis of nanocrystals with high‐index facets exposed.  相似文献   

13.
The potentiometric characteristics of a new Cu2+‐selective electrode based on 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo) phenol as an efficient ionophore has been evaluated. The effects of influential parameters on the potentiometric responses such as the amount of plasticizer, the amount of ionophore, pH of the sample solution, and the effect of coexisting ions on the electrode signal were subsequently investigated . The selectivity of the electrode was assessed by calculating the selectivity coefficients using the matched potential method. The optimum ratio of the amount of materials required for the preparation of the electrode was found to be 1.7: 32.1: 64.2: 2.0 corresponding to carboxylated PVC, dimethyl sebacate as solvent mediators, potassium tetrakis (p‐chlorophenyl) borate as the anion localizing agent, and ionophore, respectively. The electrode had a fast response (7s) as well as a satisfactory Nernstian slope (29.26±0.91 mV/decade) to Cu2+ over a wide concentration range of 2.0×10?6‐ 5.0×10?2 M with a low detection limit of 5.9×10?7 M. The developed sensor was successfully used for the potentiometric titration of Cu2+ ion with EDTA and subsequently, efficient determination of this metal ion in a mineral water sample was performed.  相似文献   

14.
The development of highly sensitive and selective methods for the detection of lead ion (Pb2+) is of great scientific importance. In this work, we develop a new surface‐enhanced Raman scattering (SERS)‐based sensor for the selective trace measurement of Pb2+. The SERS‐based sensor is assembled from gold nanoparticles (AuNPs) and graphene using cucurbit[7]uril (CB[7]) as a precise molecular glue and a local SERS reporter. Upon the addition of Pb2+, CB[7] forms stronger complexes with Pb2+ and desorbs from AuNPs, resulting in a sensitive “turn‐off” of SERS signals. This SERS‐based assay shows a limit of detection (LOD) of 0.3 nm and a linear detection range from 1 nm to 0.3 μm for Pb2+. The feasibility of the assay is further demonstrated by probing Pb2+ in real water samples. This SERS‐based analytical method is highly sensitive and selective, and therefore holds promising applications in environmental analysis.  相似文献   

15.
The competitive removal of Pb2+, Cu2+, and Cd2+ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me2+/gpolymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd2+ > Pb2+ > Cu2+ and Pb2+ > Cd2+ > Cu2+, respectively. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

16.
《Electroanalysis》2018,30(1):194-203
Glassy carbon electrode (GCE) modified with L‐cysteine and gold nanoparticles‐reduced graphene oxide (AuNPs‐RGO) composite was fabricated as a novel electrochemical sensor for the determination of Cu2+. The AuNPs‐RGO composite was formed on GCE surface by electrodeposition. The L‐cysteine was decorated on AuNPs by self‐assembly. Physicochemical and electrochemical properties of L‐cysteine/AuNPs‐RGO/GCE were characterized by scanning electron microscopy, atomic force microscopy, energy dispersive spectroscopy, Raman spectroscopy, X‐ray diffraction, cyclic voltammetry and adsorptive stripping voltammetry. The results validated that the prepared electrode had many attractive features, such as large electroactive area, good electrical conductivity and high sensitivity. Experimental conditions, including electrodeposition cycle, self‐assembly time, electrolyte pH and preconcentration time were studied and optimized. Stripping signals obtained from L‐cysteine/AuNPs‐RGO/GCE exhibited good linear relationship with Cu2+ concentrations in the range from 2 to 60 μg L−1, with a detection limit of 0.037 μg L−1. Finally, the prepared electrode was applied for the determination of Cu2+ in soil samples, and the results were in agreement with those obtained by inductively coupled plasma mass spectrometry.  相似文献   

17.
Demetalation of zinc 5,10,15,20‐tetraphenylporphyrin (ZnTPP) under acidic conditions and ion exchange with Cu2+ ions at neutral pH are both rapid reactions in the liquid medium. However, for ZnTPP monolayers adsorbed on a Au(111) surface exposed to aqueous solution, we find that, although ion exchange takes place rapidly as expected, demetalation does not occur, even at pH values as low as 0. Based on this, we conclude that metal center exchange on the surface does not proceed through a free‐base porphyrin as an intermediate. Furthermore, once formed, CuTPP is stable on the surface and the reverse exchange from CuTPP to ZnTPP in the presence of Zn2+ ions could not be achieved. The preference for copper is so strong that even an attempt to exchange adsorbed ZnTPP with Ni2+ ions in the presence of traces of Cu2+ yielded CuTPP rather than NiTPP.  相似文献   

18.
Q. Huang  G. Chen  J. Liu 《先进技术聚合物》2014,25(12):1391-1395
Polyanilines (PANIs) doped with Zn2+ and Cu2+ were synthesized by H2O2 oxidative polymerization of aniline in the presence of corresponding metal chloride in solution. The products were characterized by elemental analysis, UV‐Vis‐NIR, FTIR and Raman spectroscopies. Scanning electron micrograph was employed to examine the morphology of PANIs fabricated in the presence of different transition metals. Experimental results showed that transition metal ions had been successfully incorporated into the polymer, and there was a strong interaction between the transition metal ions and the PANI chains. The electrical conductivity of PANI doped with Zn2+ and Cu2+ is 0.37 and 0.21 S/cm, respectively, which is higher than that of HCl doping PANI corresponding to 0.052 S/cm. The cyclic voltammetric study has indicated that incorporation of metal ions in PANI backbone results in increasing of specific capacitance compared to that of HCl doping PANI. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

19.
In this study, we developed an electrochemical sensor for sensitive detection of Cu2+ based on gold nanoflowers (AuNFs)‐modified electrode and DNAzyme functionalized Au@MIL‐101(Fe) (MIL: Materials of Institute Lavoisier). The AuNFs‐modified indium tin oxide modified conductive glass electrode(AuNFs/ITO) prepared via electrodeposition showed improved electronic transport properties and provided more active sites to adsorb large amounts of oligonucleotide substrate (DNA1) via thiol‐gold bonds. The stable Au@MIL‐101(Fe) could guarantee the sensitivity because of its intrinsic peroxidase mimic property, while the Cu2+‐dependent DNA‐cleaving DNAzyme linked to Au@MIL‐101(Fe) achieved the selectivity toward Cu2+. After the DNAzyme substrate strand (DNA2) was cleaved into two parts due to the presence of Cu2+, the oligonucleotide fragment linked to MIL‐101(Fe) was able to hybridize with DNA1 adsorbed onto the surface of AuNFs/ITO. Due to the peroxidase‐like catalytic activity of MIL‐101(Fe) and the affinity recognition property of DNAzyme toward Cu2+, the electrochemical biosensor showed a sensitive detection range from 0.001 to 100 μM, a detection limit of 0.457 nM and a high selectivity, demonstrating its potential for Cu2+ detection in real environmental samples.  相似文献   

20.
New amphiphilic gelators that contained both Schiff base and L ‐glutamide moieties, abbreviated as o‐SLG and p‐SLG, were synthesized and their self‐assembly in various organic solvents in the absence and presence of metal ions was investigated. Gelation test revealed that o‐SLG formed a thermotropic gel in many organic solvents, whilst p‐SLG did not. When metal ions, such as Cu2+, Zn2+, Mg2+, Ni2+, were added, different behaviors were observed. The addition of Cu2+ induced p‐SLG to from an organogel. In the case of o‐SLG, the addition of Cu2+ and Mg2+ ions maintained the gelating ability of the compound, whilst Zn2+ and Ni2+ ions destroyed the gel. In addition, the introduction of Cu2+ ions caused the nanofiber gel to perform a chiral twist, whilst the Mg2+ ions enhanced the fluorescence of the gel. More interestingly, the Mg2+‐ion‐mediated organogel showed differences in the fluorescence quenching by D ‐ and L ‐tartaric acid, thus showing a chiral recognition ability.  相似文献   

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