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1.
A water‐soluble, high‐output fluorescent sensor, based on a lumazine ligand with a thiophene substituent for Cd2+, Hg2+ and Ag+ metal ions, is reported. The sensor displays fluorescence enhancement upon Cd2+ binding (log  β = 2.79 ± 0.08) and fluorescence quenching by chelating with Ag+ and Hg2+ (log β = 4.31 ± 0.15 and 5.42 ± 0.1, respectively). The mechanism of quenching is static and occurs by formation of a ground‐state non‐fluorescent complex followed by rapid intersystem crossing. The value of the Stern–Volmer quenching rate constant (kq) by Ag+ ions is close to 6.71 × 1012 mol/L/s at 298 K. The thermodynamic parameters (ΔG, ΔH and ΔS) were also evaluated and indicated that the complexation process is spontaneous, exothermic and entropically favourable. The quantitative linear relationship between the softness values of Klopman (σK) or Ahrland (σA) and the experimental binding constants (β) being in the order of Hg2+ > Ag+ > Cd2+ suggests that soft–soft interactions are the key for the observed sensitivity and selectivity in the presence of other metal ions, such as: Pb2+, Ni2+, Mn2+, Cu2+, Co2+, Zn2+ and Mg2+ ions. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

2.
Sodium dodecyl sulfate (SDS)-capped 1-pyrenecarboxaldehyde nanoparticles (PyalNPs) were prepared using a reprecipitation method in an aqueous medium and exhibited red-shifted aggregation-induced enhanced emission (AIEE). The dynamic light scattering (DLS) examination showed narrower particle size distribution with an average particle size of 41 nm, whereas −34.5 mV zeta potential value indicate the negative surface charge and good stability of nanoparticles (NPs) in an aqueous medium. The AIEE was seen at λmax = 473 nm in a fluorescence spectrum of a PyalNP suspension. In the presence of Cu2+ ions, the fluorescence of PyalNPs quenches very significantly, even in the presence of other metal ions like Ba2+, Ca2+, Cd2+, Co2+, Al3+, Fe2+, Hg2+, Ni2+ and Mg2+. The changes in the fluorescence lifetime of PyalNPs in the presence of Cu2+ ions suggested that the type of quenching was dynamic. The fluorescence quenching data for the NPs suspension fitted well into a typical Stern–Volmer relationship in the concentration range 1.0–25 μg/ml of Cu2+ ions. The estimated value of the correlation coefficient R2 = 0.9877 was close to 1 and showed the linear relationship between quenching data and Cu2+ ion concentration. The limit of detection (LOD) was found to be 0.94 ng/ml and is far below the tolerable intake limit value of 1.3 μg/ml accepted by the World Health Organization for Cu2+ ions in drinking water. The fluorescence quenching approach for a SDS-capped Pyal nanosuspension for copper ion quantification is of high specificity and coexisting ions were found to interfere very negligibly. The developed method was successfully applied for the estimation of copper ions in river water samples.  相似文献   

3.
A fluorescence and absorption chemosensor (SAAT) based on 5-(hydroxymethyl)-salicylaldehyde (SA) and o-aminothiophenol (AT) was designed and synthesized. SAAT in DMSO–HEPES (20.0 mM, v/v, 1:99, pH = 7.0) solution shows a highly selective and sensitive absorption and an ‘on–off’ fluorescence response to Cu2+ ions in aqueous solutions over all other competitive metal ions including Na+, Ag+, Ba2+, Ca2+, Cd2+, Mg2+, Zn2+, Cr3+, Al3+, Hg2+, K+, Mn2+, Ni2+, Sr2+, Tb3+ and Co2+. SAAT exhibits ratiometric absorption sensing ability for Cu2+ ions. Importantly, SAAT also can sense Cu2+ ions using fluorescence quenching, the fluorescence intensity of SAAT showed a good linear relationship with Cu2+ concentration, and the detection limit of Cu2+ was 0.34 μM. The results of Job's plot, Benesi–Hildebrand plot, mass spectra, and density functional theory calculations confirmed that the selective absorption and fluorescence response were attributed to the formation of a 1:1 complex between SAAT and Cu2+. SAAT in test film could identify Cu2+ in water samples using the intuitive fluorescence colour change under a UV lamp. SAAT has great application value as a selective and sensitive chemosensor to discriminate and detect Cu2+ ions.  相似文献   

4.
CdTe quantum dots (QDs) capped with different stabilizers, i.e. thioglycolic acid (TGA), 3‐mercaptopropionic acid (MPA) and glutathione (GSH) were investigated as fluorescent probes for the determination of Cu2+. The stabilizer was shown to play an important role in both the sensitivity and selectivity for the determination of Cu2+. TGA‐capped CdTe QDs showed the highest sensitivity, followed by the MPA and GSH‐capped CdTe QDs, respectively. The TGA‐ and MPA‐capped CdTe QDs were not selective for Cu2+ that was affected by Ag+. The GSH‐capped CdTe QDs were insensitive to Ag+ and were used to determine Cu2+ in water samples. Under optimal conditions, quenching of the fluorescence intensity (F0/F) increased linearly with the concentration of Cu2+ over a range of 0.10–4.0 µg/mL and the detection limit was 0.06 µg/mL. The developed method was successfully applied to the determination of Cu2+ in water samples. Good recoveries of 93–104%, with a relative standard deviation of < 6% demonstrated that the developed simple method was accurate and reliable. The quenching mechanisms were also described. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

5.
To develop conducting organic polymers (COPs) as luminescent sensors for determination of toxic heavy metals, a new benzene sulfonic acid‐doped polypyrrole (PPy‐BSA) thin film was electrochemically prepared by cyclic voltammetry (CV) on flexible indium tin oxide (ITO) electrode in aqueous solution. PPy‐BSA film was characterized by FTIR spectrometry, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The optical properties of PPy‐BSA were investigated by ultraviolet (UV)‐visible absorption and fluorescence spectrometry in dimethylsulfoxide (DMSO) diluted solutions. PPy‐BSA fluorescence spectra were strongly quenched upon increasing copper(II) ion (Cu2+) and lead(II) ion (Pb2+) concentrations in aqueous medium, and linear Stern–Volmer relationships were obtained, which indicated the existence of a main dynamic fluorescence quenching mechanism. BSA‐PPy sensor showed a high sensitivity for detection of both metallic ions, Cu2+ and Pb2+, with very low limit of detection values of 3.1 and 18.0 nM, respectively. The proposed quenching‐fluorimetric sensor might be applied to the determination of traces of toxic heavy metallic ions in water samples.  相似文献   

6.
《Free radical research》2013,47(4):205-218
In our search to establish a reference ·OH production system with respect to which the reactivity of copper(II) complexes could then be tested, the influence of free Cu2+ ions on the Cu+/H2O2 reaction has been investigated.

This influence depends on the CCu2+/CCu+ ratio. At low Cu2+ concentrations, ·OH damage to various detector molecules decreases with increasing Cu2+ concentrations until CCu2+/CCu+ reaches unity. Above this value, ·OH damage increases sharply until CCu2+/CCu+ becomes equal to 5 with salicylate and 2 with deoxyribose, ratios for which the protective effect of Cu2+ cancels. Finally, at higher concentrations, Cu2+ ions logically add their own ·OH production to that normally expected from Cu+ ions. The possible origin of this unprecedented alternate effect has been discussed. The possible influence of Cu+ ions on the generation of ·OH radicals by water gamma radiolysis has also been tested and, as already established for Cu2+ in a previous work, shown to be nonexistent. This definitely confirms that either form of ionised copper cannot scavenge ·OH radicals in the absence of a Iigand.  相似文献   

7.
In this study, fluorescent silver nanoclusters (Ag NCs) were synthesized using denatured fish sperm DNA as the template. In contrast to other methods, this method did not use artificial DNA as the template. After their reaction with denatured fish sperm DNA, Ag+ ions were reduced by NaBH4 to form Ag NCs. The Ag NCs showed a strong fluorescence emission at 650 nm when excited at 585 nm. The fluorescence intensity increased fourfold at pH 3.78, controlled with Britton–Robinson buffer solution. The fluorescence of the Ag NCs was quenched in the presence of trace mercury ions (Hg2+) in a weakly acidic medium and nitrogen atmosphere. The extent of the fluorescence quenching of Ag NCs strongly depends on the Hg2+ ion concentration over a linear range from 2.0 nmol L?1 to 3.0 μmol L?1. The detection limit (3σ/k) for Hg2+ was 0.7 nmol L?1. Thus, a sensitive and rapid method was developed for the detection of Hg2+ ions.  相似文献   

8.
This paper reports a convenient method for the synthesis of highly fluorescent Au nanoclusters (NCs) via electrostatically induced phase transfer. Furthermore, on the basis of an aggregation‐induced fluorescence quenching mechanism, the potential application for Cu2+ sensing on the fluorescence emission of the Au NCs is discussed. These prepared fluorescent Au NCs offer acceptable sensitivity, high selectivity, and a limit of quantitation of 0.02 μM for the measurement of Cu2+, which is lower than the maximum level (1 ppm, equals to 15.6 μM) of Cu2+ permitted in drinking water in China. This study contributes to the further development of practical applications with fluorescent NCs.  相似文献   

9.
A novel multifunctional fluorescent peptide sensor based on pentapeptide dansyl‐Gly‐His‐Gly‐Gly‐Trp‐COOH (D‐P5) was designed and synthesized efficiently using Fmoc solid‐phase peptide synthesis (SPPS). This fluorescent peptide sensor shows selective and sensitive responses to Hg2+ and Cu2+ among 17 metal ions and six anions studied in N‐2‐hydroxyethylpiperazine‐N‐2‐ethane sulfonic acid (HEPES) buffer solution. The peptide probe differentiates Hg2+ and Cu2+ ions by a ‘turn‐on’ response to Hg2+ and a ‘turn‐off’ response to Cu2+. Upon addition of Hg2+ or Cu2+ ions, the sensor displayed an apparent color change that was visible under an ultraviolet lamp to the naked eye. The limits of detection (LOD) of DP‐5 were 25.0 nM for Hg2+ and 85.0 nM for Cu2+; the detection limits for Cu2+ were much lower than the drinking water maximum contaminant levels set out by the United States Environmental Protection Agency (USEPA). It is noteworthy that both D‐P5‐Hg and D‐P5‐Cu systems were also used to detect S2? successfully based on the formation of ternary complexes. The LODs of D‐P5‐Hg and D‐P5‐Cu systems for S2? were 217.0 nM and 380.0 nM, respectively. Furthermore, the binding stoichiometry, binding affinity and pH sensitivity of the probe for Hg2+ and Cu2+ were investigated. This study gives new possibilities for using a short fluorescent peptide sensor for multifunctional detection, especially for anions.  相似文献   

10.
Two new twinborn benzimidazole derivates ( L and A ), which bonded pyridine via the ester space on the opposite and adjacent positions of the benzene ring of benzimidazole respectively, were designed and synthesized. Compound L displayed fluorescence quenching response only towards copper(II) ions (Cu2+) in acetonitrile solution with high selectivity and sensitivity. However, compound A presented ‘on–off’ fluorescence response towards a wide range of metal ions to different degrees and did not have selectivity. Furthermore, compound L formed a 1:1 complex with Cu2+ and the binding constant between sensor L and Cu2+ was high at 6.02 × 104 M?1. Job's plot, mass spectra, IR spectra, 1H‐NMR titration and density functional theory (DFT) calculations demonstrated the formation of a 1:1 complex between L and Cu2+. Chemosensor L displayed a low limit of detection (3.05 × 10?6 M) and fast response time (15 s) to Cu2+. The Stern–Volmer analysis illustrated that the fluorescence quenching agreed with the static quenching mode. In addition, the obvious difference of L within HepG2 cells in the presence and absence of Cu2+ indicated L had the recognition capability for Cu2+ in living cells.  相似文献   

11.
Latent fingerprints (LFPs) are one among the most important types of evidences at crime scenes because of the distinctiveness and tenacity of the friction ridges in fingerprints (FPs). Therefore, it is essential in forensic science to develop a reliable method to detect LFPs. Traditional detection methods still face a number of difficulties, such as limited sensitivity, low contrast, strong background, and complex processing stages. In this study, MgO-ZrO2:Tb3+ (1–5 mol%) (MZ:Tb) nanocomposites (NCs) were prepared via a simple solution combustion (SC) method at low temperature. The photoluminescence (PL) investigation demonstrates that when excited at 379 nm, the produced NCs emits distinctive emission peaks of terbium ions (Tb3+). According to the photometric results, the NCs can be employed as warm light NCs and emit light in the green portion of the colour spectrum. The estimated optical band gap from diffuse reflectance spectra is found to be in the range 4.84–4.97 eV. Regardless of the type of surface being used, the optimized MgO-ZrO2:Tb3+ (4 mol%) (MZ:4Tb) NCs has a strong ability to minimize background fluorescence interference. With high contrast LFP and I–V type of cheiloscopy, these NCs present a flexible fluorescent mark for the identification of levels 1–3 details in forensic investigation.  相似文献   

12.
Four series of borosilicate glasses modified by alkali oxides and doped with Tb3+ and Sm3+ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B2O3 + 10SiO2 + 5MgO + R + 0.5(Tb2O3/Sm2O3) [where R = 10(Li2O /Na2O/K2O) for series A and C, and R = 5(Li2O + Na2O/Li2O + K2O/K2O + Na2O) for series B and D]. The X‐ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the 5D47F5 (543 nm) transition of the Tb3+ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm3+ ions with the series C and D glasses showed strong reddish‐orange emission at 600 nm (4G5/26H7/2) with an excitation wavelength λexci = 404 nm (6H5/24F7/2). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb3+ and Sm3+ ions was studied to optimize the potential alkali‐oxide‐modified borosilicate glass.  相似文献   

13.
Herein, a boronic acid-based sensor was reported selectively to recognize Pd2+ ion. The fluorescence intensity increased 36-fold after sensor binding with 2.47 × 10−5 M of Pd2+ ion. It was carried out in the 99% aqueous solution for binding tests, indicating sensor having good water solubility. In addition, it is discernible that Pd2+ ion turned on the blue fluorescence of sensor under a UV–lamp (365 nm), while other ions (Ag+, Al3+, Ba2+, Ca2+, Cr2+, Cd2+, Co2+, Cs2+, Cu2+, Fe2+, Fe3+, K+, Li+, Mg2+, Mn2+, Na+, Ni2+ and Zn2+) did not show the similar change. Furthermore, sensor has a low limit of detection (38 nM) and high selectivity, which exhibits the potential for the development of Pd2+ recognition in practical environments.  相似文献   

14.
The red fluorescent protein, DsRed, and a few of its mutants have been shown to bind copper ions resulting in quenching of its fluorescence. The response to Cu2+ is rapid, selective, and reversible upon addition of a copper chelator. DsRed has been employed as an in vitro probe for Cu2+ determination by us and other groups. It is also envisioned that DsRed can serve as an intracellular genetically encoded indicator of Cu2+ concentration, and can be targeted to desired subcellular locations for Cu2+ determination. However, no information has been reported yet regarding the mechanism of the fluorescence quenching of DsRed in the presence of Cu2+. In this work, we have performed spectroscopic investigations to determine the mechanism of quenching of DsRed fluorescence in the presence of Cu2+. We have studied the effect of Cu2+ addition on two representative mutants of DsRed, specifically, DsRed-Monomer and DsRed-Express. Both proteins bind Cu2+ with micromolar affinities. Stern-Volmer plots generated at different temperatures indicate a static quenching process in the case of both proteins in the presence of Cu2+. This mechanism was further studied using absorption spectroscopy. Stern-Volmer constants and quenching rate constants support the observation of static quenching in DsRed in the presence of Cu2+. Circular dichroism (CD)-spectroscopic studies revealed no effect of Cu2+-binding on the secondary structure or conformation of the protein. The effect of pH changes on the quenching of DsRed fluorescence in the presence of copper resulted in pKa values indicative of histidine and cysteine residue involvement in Cu2+-binding.  相似文献   

15.
Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg−1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results.  相似文献   

16.
The behaviors of 15 kinds of metal ions in the thiol‐capped CdTe quantum dots (QDs)–H2O2 chemiluminescence (CL) reaction were investigated in detail. The results showed that Ag+, Cu2+ and Hg2+ could inhibit CdTe QDs and H2O2 CL reaction. A novel CL method for the selective determination of Ag+, Cu2+ and Hg2+ was developed, based on their inhibition of the reaction of CdTe QDs and H2O2. Under the optimal conditions, good linear relationships were realized between the CL intensity and the logarithm of concentrations of Ag+, Cu2+ and Hg2+. The linear ranges were from 2.0 × 10?6 to 5.0 × 10?8 mol L?1 for Ag+, from 5.0 × 10?6 to 7.0 × 10?8 mol L?1 for Cu2+ and from 2.0 × 10?5 to 1.0 × 10?7 mol L?1 for Hg2+, respectively. The limits of detection (S/N = 3) were 3.0 × 10?8, 4.0 × 10?8 and 6.7 × 10?8 mol L?1 for Ag+, Cu2+ and Hg2+, respectively. A possible mechanism for the inhibition of CdTe QDs and H2O2 CL reaction was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

17.
The addition of reducing agents, i.e., ascorbic acid or sodium borohydride, to a DNA solution containing Cu2+ ions causes changes in the DNA absorption spectra which are due to a new absorption band with a maximum at 280 mμ assigned to a DNA base–Cu1+ complex. The stoichiometry of the complex is one Cu1+ ion per four bases of DNA. The DNA–Cu1+ complex has an increased melting temperature and rather different circular dichroism curve as compared with DNA itself. It is inferred that the above effects are caused by proton transfer along the hydrogen bond from guanine to cytosine under complexing of Cu1+ ions with the N7 atom of the guanine of DNA.  相似文献   

18.
The synthesis of the Li2SO4: Cu phosphor using a wet chemical method is reported here. The XRD technique showed the crystalline nature of the prepared material. The presence of Na and K in the host affected the observed photoluminescence characteristics of Li2SO4: Cu. Photoluminsecent emission spectra of Li2SO4: Cu phosphor showed a very strong prominet peak at 387 nm in the indigo region due to 3d9 4 s1 ? 3d10 transition of the Cu+ ion. The increase in peak intensity of the PL spectrum suggests that Cu+ acts as the luminescence center in the present matrix. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

19.
Summary Micromolar concentrations of silver ion activate large Ca2+ fluxes across the plasma membrane of intact rod outer segments isolated from bovine retinas (intact ROS). The rate of Ag+-induced Ca2+ efflux from intact ROS depended on the Ag+ concentration in a sigmoidal manner suggesting a cooperative mechanism with a Hill coefficient between 2 and 3. At a concentration of 50 m Ag+ the rate of Ca2+ efflux was 7×106 Ca2+/outer segment/sec; this represents a change in total intracellular Ca2+ by 0.7mm/outer segment/sec. Addition of the nonselective ionophore gramicidin in the absence of external alkali cations greatly reduced the Ag+-induced Ca2+ efflux from intact ROS, apparently by enabling internal alkali cations to leak out. Adding back alkali cations to the external medium restored Ag+-induced Ca2+ efflux when gramicidin was present. In the presence of gramicidin, Ag+-induced Ca2+ efflux from intact ROS was blocked by 50 m tetracaine orl-cis diltiazem, whereas without gramicidin both blockers were ineffective. Bothl-cis diltiazem and tetracaine are blockers of one kinetic component of cGMP-induced Ca2+ flux across ROS disk membranes. The ion selectivity of the Ag+-induced pathway proved to be broad with little discrimination between the alkali cations Li+, Na+, K+, and Cs+ or between Ca2+ and Mg2+. The properties of the Ag+-induced pathway(s) suggest that it may reflect the cGMP-dependent conductance opened in the absence of cGMP by silver ions.  相似文献   

20.
Peng Du  Jae Su Yu 《Luminescence》2017,32(8):1504-1510
A series of Sm3+‐activated Sr3La(VO4)3 phosphors were synthesized by a facile sol‐gel method. X‐ray diffraction patterns and photoluminescence (PL)/cathodoluminescence (CL) spectra as well as PL decay curves were employed to characterize the obtained samples. Upon 402 nm light excitation, the characteristic emissions of Sm3+ ions corresponding to 4G5/26HJ transitions were observed in all the as‐prepared products. The PL emission intensity was increased with increase in Sm3+ ion concentration, while concentration quenching occurred when the doping concentration was over 4 mol%. The non‐radiative energy transfer mechanism for concentration quenching of Sm3+ ions was dominated by dipole–dipole interaction and the critical distance was around 21.59 Å. Furthermore, temperature‐dependent PL emission spectra revealed that the obtained phosphors possessed good thermal stability with an activation energy of 0.19 eV. In addition, the CL spectra of the samples were almost the same as the PL spectra, and the CL emission intensity showed a tendency to increase with increase in accelerating voltage and filament current. These results suggest that the Sm3+‐activated Sr3La(VO4)3 phosphors with good color coordinates, high color purity and superior thermal stability may be a potential candidate for applications in white light‐emitting diodes and field‐emission displays as red‐emitting phosphors.  相似文献   

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