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1.
The elemental composition (surface adsorbed and internalized fraction of Cu, Mo and P) in marine phytoplankton was first examined in cultures of the diatom Phaeodactylum tricornutum which were exposed to various levels of Cu concentrations ranging from 0.25 to 16 μmol/L with equivalent free [Cu2+] concentrations of 0.4–26 nmol/L. We observed an acceleration of algal growth rates (20–40%) with increasing ambient Cu levels, as well as slightly increased levels of internalized Cu in cells (2–13 × 10?18 mol/cell) although cellular Cu mostly accumulated onto the cell surface (>50% of the total: intracellular + surface adsorbed). In particular, we documented for the first time that the elemental composition (Mo and P) in algal cells varies dynamically in response to increased Cu levels: (1) Cellular P, predominantly in the intracellular compartment (>95%), shows with a net consumption as indicated by a gradual decrease with increasing [Cu2+] (120→50 × 10?15 mol P/cell) probably due to the fact that P, a backbone bioelement, is largely required in forming biological compartments such as cell membranes; and (2) cellular Mo, predominantly encountered in the intracellular compartment, showed up to tenfold increase in concentration in the cultures exposed to Cu, with a peak accumulation of 1.1 × 10?18 mol Mo/cell occurring in the culture exposed to [Cu2+] at 3.7 nmol/L. Such a net cellular Mo accumulation suggests that Mo might be specifically required in biological processes, probably playing a counteracting role against Cu.  相似文献   

2.
The water‐soluble luminescent CdSe quantum dots were prepared by ligand exchange with triethanolamine (TEA). Oxygen can reversibly enhance the fluorescence of the synthesized quantum dots (TEA‐CdSe‐QDs) in aqueous solution. Nitric oxide radical (NO) can react easily with dissolved oxygen in water and was found to have a significant quenching effect on the fluorescence of the TEA‐CdSe‐QDs. The fluorescence responses were concentration‐dependent and can be well described by the typical Stern–Volmer equation. A good linear relationship (R= 0.9963) was observed over the range 5.92 × 10?7 to 1.85 × 10?5 mol/L nitric oxide. Above this concentration was a second linear region ranging from 2.12 × 10?5 to 1.12 × 10?4 mol/L NO with a gentler slope. The detection limit, calculated following the 3σ IUPAC criteria, was 3.02 × 10?7 mol/L. The interference effect of some common interferents such as nitrite (NO2?), nitrate (NO3?), glucose and l ‐ascorbic acid on the detection of NO was negligible for the proposed system, demonstrating the potential utility of this probe for the detection of NO in biological systems. The possible mechanism was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

3.
Huimin Liu  Heyou Han 《Luminescence》2009,24(5):300-305
Perturbation of the tris(2,2′‐bipyridine)ruthenium(II) [Ru(bpy)32+]‐catalyzed Belousov–Zhabotinsky (BZ) oscillating chemiluminescence (CL) reaction induced by l ‐cysteine was observed in the closed system. It was found that the CL intensity was decreased in the presence of l ‐cysteine. Meanwhile, oscillation period and oscillating induction period were prolonged. The sufficient reproducible induction period was used as parameter for the analytical application of oscillating CL reaction. Under the optimum conditions, the changes in the oscillating CL induction period were linearly proportional to the concentration of l ‐cysteine in the range from 8.0 × 10?7 to 5.0 × 10?5 mol L?1 (r = 0.997) with a detection limit of 4.3 × 10?7 mol L?1. The possible mechanism of l ‐cysteine perturbation on the oscillating CL reaction was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
The main purpose of this study was to develop an inexpensive, simple, rapid and sensitive chemiluminescence (CL) method for the determination of glutamine (Gln) using a flow‐injection (FI) system. Gln was found to strongly inhibit the CL signal of the luminol–H2O2–CuSO4 system in Na2B4O7 solution. A new FI‐CL method was developed for the determination of Gln. Parameters affecting the reproducibility and CL detection were optimized systematically. Under the optimized conditions, the corresponding linear regression equation was established over the range of 5.0 × 10?7 to 2.5 × 10?6 mol/L with the detection limit of 1.8 × 10?8 mol/L. The relative standard deviation was found to be 1.8% for 11 replicate determinations of 1.5 × 10?6 mol/L Gln. The proposed method has been satisfactorily applied for the determination of Gln in real samples (Marzulene‐s granules) with recoveries in the range of 98.7–108.6%. The minimum sampling rate was about 100 samples/h. The possible mechanism of this inhibitory CL was studied by fluorescence spectrophotometer and UV–vis spectrophotometer. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

5.
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   

6.
A new 2,5‐diphenyl‐1,3,4‐oxadiazole‐based derivative (L) was synthesized and applied as a highly selective and sensitive fluorescent sensor for relay recognition of Cu2+ and S2? in water (Tris–HCl 10 mM, pH = 7.0) solution. L exhibits an excellent selectivity to Cu2+ over other examined metal ions with a prominent fluorescence ‘turn‐off’ at 392 nm. L interacts with Cu2+ through a 1:2 binding stoichiometry with a detection limit of 4.8 × 10–7 M. The on‐site formed L–2Cu2+ complex exhibits excellent selectivity to S2? with a fluorescence ‘off–on’ response via a Cu2+ displacement approach. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

7.
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   

8.
Both the molecular recognition and interaction of metallo‐β‐lactamase CcrA with l ‐captopril were studied by the combined use of fluorescence spectra and molecular dynamic simulation. The results showed that the binding constant was 8.89 × 104 L mol?1 at 296 K. Both Zn1 and Zn2 displayed tetrahedral coordination geometries in the CcrA–Lcap complex, the S atom in l ‐captopril displaced the nucleophilic hydroxide in apo CcrA and occupied the fourth coordination site for each ion, resulting in a competitively inhibited CcrA enzyme. Strong electrostatic interaction between the two zinc ions in CcrA and negatively charged l ‐captopril provided the main driving force for the binding affinity. Through a partly structural transformation from β‐sheet to random coil, loop 1 (residues 24–34) completely opened the binding pocket of CcrA to allow an induced fit of the newly introduced ligand. This study may provide some valuable information for designing and developing a more tightly binding inhibitor to resist superbugs.  相似文献   

9.
In this paper, an innovative and facile one‐pot method for synthesizing water‐soluble and stable fluorescent Cu nanoclusters (CuNCs), in which glutathione (GSH) served as protecting ligand and ascorbic acid (AA) as reducing agent was reported. The resultant CuNCs emitted blue‐green fluorescence at 440 nm, with a quantum yield (QD) of about 3.08%. In addition, the prepared CuNCs exhibited excellent properties such as good water solubility, photostability and high stability toward high ionic strength. On the basis of the selective quenching of Hg2+ on CuNCs fluorescence, which may be the result of Hg2+ ion‐induced aggregation of the CuNCs, the CuNCs was used for the selective and sensitive determination of Hg2+ in aqueous solution. The proposed analytical strategy permitted detection of Hg2+ in a linear range of 4 × 10?8 to 6 × 10?5 M, with a detection limit of 2.2 × 10?8 M. Eventually, the practicability of this sensing approach was confirmed by its successful application to assay Hg2+ in tap water, Lotus lake water and river water samples with the quantitative spike recoveries ranging from 96.9% to 105.4%.  相似文献   

10.
Lili Li  Hui Li  Gang Liu  Shouzhi Pu 《Luminescence》2017,32(8):1473-1481
A new photochromic diarylethene based on benzophenone hydrazone has been synthesized. Its photochromic and fluorescent properties changed upon alternating irradiation with UV /Vis light and adding Cu2+/EDTA in methanol, which showed that the diarylethene could be served as a colorimetric and fluorescent chemosensor for selective detection of Cu2+ based on internal charge transfer processes. The colorimetric and turn‐off fluorescent selective detection of Cu2+ was attributed to the 2:1 complex of the diarylethene and Cu2+. The binding constant (Ka ) was 1.53 × 104 L mol?1 and the limit of detection of the diarylethene for Cu2+ was calculated to be 1.45 × 10?6 mol L?1. In addition, the metal‐responsive photochromic behavior of diarylethene was applied successfully to the construction of a molecular logic circuit.  相似文献   

11.
This method is based on the enhancing effect of codeine (COD) and paracetamol (PAR) on the chemiluminescence (CL) reaction of Ru(phen)32+ with Ce(IV). In the batch mode, COD gives a relatively sharp peak with the highest CL intensity at 4.0 s, whereas the maximum CL intensity of the PAR appears at ~60 s after injection of Ce(IV) solution. Whole CL time profiles allowed use of the time‐resolved CL data in combination with multiway calibration techniques, as multiway partial least squares (N‐PLS), for the quantitative determination of both COD and PAR in binary mixtures. In this work, we found that the impact of Ce(IV) concentration on the CL intensity was different for COD and PAR. Therefore, a Ce(IV) concentration mode was added to the time and sample modes to obtain 3D data. The percent relative standard deviation (%RSD) values for 10 determinations of 1.0 × 10?5 mol/L of COD and 1.0 × 10?4 mol/L of PAR were 6.1% and 8.7%, respectively. The limit of detection (LOD) values (S/N = 3) were 0.9 × 10?8 mol/L and 1.0 × 10?6 mol/L for COD and PAR, respectively. The proposed method was successfully applied to the determination of PAR and COD in commercial pharmaceutical formulations. Acceptable recoveries (90–110%) were obtained for the quantification of these drugs in the real samples. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

12.
We investigated the effects of zinc or lead on growth and on exudation of fluorescent dissolved organic matter (FDOM) by the marine toxic dinoflagellate Alexandrium catenella (Whedon & Kofoid) Balech. The species was exposed to increasing free zinc (1.34 × 10?7 M–3.98 × 10?6 M) or lead (5.13 × 10?9 M–1.82 × 10?7 M) concentra‐tions. Low metal levels ([Zn2+] = 1.34 × 10?7 M; [Pb2+] = 5.13 × 10?9 M) had no effect on cell growth. Toxic effects were observed from higher metal contamination ([Zn2+] = 3.98 × 10?6 M; [Pb2+] = 6.54 × 10?8 M), as a conversion of vegetative cells into cysts. Analysis of the released FDOM by three‐dimensional (3‐D) fluorescence spectroscopy was achieved, using the parallel factor analysis (PARAFAC). The PARAFAC modeling revealed four components associated with two contributions: one related to the biological activity; the other linked to the organic matter decomposition in the culture medium. The C1 component combined a tryptophan peak and characteristics of humic substances, whereas the C2 component was considered as a tryptophan protein fluorophore. The two others C3 and C4 components were associated with marine organic matter production. Relea‐sed fluorescent substances were induced by low ([Zn2+]= 1.34 × 10?7 M; [Pb2+] = 5.13 × 10?9 M) and moderate ([Zn2+] = 6.21 × 10?7 M; [Pb2+] = 2.64× 10?9 M) metal concentrations, suggesting the activation of cellular mechanisms in response to metal stress, to exudate FDOM that could complex metal cations and reduce their toxicity toward A. catenella cells.  相似文献   

13.
A post‐chemiluminescence (PCL) phenomenon was observed when chloramphenicol was injected into a mixture of luminol and potassium periodate after the chemiluminescence (CL) reaction of luminol–potassium periodate had finished. The possible reaction mechanism was proposed based on studies of the CL kinetic characteristics, the CL spectra, the fluorescence spectra and the UV‐vis absorption spectra of the related substances. Based on the PCL reaction, a rapid and sensitive method for the determination of chloramphenicol was established. The linear response range was 6.0 × 10?7–1.0 × 10?5 mol/L, with a correlation coefficient of 0.9986. The relative standard deviation (RSD) for 5.0 × 10?6 mol/L chloramphenicol was 2.3% (n = 11). The detection limit was 1.6 × 10?7 mol/L. The method has been applied to the determination of chloramphenicol in pharmaceutical samples with satisfactory results. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

14.
The removal efficiency of Cu2+ by Spirulina platensis (strain FACHB‐834), in viable and heat‐inactivated forms, was investigated in the presence and absence of linear alkylbenzene sulfonate (LAS). When the initial Cu2+ concentration was in the range of 0.5–1.5 mg · L?1, a slight increase in growth rate of FACHB‐834 was observed. In contrast, when Cu2+ or LAS concentrations were at or higher than 2.0 or 6.0 mg · L?1, respectively, the growth of FACHB‐834 was inhibited and displayed yellowing and fragmentation of filaments. The presence of LAS improved Cu2+ removal by ~20%, and accelerated attainment of Cu2+ retention equilibrium. For the 2‐ mg · L?1 Cu2+ treatments, retention equilibrium occurred within 2 d and showed maximum Cu2+ removal of 1.83 mg · L?1. In the presence of LAS, the ratio of extracellular bound Cu2+ to intracellular Cu2+ taken up by the cells was lower (1.05–2.26) than corresponding ratios (2.46–7.85) in the absence of LAS. The percentages of extracellular bound Cu2+ to total Cu2+ removal (both bound and taken up by cells) in the presence of LAS ranged from 51.2% to 69.3%, which was lower than their corresponding percentages (71.1%–88.7%) in the absence of LAS. LAS promoted biologically active transport of the extracellular bound form of Cu2+ into the cell. In contrast, the addition of LAS did not increase the maximum removal efficiency of Cu2+ (61.4% ± 5.6%) by heat‐inactivated cells compared to that of living cells (59.6% ± 6.0%). These results provide a theoretical foundation for designing bioremediation strategies using FACHB‐834 for use in surface waters contaminated by both heavy metals and LAS.  相似文献   

15.
A new fluorescent Al3+‐probe, N‐allyl‐4‐[3,3′‐((2‐aminoethyl)azanediyl)‐bis(N´‐(2‐hydroxybenzylidene)propanehy‐drazide)]‐1,8‐naphthalimide ( L ), was designed and synthesized based on 1,8‐naphthalimide. The probe L contains 1,8‐naphthalimide moiety as the fluorophore and a Schiff base as the recognition group. The structure of L was determined by single crystal X‐ray. L emission at 526 nm increased on addition of Al3+ under excitation wavelength at 350 nm. L exhibited high selectivity and sensitivity fluorescence emission towards to Al3+ in ethanol/Tris–HCl buffer solution (1:1, v/v, pH = 7.2) as compared with other tested metal ions. A good linearity with a correlation coefficient (R2) of 0.99 was observed in the concentration range 2–10 μM. The binding constant and the detection limit of L for Al3+ were calculated to 2.6 × 104 M?1 and 0.34 μM, respectively. The results of experiments that including Job plot, ultraviolet–visible (UV–Vis) light titration, fluorescence titration, ESI‐MS and 1H NMR titration, indicated a 1:1 stoichiometric complex between L and Al3+. L was highly effective in monitoring Al3+ in real‐life Yellow River and tap water samples.  相似文献   

16.
A flow injection (FI) method is reported for the determination of l‐ cysteine, based on its enhancement on chemiluminescence (CL) emission of luminol oxidized by sodium persulphate in alkaline solution. The calibration graph was linear over the range 1.0 × 10–9–5.0 × 10–7 mol/L (r2 = 0.9992), with relative standard deviations (RSDs) in the range 1.1–2.3% (n = 4). The limit of detection (3σ blank) was 5.0 × 10–10 mol/L with a sample throughput of 120/h. The method was applied to pharmaceuticals and the results obtained were in reasonable agreement with the amount labelled. The proposed method was also applied to cysteine in synthetic amino acid mixtures. Calibration graphs of N‐acetylcysteine and glutathione over the range 1.0–50 × 10–8 and 0.5–7.5 × 10–7 mol/L were also established (r2 = 0.998 and 0.9986) with RSDs in the range 1.0–2.0% (n = 4), and the limits of detection (3σ blank) were 5.0 × 10–9 and 1.0 × 10–8 mol/L, respectively. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

17.
A sensitive and simple flow‐injection chemiluminescence (FI‐CL) method, which was based on the CL intensity generated from the redoxreaction of potassium permanganate (KMnO4)–formaldehyde in vitriol (H2SO4) medium, has been developed, validated and applied for the determination of naphazoline hydrochloride and oxymetazoline hydrochloride. Besides oxidants and sensitizers, the effect of the concentration of H2SO4, KMnO4 and formaldehyde was investigated. Under the optimum conditions, the linear range was 1.0 × 10?2–7.0 mg/L for naphazoline hydrochloride and 5.0 × 10?2–10.0 mg/L for oxymetazoline hydrochloride. During seven repeated inter‐day and intra‐day precision tests of 0.1, 1.0 and 10.0 mg/L samples, the relative standard deviations all corresponded to reference values. The detection limit was 8.69 × 10?3 mg/L for naphazoline hydrochloride and 3.47 × 10?2 mg/L for oxymetazoline hydrochloride (signal‐to‐noise ratio ≤3). This method has been successfully implemented for the determination of naphazoline hydrochloride and oxymetazoline hydrochloride in pharmaceuticals. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

18.
In this paper, a simple and highly sensitive spectrofluorimetric method was developed and validated for the determination of entacapone (ETC). The proposed method is based on forming a highly fluorescent product through the reduction of ETC with Zn/HCl. The produced fluorophore exhibits strong fluorescence at λem 345 nm after excitation at λex 240 nm. The use of fluorescence enhancers such as Tween‐80 and carboxy methyl cellulose (CMC) greatly enhanced the fluorescence of the produced fluorophore by 150% and 200%, respectively. Calibration curves showed good linear regression (r2 > 0.9998) within test ranges of 0.05–2.0 and 0.02–1.80 μg mL?1 with lower detection limits of 1.27 × 10?2 and 4.8 × 10?3 μg mL?1 and lower quantification limits of 4.21 × 10?2 and 1.61 × 10?2 μg mL?1 upon using Tween‐80 and or CMC, respectively. The method was successfully applied to the analysis of ETC in its pharmaceutical formulations (either alone or in presence of other co‐formulated drugs). The results were in good agreement with those obtained using the official method. The methods were further extended to determine the drug in human plasma samples, and to study the pharmacokinetics of ETC. The paper is the first report on the spectrofluorimetric determination of entacapone.  相似文献   

19.
A europium‐sensitized fluorescence spectrophotometry method using an anionic surfactant, sodium dodecyl benzene sulphonate (SDBS), was developed for the determination of gatifloxacin (GFLX). The GFLX–Eu3+–SDBS system was studied and it was found that SDBS significantly enhanced the fluorescence intensity of the GFLX–Eu3+ complex (about 25‐fold). The optimal experimental conditions were determined as follows: excitation and emission wavelengths of 338 and 617 nm, pH 7.5, 3.0 × 10–6 mol/L europium(III), and 5.0 × 10–5 mol/L SDBS. The enhanced fluorescence intensity of the system (ΔIf) showed a good linear relationship with the concentration of GFLX over the range 1.0 × 10–8–8.0 × 10–7 mol/L with a correlation coefficient of 0.9990. The detection limit (S:N = 3) was determined as 1.0 × 10–9 mol/L. This method has been successfully applied for the determination of GFLX in pharmaceuticals and human urine/serum samples. Compared with most other methods reported, the rapid and simple procedure proposed here offered higher sensitivity, wider linear range and good stability. The luminescence mechanism of the system is also discussed in detail. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

20.
Herein, a new recipe is introduced for the preparation of hydrogen phosphate ion‐imprinted polymer nanoparticles (nano‐IIP) in acetonitrile/water (63.5:36.5) using phosphoric acid as the template. The nano‐IIP obtained was used as the recognition element of a carbon paste potentiometric sensor. The IIP electrode showed a Nernstian response to hydrogen phosphate anion; whereas, the non‐imprinted polymer (NIP)‐based electrode had no considerable sensitivity to the anion. The presence of both methacrylic acid and vinyl pyridine in the IIP structure, as well as optimization of the functional monomers‐template proportion, was found to be important to observe the sensing capability of the IIP electrode. The nano‐IIP electrode showed a dynamic linear range of 1 × 10?5‐1 × 10?1 mol L‐1, Nernstian slope of 30.6 ± (0.5) mV decade ?1, response time of 25 seconds, and detection limit of 4.0 × 10?6 mol L?1. The utility of the electrodes was checked by potentiometric titration of hydrogen phosphate with La3+ solution.  相似文献   

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