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1.
A novel method of first derivative synchronous fluorescence was developed for the rapid simultaneous analysis of trace 1-hydroxypyrene (1-OHP), 1-naphthol (1-NAP), 2-naphthol (2-NAP), 9-hydroxyphenanthrene (9-OHPe) and 2-hydroxyfluorene (2-OHFlu) in human urine. Only one single scan was needed for quantitative determination of five compounds simultaneously when Δλ = 10 nm was chosen. In the optimal experimental conditions, there was a linear relationship between the fluorescence intensity and the concentration of 1-OHP, 1-NAP, 2-NAP, 9-OHPe and 2-OHFlu in the range of 1.75 × 10−9 to 4.50 × 10−6 mol L−1, 3.64 × 10−8 to 2.20 × 10−4 mol L−1, 8.18 × 10−9 to 1.20 × 10−4 mol L−1, 3.26 × 10−9 to 8.50 × 10−5 mol L−1 and 4.88 × 10−9 to 5.50 × 10−6 mol L−1, respectively. The limits of detection (LOD) were found to be 5.25 × 10−10 mol L−1 for 1-OHP, 1.10 × 10−8 mol L−1 for 1-NAP, 2.46 × 10−9 mol L−1 for 2-NAP, 9.77 × 10−10 mol L−1 for 9-OHPe and 1.46 × 10−9 mol L−1 for 2-OHFlu. The proposed method is reliable, selective and sensitive, and has been used successfully in the determination of traces of 1-OHP, 1-NAP, 2-NAP, 9-OHPe and 2-OHFlu in human urine samples, whose results were in good agreement with those gained by the HPLC method.  相似文献   

2.
A method for determination of nine brominated phenols as environmental risk compounds was developed by on-line coupled capillary isotachophoresis and capillary zone electrophoresis (ITP–CZE). For ITP step, 1 × 10−2 mol L−1 hydrochloric acid with 3 × 10−2 mol L−1 ammediol pH 9.1 was used as the leading electrolyte, and 3 × 10−2 mol L−1 β-alanine with 2 × 10−2 mol L−1 sodium hydroxide pH 10.05 was used as the terminating electrolyte. As the background electrolyte for CZE separation, 2.5 × 10−2 mol L−1 β-alanine with 2.5 × 10−2 mol L−1 lysine pH 9.6 was used. All electrolytes contained 0.05% or 0.1% (m/v) hydroxyethylcellulose to suppress the electroosmotic flow. UV detection at wavelength 220 nm was used. Detection limits in order of tens of nmol L−1 were achieved. Good repeatability of migration times (less than 0.33% RSD) and good repeatability of peak areas (less than 7.19% RSD) at concentration level 5 × 10−8 mol L−1 were observed. Developed ITP–CZE method was applied to determination of brominated phenols in spiked tap and river water samples.  相似文献   

3.
A fluorometric method for quantity analysis of biothiols was developed using a graphene oxide (GO)-based “molecular beacon”-like probe, which consisted of FITC labeled thymine (T)-rich single-stranded DNA (ssDNA), GO and Hg2+ ions. The labeled ssDNA containing T–T mismatches would self-hybridize to duplex in the presence of Hg2+, which can avoid its adsorption on GO and the fluorescence of this GO-based probe was recovered. The fluorescence of the probe quenched after the addition of biothiols such as glutathione (GSH) and cysteine (Cys) owing to thiol groups can selectively competitive ligation of Hg2+ ions with T–T mismatches. In the present work, the GO-based probe was used for the determination of GSH and Cys. Under the optimal conditions, a linear correlation was established between fluorescence intensity ratio I0/I and the concentration of GSH in the range of 2.0 × 10−9–5.0 × 10−7 mol L−1 with a detection limit of 1.0 × 10−9 mol L−1. The linear range for Cys is from 5.0 × 10−9 to 4.5 × 10−7 mol L−1 with a detection limit of 2.0 × 10−9 mol L−1. The proposed method was applied to the determination of GSH in human serum and cell extract samples with satisfactory results.  相似文献   

4.
The simultaneous determination of levodopa (LD) and propranolol (PRO) using fluorescence spectrometric technique is described. The method involves measuring the natural fluorescence of these drugs in the micellar media of sodium dodecyl sulfate (SDS) using principal component analysis-feed-forward neural networks (PC-FFNNs). Experimental conditions such as effect of pH and SDS concentration were optimized. Under the optimum conditions, the linear determination ranges of LD and PRO are 2.0 × 10−8 to 1.0 × 10−5 mol L−1 and 3.6 × 10−9 to 1.8 × 10−6 mol L−1, respectively. A set of synthetic binary mixtures of LD and PRO was prepared and their concentrations were predicted by the proposed method. Satisfactory results were obtained by the combination of fluorescence technique with chemometrics methods. The method was successfully applied to the determination of LD and PRO in tap water and in urine samples.  相似文献   

5.
Ultrasensitive cysteine sensing using citrate-capped CdS quantum dots   总被引:1,自引:0,他引:1  
Wang GL  Dong YM  Yang HX  Li ZJ 《Talanta》2011,83(3):943-947
The importance of cysteine (Cys) in biological systems has stimulated a great deal of efforts in the development of analytical methods for the determination of this amino acid. In this work, a novel fluorescent probe for Cys based on citrate (Cit)-capped CdS quantum dots (QDs) is reported. The Cit-capped CdS QDs fluorescent probe offers good sensitivity and selectivity for detecting Cys. A good linear relationship was obtained from 1.0 × 10−8 mol L−1 to 5.0 × 10−5 mol L−1 for Cys. The detection limit was calculated as 5.4 × 10−9 mol L−1. The proposed method was applied to detect Cys in human urine samples, which showed satisfactory results. This assay is based on both the lability of Cit and the strong affinity of thiols to the surface of CdS QDs. The addition of Cys improved the passivation of the surface traps of CdS QDs and enhanced the fluorescence intensity.  相似文献   

6.
Based on the characteristics of synchronous fluorescence spectroscopy (SFS), a new method with high sensitivity and selectivity was developed for rapid determination of silver ion with functional cadmium sulphide (CdS) nanoparticles as a fluorescence probe. When Δλ (λem − λex) = 215 nm, maximum synchronous fluorescence is produced at 304 nm. Under optimal conditions, functional cadmium sulphide displayed a calibration response for silver ion over a wide concentration range from 0.8 × 10−10 to 1.5 × 10−8 mol L−1. The limit of detection was 0.4 × 10−10 mol L−1 and the relative standard deviation of seven replicate measurements for the lowest concentration (0.8 × 10−10 mol L−1) was 2.8%. Compared with several fluorescence methods, the proposed method had a wider linear range and improved the sensitivity. Furthermore, the concentration dependence of the synchronous fluorescence intensity is effectively described by a Langmuir-type binding isotherm.  相似文献   

7.
Pyrolytic graphite electrodes (PGE) were modified into dopamine solutions using phosphate buffer solutions, pH 10 and 6.5, as supporting electrolyte. The modification process involved a previous anodization of the working electrode at +1.5 V into 0.1 mol L−1 NaOH followed by other anodization step, in the same experimental conditions, into dopamine (DA) solutions. pH of the supporting electrolyte performed an important role in the production of a superficial melanin polymeric film, which permitted the simultaneous detection of ascorbic acid (AA), (DA) and uric acid (UA), ΔEAA-DA = 222 mV; ΔEAA-UA = 360 mV and ΔEDA-UA = 138 mV, avoiding the superficial poisoning effects. The calculated detection limits were: 1.4 × 10−6 mol L−1 for uric acid, 1.3 × 10−5 mol L−1 for ascorbic acid and 1.1 × 10−7 mol L−1 for dopamine, with sensitivities of (7.7 ± 0.5), (0.061 ± 0.001) and (9.5 ± 0.05) A mol−1 cm−2, respectively, with no mutual interference. Uric acid was determined in urine, blood and serum human samples after dilution in phosphate buffer and no additional sample pre-treatment was necessary. The concentration of uric acid in urine was higher than the values found in blood and serum and the recovery tests (92-102%) indicated that no matrix effects were observed.  相似文献   

8.
A novel method for the simultaneous determination of 1-hydroxypyrene (1-OHP), β-naphthol (β-NAP) and 9-hydroxyphenanthrene (9-OHPe) in human urine has been established by using synchronous fluorescence spectrometry. It was based on the fact that synchronous fluorescence spectrometry can resolve the broad-band overlapping of conventional fluorescence spectra, which arise from their similar molecular structures. Only one single scan is needed for quantitative determination of three compounds simultaneously when Δλ = 15 nm is chosen. The signals detected at these three wavelengths, 369.6, 330.0 and 358.0 nm, vary linearly when the concentration of 1-OHP, β-NAP and 9-OHPe is in the range of 2.16 × 10−8-1.50 × 10−5 mol L−1, 1.20 × 10−7-1.10 × 10−5 mol L−1 and 1.07 × 10−7-3.50 × 10−5 mol L−1, respectively. The correlation coefficients for the standard calibration graphs were 0.994, 0.999 and 0.997 (n = 7) for 1-OHP, β-NAP and 9-OHPe, respectively. The limits of detection (LOD) for 1-OHP, β-NAP and 9-OHPe were 6.47 × 10−9 mol L−1, 3.60 × 10−8 mol L−1 and 3.02 × 10−8 mol L−1with relative standard deviations (R.S.D.) of 4.70-6.40%, 2.80-4.20%, 3.10-4.90% (n = 6), respectively. The method described here had been applied to determine traces of 1-OHP, β-NAP and 9-OHPe in human urine, and the obtained results were in good agreement with those obtained by the HPLC method. In addition, the interaction modes between β-cyclodextrin (β-CD) and 1-OHP, β-NAP or 9-OHPe, as well as the mechanism of the fluorescence enhancement were also discussed.  相似文献   

9.
Tang B  Zhang L  Xu KH 《Talanta》2006,68(3):876-882
A new kind of near-infrared fluorescence agent, tricarbochlorocyanine dye (Cy.7.Cl), had been synthesized in house and used for near-infrared spectrofluorimetric determination of hydrogen peroxide (H2O2) by flow injection analysis (FIA) for the first time. The oxidation reaction of Cy.7.Cl with H2O2 occurred under the catalysis of horseradish peroxidase (HRP) and it was studied in detail. The possible reaction mechanism was discussed. Under optimal experimental conditions, fluorescence from Cy.7.Cl displayed excitation and emission maxima (ex/em) at 780 and 800 nm, respectively. The two linear working ranges were 1.86 × 10−7 to 4.11 × 10−7 mol L−1 and 4.11 × 10−7 to 7.19 × 10−6 mol L−1, respectively. The detection limit was 5.58 × 10−8 mol L−1 of H2O2. The effect of interferences was studied. The proposed method was successfully applied to the determination of hydrogen peroxide in rainwater, serum and plant samples.  相似文献   

10.
Under the conditions of 0.04 mol L−1 HCl-8.0 × 10−4 mol L−1 KI, there is a fluorescence peak at 540 nm and a synchronous fluorescence peak at 540 nm for rhodamine 6G (RhG). When there is IO3, it reacts with exceed I to form I3. And I3 and RhG combine into ion association particles. The particles exhibit three resonance scattering peaks at 320, 400 and 595 nm. And there is fluorescence quenching at 540 nm. Iodine concentration is proportional to the intensity of the resonance scattering intensity at 400 nm in the range of 1.0-20 × 10−7 mol L−1. And a new resonance scattering spectral (RSS) method has been described for the determination of IO3 in salt samples. The spectral results have been verified that the formation of (RhG-I3)n association particles and solid-liquid interfaces are the main factor that cause the fluorescence quenching and resonance scattering effects.  相似文献   

11.
High-performance liquid chromatography (HPLC) with tris(2,2′-bipyridyl)ruthenium(II) chemiluminescence detection methodology is reported for the determination of the atypical antipsychotic drug quetiapine and the observation of its major active and inactive metabolites in human urine and serum. The method uses a monolithic chromatographic column allowing high flow rates of 3 mL min−1 enabling rapid quantification. Flow injection analysis (FIA) with tris(2,2′-bipyridyl)ruthenium(II) chemiluminescence detection and HPLC time of flight mass spectrometry (TOF-MS) were used for the determination of quetiapine in a pharmaceutical preparation to establish its suitability as a calibration standard. The limit of detection achieved with FIA was 2 × 10−11 mol L−1 in simple aqueous solution. The limits of detection achieved with HPLC were 7 × 10−8 and 2 × 10−10 mol L−1 in urine and serum, respectively. The calibration range for FIA was between 5 × 10−9 and 1 × 10−6 mol L−1. The calibration ranges for HPLC were between 1 × 10−7-1 × 10−4 and 1 × 10−8-1 × 10−4 mol L−1 in urine and serum, respectively. The quetiapine concentrations in patient samples were found to be 3 × 10−6 mol L−1 in urine and 7 × 10−7 mol L−1 in serum. Without the need for preconcentration, the HPLC detection limits compared favourably with those in previously published methodologies. The metabolites were identified using HPLC-TOF-MS.  相似文献   

12.
Morales L  Toral MI  Alvarez MJ 《Talanta》2007,74(1):110-118
In this work, a characterization of reagent chromophere 5-(4-sulphophenylazo)-8-aminoquinoline [SPA] by IR and 1H RMN was carried out and a pKa value of 3.55 ± 0.03 was found as well. An 1:2 stoichiometry for the Cu(II)-SPA complex was determined at pH 9 by Job and molar ratio methods. A value of 1.4 × 1014 for the stability constant was also found. Based on the formation of this complex a new method for the copper determination in presence of gold and silver was developed by derivative spectrophotometry using a previous preconcentration on solid phase. In this method, the analytical measures were executed directly in the solid phase containing the complex. The Cu(II) reacts with the reagent chromophere SPA previously retained in the anionic exchange DEAE Sephadex A25. In this determination, the first derivative at 605 nm was used. The quantification range was between (3.2 ± 0.3 × 10−1) × 10−8 and (94.4 ± 0.9) × 10−8 mol L−1 (3.2 ± 0.3 × 10−1) × 10−8 , and (94.4 ± 0.9) × 10−8 mol L−1. The repeatability expressed as RSD was between 1.1 and 2.0%. The method was applied successfully for the copper determination in mineral residuals and natural water samples. The results were consistent with those provided by ICP-mass spectrometry.  相似文献   

13.
A novel optical sensor based on a redox reaction for the determination of iodide has been developed. The optode membrane is constructed by immobilization of methyltrioctylammonium chloride on triacetylcellulose polymer. The exchange of chloride as counter ion with iodate in the membrane changes the color to yellow, when it is placed in acidic solution of iodide. The sensor can readily be regenerated by 0.1 mol L−1 NaOH in less than 15 s. The optode has a linear range of 3.94 × 10−6 to 5.51 × 10−5 mol L−1 of iodide ions with a limit of detection 7.44 × 10−7 mol L−1. The relative standard deviation for eight replicate measurements of 3.94 × 10−6 and 1.57 × 10−5 mol L−1 of iodide was 2.83 and 1.38%, respectively. The sensor was successfully applied to the determination of iodide in tablet, powdered milk and urine samples.  相似文献   

14.
Herein, an innovative and simple strategy for synthesizing high fluorescent Cu nanoclusters was successfully established while l-cysteine played a role as the stabilizer. Meaningfully, the current Cu nanoclusters together with a quantum yield of 14.3% were prepared in aqueous solution, indicating their extensive applications. Subsequently, the possible fluorescence mechanism was elucidated by fluorescence, UV–vis, HR-TEM, FTIR, XPS, and MS. Additionally, the CuNCs were employed for assaying Hg2+ on the basis of the interactions between Hg2+ and l-cysteine; thus facilitating the quenching of their fluorescence. The proposed analytical strategy permitted detections of Hg2+ in a linear range of 1.0 × 10−7 mol L−1 × 10−3 mol L−1, with a detection limit of 2.4 × 10−8 mol L−1 at a signal-to-noise ratio of 3. Significantly, this CuNCs described here were further applied for coding and fluorescent staining, suggesting may broaden avenues toward diverse applications.  相似文献   

15.
Quinolones (Qs) can form the complex with Tb(III) ion, and the intramolecular energy transfer from Qs to Tb(III) takes place when excited. And thus the characteristic fluorescence of Tb(III) ion was enhanced and the maximum fluorescence peak locates at 545 nm. The second-order scattering (SOS) peak at 545 nm also appears for the Tb(III)-Qs complexes with the exciting wavelength of 274 nm. When the silver nanoparticles were added to the Tb(III)-Qs system, the luminescence intensity at 545 nm greatly increased. And the relative intensity is proportional to the amount of Qs. Based on this phenomenon, a novel method for determination of quinolones has been developed by using a common spectrofluorometer to measure the intensity of fluorescence and SOS. The luminescence intensity is greatly enhanced by silver nanoparticles in the pH range 5.5-6.2. The calibration graphs for pipemidic acid (PPA) and lomefloxacin (LMFX) are linear in the range 2.0 × 10−10 to 1.0 × 10−5 and 1.0 × 10−9 to 1.0 × 10−5 mol L−1, respectively. The limits of detection are 4.7 × 10−11 mol L−1 for PPA and 1.1 × 10−10 mol L−1 for LMFX. The method was applied satisfactorily to the determination of the two quinolones (Qs) in tablet, capsule, urine and serum samples. The experimental results showed that it is the certain size and certain concentration of silver nanoparticles that can greatly enhance the fluorescence -SOS intensity.  相似文献   

16.
An optical sensor for mercury ion (Hg2+), based on quenching the fluorescence of the sensing reagent porphyrin immobilized in plasticized poly(vinyl chloride) (PVC) membrane, has been developed. The responses to mercury ion were compared for the sensors modified with three porphyrin compounds including 5,10,15,20-tetraphenylporphyrin (TPP), tetra(p-dimethylaminophenyl)porphyrin (TDMAPP) and tetra(N-phenylpyrazole) porphyrin (TPPP). Among them, TDMAPP showed the most remarkable response to Hg2+. The drastic decrease of the TDMAPP fluorescence intensity was attributed to the formation of a complex between TDMAPP and Hg2+, which has been utilized as the fabrication basis of a Hg2+-sensitive fluorescence sensor. The analytical performance characteristics of the TDMAPP modified sensor was investigated. The response mechanism, especially involving the response difference of three porphyrin compounds, was discussed in detail. The sensor can be applied to the quantification of Hg2+ with a linear range covering from 4.0 × 10−8 mol L−1 to 4.0 × 10−6 mol L−1. The limit of detection was 8.0 × 10−9 mol L−1. The sensor exhibited excellent reproducibility, reversibility and selectivity. Also, the TDMAPP-based sensor was successfully used for the determination of Hg2+ in environmental water samples.  相似文献   

17.
Three Mn(III) porphyrins were used for the design of carbon paste and diamond paste based microelectrodes, which were employed for the determination of dopamine in pharmaceutical and biological samples using differential pulse voltammetry (DPV). The limits of detection lie between 1.6 × 10−13 and 2.0 × 10−6 mol L−1 while the sensitivities were between 230 pA μmol L−1 and 3.24 μA mol L−1. Dopamine was recovered reliable from pharmaceutical and biological samples in percentages higher than 91.00% and 92.00%, respectively. The surface of the microelectrodes can easily be renewed by simple polishing, obtaining a fresh surface ready for use in a new assay.  相似文献   

18.
Chung KH  Lee W  Cho YH  Choi GS  Lee CW 《Talanta》2005,65(2):389-395
The complexation of europium ion (Eu(III)) with a soil fulvic acid (FA) has been studied at pH 5 in 0.01 M NaClO4 by different experimental methods, i.e. synchronous fluorescence spectroscopy (SyFS) and time resolved laser-induced fluorescence spectroscopy (TRLFS). A series of SyFS quenching spectra was obtained by increasing the Eu(III) concentration and keeping the FA concentration constant. The emission spectra and fluorescence lifetimes of the Eu(III) bound to the FA were also measured by a TRLFS system using the same solution used in the SyFS spectral measurement. From the analysis of the fluorescence data obtained by the SyFS and the TRLFS using a non-linear least-squares method, the concentration of the binding sites (CL) of the FA accessible for the Eu(III) and the corresponding conditional stability constants (log K) were estimated. The two different methods gave rise to constants being comparable with one another. The log K and CL values (mean ± standard deviation of three determinations) determined by the SyFS were 6.4 ± 0.2 (6.7 ± 0.1 μmol L−1: by the TRLFS) and 10 ± 1 μmol L−1 (7 ± 1 μmol L−1: by the TRLFS), respectively. The applicability of the FA fluorescence quenching techniques for estimating the europium binding parameters was proved by the direct monitoring of the Eu(III) bound to the FA using the TRLFS system.  相似文献   

19.
The carbazole derivative, 9-ethyl-3-carbazylidene carbazole hydrazone (ECCH) with two conjugated carbazole rings have been applied as a fluorescence carrier for preparation of an iodine sensitive optical chemical sensor. The response of the sensor is based on quenching of the fluorescence of ECCH by iodine. The conjugated carbazole dimer based sensor shows a linear response toward iodine in the concentration range 1.0 × 10−6 to 1.0 × 10−4 mol L−1, with a detection limit of 8.0 × 10−7 mol L−1 at pH of 7.0. The effect of composition of the sensor membrane was studied, and the experimental conditions were optimized. Most commonly coexisting ions do not interfer with the iodine assay. The sensor shows sufficient repeatability, selectivity, operational lifetime of two months and a fast response of less then 50 s. The sensor has been used for determination of iodine in water samples.  相似文献   

20.
Ayman A. Abdel Aziz 《Talanta》2010,80(3):1356-1363
A highly selective membrane electrodes based on a two newly synthesized nickel (II) Schiff bases, [NiL1] and [NiL2] where L1 and L2 are N,N/bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L1) and N,N/bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L2) were used as a neutral carrier ionophores for static and hydrodynamic potentiometric mode of operations for the determination of periodate. Under static mode of operation, the sensors displayed a near-Nernstian slope of −66.1 ± 0.8 and −59.9 ± 1.1 mV decade−1 of activity and detection limits to 5.2 × 10−6 and 7.3 × 10−6 mol L−1 for the sensors based on [NiL1] and [NiL2], respectively. Under hydrodynamic mode of operation (FIA), the slope of the calibration plot, limit of detection, and working linear range were −71.1 mVdecade−1 of activity, 7.3 × 10−6 and 1.0 × 10−5 to 1.0 × 10−3 mol L−1, respectively. The response time of the sensors in whole concentration ranges was very short (<10 s). The response of the sensors was independent on the pH range of 3-8. A tubular version was further developed and coupled to a flow injection system for ascorbic acid (AA) determination in beverages and pharmaceutical preparations. This approach was achieved by selecting a 50-cm reactor and an overall flow of 3 mL min−1, and injecting volume 100 μL of AA standards in a 1.0 × 10−4 mol L−1 IO4 solution. Under these conditions, a linearity range of 2-13 μg mL−1, with a slope of 4.97 mV (mg/L)−1 (r2 = 0.9995), detection limit 0.9 mg L−1 and a reproducibility of ±1.1 mV (n = 5) was recorded. This simple and inexpensive flow injection analysis manifold, with a good potentiometric detector, enabled the analysis of ∼50 samples h−1 without requiring pretreatment procedures. An average recovery of 98.8% and a mean standard deviation of 1.3% were obtained.  相似文献   

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