Flow-through sensor based on derivative synchronous fluorescence spectrometry for the simultaneous determination of pyrene,benzo(e)pyrene and benzo(ghi)perylene in water

A flow-through/first derivative synchronous spectrofluorimetric sensor for the determination of PAH has been described. This sensor has been used for the simultaneous determination of PAH mixtures (pyrene, benzo(e)pyrene and benzo(ghi)perylene). Linear calibration ranges between 10 and 500 ng/ml with acceptable precision (repeatability, expressed as relative standard deviation, smaller than 4.6%, and sampling frequency of 12 h(-1)) have been obtained. The method has been applied to the determination of the target analytes in spiked water samples with excellent results (recoveries between 94 and 108%).     

Micelle-sensitized constant-energy synchronous fluorescence spectrometry for the simultaneous determination of pyrene, benzo[a]pyrene and perylene.

The use of micellar media in constant-energy synchronous fluorescence spectrometry has been proposed. The influence of some aqueous micellar systems on the determination of pyrene, perylene and benzo[a]pyrene has been investigated. The presence of these micellar systems allows their determination in aqueous media, thus avoiding the use of an organic solvent, and greatly enhances the fluorescence signals. The combination of a constant-energy synchronous scanning technique and a micellar system provided a single spectrum for the simultaneous identification and quantitative determination of the three polycyclic aromatic hydrocarbons (PAHs). Further there was no energy transfer among them, making the measurement simple and fast. A constant-energy difference of 2800 cm(-1) was selected. The analytical characteristics of the proposed method in the presence of anionic micelles of sodium dodecylsulfate (SDS) were studied. The detection limits were at a level of ng ml(-1). Analysis of water samples from two different origins spiked with known amount of pyrene, perylene and benzo[a]pyrene also gave satisfactory results, and total average recoveries were greater than 97.1%.     

Sensitive simultaneous determination of benzo(a)pyrene, perylene and chrysene by synchronous spectrofluorometry in nonionic micellar media

A synchronous spectrofluorometric method was developed for the simultaneous determination of benzo(a)pyrene, perylene and chrysene in a POLE micellar medium, with detection limits of 0.05 ng/ml, 0.28 ng/ml and 0.64 ng/ml, respectively. Good recoveries were obtained for sea water samples spiked with each hydrocarbon.     

Determination of pyrene and benzo(a)pyrene residues in water by derivative synchronous solid-phase spectrofluorimetry

Benzo(a)pyrene (BaP) and pyrene (Pyr) are two polycyclic aromatic hydrocarbons (PAHs) showing native fluorescence in solution. Both compounds have been determined in water at trace levels by solid-phase spectrofluorimetry, in which BaP and Pyr are fixed on Sephadex G-25 gel and the relative fluorescence intensity is measured after the system is packed in a 1-mm silica cell. First-derivative synchronous spectra obtained at =38 nm were used to determine BaP and Pyr in the presence of other potentially interferent PAHs. The spectral characteristics of the PAHs-gel system are described, the applicable concentration ranges being 0.4–2.5 ng/ml for BaP and 0.7–4.5 ng/ml for Pyr. The relative standard deviations were 1.1% and 1.4% for BaP and Pyr respectively. The detection limits were 0.04 ng/ml for BaP and 0.1 ng/ml for Pyr. The method was applied to the analysis of both compounds in water at trace levels and a recovery study on tap, natural and sea waters was carried out.     

Supersonic jet fluorescence spectrometry of perylene and benzo[a]pyrene

A supersonic jet instrument for fluorescence spectrometry is described. It consists of a high-temperature free expansion nozzle for continuous sample introduction and a vacuum chamber equipped with a high-speed pumping system. Rotationally cooled spectra obtained with the supersonic jet are compared with gas-phase spectra measured at high temperature for perylene and benzo[a]pyrene molecules. Each component of the unresolved band structure in the high-temperature spectra was found to be composed of a rotational congestion of several vibrational bands. For a 1:1 mixture of perylene and benzo[a]pyrene, selective detection is possible by using supersonic jet spectrometry. The detection limit for perylene is 100 ng. The advantage of this technique over other low-temperature spectrometric methods based on Shpol'skii and matrix isolation effects are discussed.     

Evolution of absorption, fluorescence, laser and chemical properties in the series of compounds perylene, benzo(ghi)perylene and coronene.

Absorption. fluorescence and laser properties of perylene, benzo(ghi)perylene and coronene are studied experimentally (under the same conditions) and quantum chemically at room (293 K) and at low (77 and 4 K) temperatures and direct comparison is made between the results for each molecule. All the main absorption and fluorescence parameters such as oscillator strength, fe, quantum yield, gamma, decay time, tauf, fluorescence rate constant, kf (Einstein coefficient, A) and intersystem crossing rate constant, kST, are measured or calculated. The systems of singlet and triplet levels for these compounds are simulated and analyzed. Triplet states mixing with the lowest singlet S1 state are determined. The low values of kST found are explained. The possible vibronic coupling in the molecule coronene is discussed. The nature of the three fluorescence bands of coronene observed is interpreted. The change in the arrangement of the singlet and triplet levels of the studied compounds is interpreted quantum-chemically. It is found that at room temperature (293 K), only perylene shows laser action, while all three compounds show good laser oscillation at low temperature (< 100 K). The differences in the laser properties of these compounds are explained by the inversion of the Sp(1La) and Sinfinity(1Lb) levels which occurs in the transition from perylene to benzo(ghi)perylene. Chemical properties of the compounds studied are outlined. Linear and quasi-linear fluorescence spectra of perylene and benzo(ghi)perylene, obtained at 77 and 4 K. can be used in the identification of these compounds.     

Simultaneous determination of perylene and benzo[g,h,i]perylene by synchronous fluorescence using a micellar system

Summary Perylene and benzo[g,h,i]perylene have been studied in the presence of several surfactants. A synchronous spectrofluorimetric method has been developed for simultaneous determination of perylene and benzo[g,h,i]perylene in a hexadecyltrimethylammonium bromide (HDTAB) micellar medium, with detection limits of 0.12 and 0.21 ng/ml for perylene and benzo[g,h,i]perylene, respectively. The method has been applied to the determination of both hydrocarbons added to sea water with acceptable results.     

比值导数荧光光谱法同时测定色氨酸和5-羟基色氨酸

建立了比值导数荧光光谱法同时测定色氨酸和5-羟基色氨酸的方法。在比值导数荧光光谱法中,色氨酸浓度在4.0×10-6~2.0×10-5mol/L范围内比值导数荧光光谱峰高与其浓度成正比,线性相关系数为0.9901,检出限为1.3×10-7mol/L。5-羟基色氨酸浓度在4.0×10-8~2.0×10-5mol/L范围内比值导数光谱峰高与其浓度成正比,线性相关系数为0.9996,检出限为1.3×10-8mol/L。同时测定了实际样品中的色氨酸和5-羟基色氨酸,测定结果与高效液相色谱法有良好的一致性。     

Simultaneous determination of warfarin and bromadiolone by derivative synchronous fluorescence spectrometry

By using second derivative synchronous fluorescence spectrometry the simple resolution of mixtures of the anticoagulant rodenticides warfarin and bromadiolone in the presence of beta-cyclodextrin is accomplished which causes a differential effect on the fluorescence intensity of these compounds. The determination method developed is simple, fast and inexpensive; in addition, measurements are performed in a single scan. Mixtures of warfarin and bromadiolone in ratios between 4:1 and 1:10 were satisfactorily resolved.     

Second derivative synchronous fluorescence spectroscopy for the simultaneous determination of metoclopramide and pyridoxine in syrup and human plasma

A rapid, simple, and highly sensitive second derivative synchronous fluorometric method has been developed for the simultaneous determination of metoclopramide (MT) and pyridoxine (PY) in a binary mixture. The method is based on measurement of the native fluorescence of these drugs at delta lambda = 80 nm in methanol. The different experimental parameters affecting the native fluorescence of the drugs were carefully studied and optimized. The fluorescence-concentration plots were rectilinear over the ranges of 0.02-0.4 and 0.1-2 microg/mL for MT and PY, respectively. The limits of detection were 0.003 and 0.007 microg/mL and the limits of quantification were 0.008 and 0.02 microg/mL for MT and PY, respectively. The proposed method was successfully applied to the determination of MT and PY in synthetic mixtures and in commercial syrup. The results were in good agreement with those obtained with a reported method. The high sensitivity attained by the proposed method allowed the determination of MT in spiked and real human plasma samples. The mean percent recoveries of MT from spiked and real human plasma (n = 3) were 93.72 +/- 3.15 and 89.72 +/- 2.19 respectively.     

Admicelle-enhanced synchronous fluorescence spectrometry for the selective determination of polycyclic aromatic hydrocarbons in water

A simple and rapid method for the highly sensitive determination of polycyclic aromatic hydrocarbons (PAHs) in water was developed. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene in water were concentrated into sodium dodecyl sulfate (SDS)-alumina admicelles. The collection was performed by adding SDS and alumina particles into the sample solution at pH 2. After gentle mixing, the resulting suspension was passed through a membrane filter to collect the SDS admicelles containing highly concentrated PAHs. The filter was placed on a slide glass and then covered admicellar layer with a fused silica glass plate before setting in a fluorescence spectrometer. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene were selectively determined by the synchronous fluorescence scan (SFS) analysis with keeping wavelength intervals between excitation and emission to 98, 35, 29, and 45 nm, respectively. Because of the minimum spectral overlapping, 1-40 ng l⁻¹ of benzo[a]pyrene, benzo[k]fluoranthene, and perylene as well as 10-150 ng l⁻¹ of pyrene were selectively determined with eliminating the interferences of other 12 PAHs. The detection limits were 0.3 ng l⁻¹ for benzo[a]pyrene, benzo[k]fluoranthene, and perylene, and 1 ng l⁻¹ for pyrene. They were 2-3 orders of magnitude lower than the detection limits in normal aqueous micellar solutions. The application to water analysis was studied.     

Second-derivative constant-wavelength synchronous scan spectrofluorimetry for determination of benzo[b]fluoranthene, benzo[a]pyrene and indeno[1,2,3-cd]pyrene in drinking water

The use of derivative constant-wavelength synchronous scan fluorimetry is reported for the determination of three polycyclic aromatic hydrocarbon pollutants in drinking water (linearity range 0.4-4 mug 1(-1)). The limits of detection (LD) and quantification (LQ) (mug 1(-1)) are 0.01 and 0.07 for benzo[b]fluoranthene, 0.03 and 0.12 for benzo[a]pyrene and 0.19 and 0.57 for indeno[1,2,3-cd]pyrene in the presence of three other pollutants, benzo[k]fluoranthene, benzo[ghi]perylene and fluoranthene. The precision (RSD /= 85%) were satisfactory.     

Simultaneous determination of norfloxacin and lomefloxacin in milk by first derivative synchronous fluorescence spectrometry using Al (III) as an enhancer

A novel method for the simultaneous determination of norfloxacin (NFLX) and lomefloxacin (LFLX) in milk samples was developed by using first derivative synchronous fluorimetry. The synchronous fluorescence (Δλ=160 nm) spectra and first derivative synchronous fluorescence spectra of NFLX, LFLX and their mixture were studied. The zero-crossing method was utilized to measure the first derivative value of the derivative spectrum. The zero-crossing points were located at 275.0 nm for NFLX and at 283.8 nm for LFLX, in first derivative synchronous fluorescence spectra. Therefore, 283.8 nm and 275.0 nm were selected for the determination of NFLX and LFLX. The first derivative values varied linearly with the concentrations in the range of 1.68×10(-8)-5.64×10(-6) mol L(-1) for NFLX and 1.89×10(-8)-6.19×10(-6) mol L(-1) for LFLX. The detection limits were 5.03×10(-9) mol L(-1) for NFLX and 7.58×10(-9) mol L(-1) for LFLX. The proposed method is reliable, selective and sensitive, and has been used successfully in the simultaneous determination of NFLX and LFLX in milk samples, whose results were in good agreement with those obtained by HPLC.     

Simultaneous determination of gallium and aluminium in biological samples by conventional luminescence and derivative synchronous fluorescence spectrometry

The simultaneous determination of gallium and aluminium by using conventional fluorimetry and derivative synchronous fluorescence spectrometry has been studied. These determinations are based on the formation of fluorescent complexes of gallium and aluminium with salicylaldehyde carbohydrazone (SACH). In the conventional method, two samples are analysed under different analytical conditions, and the results are evaluated by solving a system of two simultaneous equations. In the derivative synchronous method (at pH = 2.6, in an ethanol-water medium containing 72% of ethanol), the following conditions are used: a constant wavelength difference of 20 nm between the monochromator settings, a time-constant of 1.5 sec, a scan-speed of 120 nm/min, and a derivative wavelength difference of 10 nm; gallium can be determined in the range 7-38 ng/ml, and aluminium between 6 and 45 ng/ml. The synchronous method shows more advantages, and has been used in the determination of both metal ions in diverse biological samples (animal tissues and human serum) with good results.     

A novel approach for simultaneous determination of polycyclic aromatic hydrocarbons by Shpol'skii non-linear variable-angle synchronous fluorescence spectrometry

A new method of combining low-temperature Shpol'skii effect with non-linear variable-angle synchronous fluorescence spectrometry (L-NLVASFS) has been proposed to increase spectral resolution. This coupled method was applied successfully to the simultaneous identification and quantification of some polycyclic aromatic hydrocarbons (PAHs) in mixtures, which cannot be determined by non-linear variable-angle synchronous fluorescence spectrometry at room-temperature (R-NLVASFS). The usefulness of this method is demonstrated by the analyses of synthetic mixtures and several real samples of airborne particulates.     

Solvent effect on the simultaneous determination of anthracene and 5h-benzo[b]carbazole by synchronous fluorescence spectrometry

The effect of the solvent on the peak resolution between the peaks of the two analytes is investigated. Ethylene glycol mono-t-butyl ether is selected as the most favorable medium in terms of spectral resolution and sensitivity. Both compounds contained in carbazole can be determined simultaneously up to 0.01%.     

Room-temperature excitation-emission phosphorescence matrices and second-order multivariate calibration for the simultaneous determination of pyrene and benzo[a]pyrene

The present article describes the simultaneous phosphorimetric determination of pyrene and benzo[a]pyrene, two highly toxic polycyclic aromatic hydrocarbons, through excitation-emission phosphorescence matrices (EEPMs) and second-order calibration. The developed approach enabled us to determine both compounds at μg L⁻¹ concentration levels without the necessity of applying separation steps, as well as significantly reducing the experimental time. An artificial neural network (ANN) approach was applied to optimize the chemical variables which have an influence on the room-temperature phosphorescence emission of the studied analytes. The present study was employed for the discussion of the scopes of the applied second-order chemometric tools: parallel factor analysis (PARAFAC) and partial least-squares with residual bilinearization (PLS/RBL). The superior capability of PLS/RBL to model the profiles of other potentially interferent polycyclic aromatic hydrocarbons (PAHs) was demonstrated. The quality of the proposed method was established with the determination of both pyrene and benzo[a]pyrene in artificial and real water samples.