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A simple, sensitive, and rapid spectrofluorimetric method was developed for the determination of the β-blocker pindolol. The native fluorescence of pindolol was measured in different organic solvents and in cyclodextrin aqueous media. The highest fluorescence signal was obtained in 2-propanol at λ em = 303 nm with λ ex = 260 nm. Analytical figures of merit for the spectrofluorimetric determination of pindolol were satisfactory, with wide linear dynamic range (LDR) values of two orders of magnitude, and rather low limit of detection (LOD) values between 0.2 and 8.7 ng/mL. Moreover, the addition of cyclodextrins (HP-β-CD and β-CD) in aqueous media enhanced the fluorescence of pindolol. In addition, the inclusion complexes of pindolol with cyclodextrins were investigated and the stability constants of complexes were calculated by means of the method of nonlinear regression (NLR). The method was successfully applied to the analysis of tap water and natural water samples, spiked with pindolol., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Water pollution by heavy metals has many human origins, such as the burning of fossil fuels, exhaust gases of vehicles, mining, agriculture, and incineration of solid and liquid wastes. Heavy metals also occur naturally, due to volcanoes, thermal springs activity, erosion, infiltration, etc. This water contamination is a threat for living beings because most heavy metals are toxic to humans and to aquatic life. Hence, it is important to find effective techniques for removing these contaminants in order to reduce the level of pollution of the natural waters. In this work, we have reviewed the toxicity of several heavy metals (mercury, lead, cadmium, chromium, nickel), their impact on the environment and human health, and the synthesis and characterization methods of conducting organic polymers (COPs) utilized for the removal of heavy metals from the environment. Therefore, this review was essentially aimed to present recent works and methods (2000-2020) on the environmental impact and toxicity of heavy metals and on the removal of toxic heavy metals, using chemically and/or electrochemically synthesized COPs. We have also stressed the great interest of COPs for the removal of toxic heavy metals from waters.

Highly sensitive multicomponent materials designed for the recognition of hazardous compounds request control over interfacial chemistry. The latter is a key parameter in the construction of the sensing (macro) molecular architectures. In this work, multi-walled carbon nanotubes (CNTs) were deposited on diazonium-modified, flexible indium tin oxide (ITO) electrodes prior to the electropolymerization of pyrrole. This three-step process, including diazonium electroreduction, the deposition of CNTs and electropolymerization, provided adhesively-bonded, polypyrrole-wrapped CNT composite coatings on aminophenyl-modified flexible ITO sheets. The aminophenyl (AP) groups were attached to ITO by electroreduction of the in-situ generated aminobenzenediazonium compound in aqueous, acidic medium. For the first time, polypyrrole (PPy) was electrodeposited in the presence of both benzenesulfonic acid (dopant) and ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA), which acts as a chelator. The flexible electrodes were characterized by XPS, Raman and scanning electron microscopy (SEM), which provided strong supporting evidence for the wrapping of CNTs by the electrodeposited PPy. Indeed, the CNT average diameter increased from 18 ± 2.6 nm to 27 ± 4.8, 35.6 ± 5.9 and 175 ± 20.1 after 1, 5 and 10 of electropolymerization of pyrrole, respectively. The PPy/CNT/NH 2 -ITO films generated by this strategy exhibit significantly improved stability and higher conductivity compared to a similar PPy coating without any embedded CNTs, as assessed by from electrochemical impedance spectroscopy measurements. The potentiometric response was linear in the 10 -8 -3 × 10 -7 mol L -1 Pb(II) concentration range, and the detection limit was 2.9 × 10 -9 mol L -1 at S/N = 3. The EGTA was found to drastically improve selectivity for Pb(II) over Cu(II). To account for this improvement, the density functional theory (DFT) was employed to calculate the EGTA-metal ion interaction energy, which was found to be -374.6 and -116.4 kJ/mol for Pb(II) and Cu(II), respectively, considering solvation effects. This work demonstrates the power of a subtle combination of diazonium coupling agent, CNTs, chelators and conductive polymers to design high-performance electrochemical sensors for environmental applications., Competing Interests: The authors declare no conflict of interest.

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 (Cu 2+ ) and lead(II) ion (Pb 2+ ) 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, Cu 2+ and Pb 2+ , 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., (© 2019 John Wiley & Sons, Ltd.)

Diflubenzuron (DFB) and fenuron (FEN) are benzoylurea and phenylurea pesticides, widely used in Senegal, that do not exhibit any natural fluorescence, but can be determined by means of photoinduced fluorescence (PIF) methods. Photodegradation of DFB and FEN yielded a number of fluorescent and non-fluorescent photoproducts. For both pesticides, at least 10 photoproducts were detected and identified by gas chromatography-mass spectrometry (GC/MS). To identify the formed fluorescent DFB and FEN photoproducts, their fluorescence spectra were compared with those of standard compounds, including phenol and p-hydroxyaniline., (© 2019 John Wiley & Sons, Ltd.)

An EC 50 database was established to assess the acute toxicity of 16 PESTANAL pesticide standards and of seven pesticide commercial formulations using a Vibrio fischeri bioluminescence method. Half maximal effective concentration (EC 50 ) is defined as the concentration of pollutant (in this case, pesticide) destroying 50% of the bacteria population and causing 50% bioluminescence inhibition, after a specified exposure time. Linear curves of bioluminescence inhibition versus pesticide concentration and EC 50 values were obtained for exposure times (t) of 5 or 15 min for these pesticides. The EC 50 values ranged from 6.90 × 10 -4 to 0.83 mg/ml (t = 5 min), and from 9.00 × 10 -4 to 0.37 mg/ml (t = 15 min) for pesticide standards, plus from 0.0077 to 0.74 mg/ml (t = 5 min), and from 0.0076 and 0.57 mg/ml (t = 15 min) for pesticide commercial formulations. The EC 50 database allowed classification of the pesticides under study into three categories according to their toxicity: very toxic, toxic and moderately toxic. These results demonstrated that the establishment of an EC 50 database and of linear curves of bioluminescence inhibition versus the pesticide concentration resulted in very important and irreplaceable tools to estimate the global and individual toxicity of pesticides present in environmental samples., (© 2019 John Wiley & Sons, Ltd.)

Prototypes of on-site automatic photo induced fluorescence detectors of pesticide in natural waters are set up and applied for the determination of the benzoyl- and phenylurea pesticides, namely fluometuron, monolinuron and diflubenzuron. As these pesticides present no native fluorescence the set up system use the photo conversion under UV irradiation of these pesticides into highly fluorescent photoproducts. A first system, called AUTOPIF, (evolution the commercial AQUAPOD system) is develop using a detection via a diode array spectrometer. To improve the sensitivity of the method, a second system, called AUTOPIF+, is developed with a more resolute spectrometer and an intensified CCD camera detection. Analytical applications were carried out in aqueous solution and detected on line with the AUTOPIF and AUTOPIF+ system. The calibration curves are linear over one order of magnitude, and the limits of detection are in the μg mL -1 range. The analytical performances of these methods for the determination of the three pesticides are satisfactory in comparison to other classical PIF methods published for the determination of phenylurea pesticides in aqueous solutions. Our results show that the AUTOPIF and AUTOPIF+ methods are versatile, sensible and can be easily applied as an alert system to detect pollutant residues in naturals waters over a threshold value., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

Permanent online monitoring of water supply pollution by hydrocarbons is needed for various industrial plants, to serve as an alert when thresholds are exceeded. Fluorescence spectroscopy is a suitable technique for this purpose due to its sensitivity and moderate cost. However, fluorescence measurements can be disturbed by the presence of suspended organic matter, which induces beam scattering and absorption, leading to an underestimation of hydrocarbon content. To overcome this problem, we propose an original technique of fluorescence spectra correction, based on a measure of the excitation beam scattering caused by suspended organic matter on the left side of the Rayleigh scattering spectral line. This correction allowed us to obtain a statistically validated estimate of the naphthalene content (used as representative of the polyaromatic hydrocarbon contamination), regardless of the amount of suspended organic matter in the sample. Moreover, it thus becomes possible, based on this correction, to estimate the amount of suspended organic matter. By this approach, the online warning system remains operational even when suspended organic matter is present in the water supply., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Water pollution by heavy metals is a great health concern worldwide. Lead and cadmium are among the most toxic heavy metals because they are dangerous for the human and aquatic lives. In this work, the removal of lead and cadmium from aqueous solutions has been studied using electrosynthesized 4-amino-3-hydroxynaphthalene-1-sulfonic acid-doped polypyrrole (AHNSA-PPy) films as a new adsorbent. Two distinct methods, including the immersion method, based on the Pb 2+ and Cd 2+ spontaneous removal by impregnation of the polymer in the solution, and the electro-elimination method, consisting of removal of Pb 2+ and Cd 2+ ions from the solution by applying a small electrical current (5 mA) to the polymer film, were developed: the evolution of Pb 2+ and Cd 2+ concentrations with time was monitored by inductively coupled plasma optical emission spectrometry (ICP-OES). The effect of pH on the adsorption and electro-elimination of Pb 2+ and Cd 2+ using the AHNSA-PPy film was investigated and optimized, showing that the ionic adsorption and electro-elimination processes were highly pH-dependent. The kinetics of Pb 2+ and Cd 2+ adsorption and electro-elimination were found to follow second-order curves. The maximum adsorption capacity values of the AHNSA-PPy film were 64.0 and 50.4 mg/g, respectively, for Pb 2+ and Cd 2+ . The removal efficiency values were, respectively, for Pb 2+ and Cd 2+ , 80 and 63% by the immersion method, and 93 and 85% by the electro-elimination method. Application of both methods to Senegal natural waters, fortified with Pb 2+ and Cd 2+ , led to removal efficiency values of, respectively for Pb 2+ and Cd 2+ , 76-77 and 58-59% by the immersion method, and of 82-90 and 80-83%, by the electro-elimination method.

Polypyrrole (PPy) conducting films, doped with 4-amino-3-hydroxynaphthalene sulfonic acid (AHNSA), were electrosynthesized by anodic oxidation of pyrrole on Pt and steel electrodes in aqueous medium (0.01 M AHNSA +0.007 M NaOH, using cyclic voltammetry (CV), and their electrochemical properties were studied. Fourier-transform infrared (FT-IR) spectroscopy confirmed the formation of AHNSA-PPy films. Their morphology was characterized by scanning electron microscopy (SEM), and their optical properties, including UV-VIS absorption and fluorescence spectra, were also investigated. AHNSA-PPy films were used for the removal of chromium(VI) from aqueous solution, by means of the immersion method and the Cr(VI) electro-reduction method. The effect of various experimental parameters, including the adsorbent (polymer) mass, pH, type of electrodes, and current intensity, on the adsorption of chromium by the polymer was performed and optimized. The adsorption and electro-reduction of (Cr VI) on the AHNSA-PPy film surface were found to be highly pH-dependent, and the kinetics of Cr(VI) adsorption and electro-reduction followed second-order kinetic curves. Apparent second-order rate constants were about three times higher for the Cr(VI) electro-reduction method than for the immersion method, indicating that the use of electro-reduction method significantly accelerated the chromium adsorption process on polymer. The maximum adsorption capacity of the AHNSA-PPy film for chromium was 224 mg g -1 . A 96% chromium removal from pure aqueous solution was reached within about 48 h by the immersion method, but only within about 6 h by the Cr(VI) electro-reduction method. Application of both methods to Cr(VI) fortified natural waters of Senegal led to chromium removal efficiency high values (93 to 96% according to the type of natural water).

The effects of various trivalent lanthanide ions (acetates of Ce 3+ , Er 3+ , Eu 3+ , Nd 3+ ) on the electronic absorption and fluorescence spectra of un-substituted coumarin-3-carboxylic acid (CCA) and 7-N,N-diethylamino-coumarin-3-carboxylic acid (DECCA) have been investigated in dimethylsulfoxide (DMSO) at room temperature. Depending on the lanthanide ion nature and concentration, significant spectral changes of absorption bands occurred for both coumarin derivatives. These spectral changes were attributed to the formation of ground-state complexes between the coumarin carboxylate derivatives and lanthanide ions. The fluorescence quenching of CCA and DECCA upon increasing the lanthanide ion concentration was studied. Different quantitative treatments, including the Stern-Volmer equation, the Perrin equation and a polynomial equation, were applied and compared in order to determine the nature of the quenching mechanisms for both coumarin derivatives. The results suggested the contribution of both dynamic and static quenching. Significant differences of CCA and DECCA fluorescence quenching efficiency were also observed, depending on the lanthanide ion. DECCA fluorescence lifetime measurements, performed in the absence and in the presence of Ln 3+ , confirmed a contribution of static quenching.

Electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles (N-PhPys), including HOPhPy, MeOPhPy, ThPhPy, PhDPy, DPhDPy, PyPhThThPhPy, and their available, electrosynthesized polymers were investigated. Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), and other photophysical parameters of these N-PhPy derivatives and their polymers were measured in DMF, DMSO diluted solutions and/or solid state at room temperature. The electronic absorption spectra of N-PhPy derivatives and their polymers included one to several bands, located in the 270-395 nm region, according to the p-phenyl substituent electron-donating effect and conjugated heteroaromatic system length. The fluorescence excitation spectra were characterized by one broad main peak, with, in most cases, one (or more) poorly resolved shoulder (s), appearing in the 270-405 nm region, and their emission spectra were generally constituted of several bands located in the 330-480 nm region. No significant shift of the absorption, fluorescence excitation and emission spectra wavelengths was found upon going from the monomers to the corresponding polymers. ΦF values were high, varying between 0.11 and 0.63, according to the nature of substituents(s) and to the conjugated system extension. Fluorescence decays were mono-exponential for the monomers and poly-exponential for PyPhThThPhPy and for polymers. τF values were relatively short (0.35-5.17 ns), and markedly decreased with the electron-donor character of the phenyl group p-substituent and the conjugated system extension., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A new direct laser photo-induced fluorescence high performance liquid chromatography (DL-PIF-HPLC) method is developed for the simultaneous determination of three anilide pesticides, namely carboxin, monalide and propanil. DL-PIF-HPLC uses a tunable Nd:YAG-OPO laser to obtain fluorescent photoproduct(s) and to simultaneously analyze their fluorescence in a short acquisition time with an intensified CCD camera, which improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the laser beam) and reduces the time of analysis, relative to the classical PIF methods. However, one of the main drawbacks of PIF methods is the presence of interferences with other compounds, such as other pesticides from the same group yielding similar fluorescent photoproducts, which reduces their selectivity. The analytical interest of DL-PIF-HPLC to avoid these interferences is demonstrated. The DL-PIF spectra, chromatographic conditions and analytical performances of DL-PIF-HPLC are presented for the simultaneous determination of three anilide pesticides. The calibration curves are linear over one order of magnitude and the limits of detection are in the ng mL(-1) range. The new DL-PIF-HPLC system has the advantage to combine the performances of both techniques, DL-PIF and liquid chromatography, and to improve the analysis selectivity., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A photo-induced fluorescence (PIF) method was developed for the determination of two benzoyl- and phenylurea pesticides, namely diflubenzuron (DFB) and fenuron (FEN). The photoconversion under UV irradiation of both pesticides into strongly fluorescent photoproducts was performed in several media (methanol, ethanol, acetonitrile, pH4 aqueous solution and pH4 water-methanol (30:70, v/v) mixture). PIF parameters were optimized. Analytical figures of merit for the PIF determination of DFB and FEN were satisfactory, with rather wide linear dynamic range (LDR) values of one to two orders of magnitude, relatively low limit of detection (LOD) values of, respectively, 9-24 ng/mL for DFB and 1-28 ng/mL for FEN, and limit of quantification (LOQ) values of, respectively, 30-80 ng/mL for DFB and 4-95 ng/mL for FEN, according to the medium. Relative standard deviation (RSD) values were in the range 1.7-5.6%. PIF was validated by comparing its analytical performances to those of a standard UV absorption spectrophotometric method. The optimized PIF method was applied to the quantitative analysis of both pesticides in various spiked natural water samples collected in a Senegal agricultural area by the standard addition procedure prior to extraction steps in dichloromethane, with satisfactory mean recovery percentage values (97.0-105.3 for DFB and 98.3-102.8% for FEN). An interference study of foreign species, including pesticides and inorganic ions, likely to be present in natural waters, was also carried out.

The synthesis and optical properties of three new fluorescent alkoxy-substituted thieno[3,2-b]indole (TI) derivatives, including 7-methoxy thieno[3,2-b]indole (7-MeOTI), 6,7- methylenedioxythieno[3,2-b]indole (6,7-MDTI) and 6,7-dihexyloxythieno[3,2-b]indole, (6,7-DHTI), were investigated. Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF), lifetimes (τF), and other photophysical parameters of the three TI derivatives were measured in DMSO solutions at room temperature. Theoretical electronic absorption and fluorescence spectra were also calculated by means of a molecular orbital (MO) method. For all three alkoxy-TI derivatives, the fluorescence emission maximum wavelength was significantly red shifted relative to un-substituted TI, which was attributed to delocalization of the fused hetero-aromatic ring π electronic system by the electron-donating alkoxy group(s). ΦF values varied from 0.12 to 0.19, according to the compound. τF were short, in the range 0.56-1.13 ns., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A direct Laser Photo-Induced Fluorescence (DL-PIF) method is developed for the determination of two phenylurea pesticides, namely fenuron and diflubenzuron. The DL-PIF method uses a tunable Nd:YAG-OPO Laser to obtain the photoproduct(s) and to simultaneously analyse their fluorescence in a short acquisition time on an intensified CCD camera. Compared to classical PIF methods, the use of a tunable laser improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the beam) and also reduces the time of analysis. The analytical performances of this method for the determination of both pesticides are satisfactory in comparison to other classical PIF methods published for the determination of phenylurea pesticides. The calibration curves were linear over one order of magnitude and the limits of detection were in the ng mL(-1) range. Satisfactory recoveries were obtained in the analysis of both pesticides in river and sea water spiked samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Introduction: The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium., Methods: The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH 3.0 were determined by the competitive kinetics method., Results and Discussion: The hydroxylation absolute rate constant (k(abs)) values of both TRK herbicides ranged from 8.20 × 10(8) (sulcotrione) to 1.01 × 10(9) (mesotrione) L mol(-1) s(-1), whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione, (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90 × 10(8) and 3.29 × 10(9) L mol(-1) s(-1). The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97-98% were reached in optimal conditions for a 6-h electro-Fenton treatment time., Conclusions: The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.

The electronic absorption, fluorescence excitation and emission spectra, and fluorescence quantum yields of novel fused thienobenzofurans, including thieno[3,2-b][1]benzofuran (1), [1]benzothieno[3,2-b]furan (2), and [1]benzothieno[3,2-b][1]benzofuran (3), were recorded in fourteen solvents of different polarities at room temperature. Compound 2 was not fluorescent. Experimental ground-state dipole moments of compounds 1-3 were measured in benzene at 298 K and compared with the corresponding theoretical dipole moment values. The solvent effects on the electronic absorption and fluorescence spectra of these thienobenzofurans were quantitatively investigated by means of solvatochromic correlations based on the Kawski-Chamma-Viallet and McRae equations. A weak negative solvatochromic behavior was found for these compounds, showing that their dipole moments are slightly lower in the excited singlet-state than in the ground-state. Kamlet-Abboud-Taft multiparameter relationships were also established for electronic absorption and fluorescence wavenumbers, and fluorescence quantum yields in most solvents, demonstrating the occurrence of specific solute-solvent interactions.

The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Sulfamethoxazole (SMX) is a synthetic antibiotic widely applied as a bacteriostatic drug to treat a number of diseases. SMX can persist in the environment for long periods of time because of its low biodegradability, which may result in various, direct and indirect, toxicological effects on the environment and on human health. Therefore, we have developed the electrochemical advanced oxidation process (AOP) "electro-Fenton" to degrade SMX in aqueous media. In this work, a detailed study of the evolution of toxicity of SMX and its degradation products in aqueous solutions, during treatment by the electro-Fenton AOP, is described, using the bioluminescence Microtox® method, based on the inhibition of luminescence of marine bacteria Vibrio fischeri. Samples were collected at various electrolysis times and analyzed by HPLC for quantifying the evolution of the degradation products, and their toxicity was measured by the Microtox® method. Our results demonstrated that the toxicity of SMX aqueous solutions varied considerably with the electrolysis time and the applied current intensity. This phenomenon could be explained by the formation and disappearance of several degradation products, including cyclic and/or aromatic intermediates, and short-chain acid carboxylic acids, having a toxicity different of the initial antibiotic. The curves of the % of bacterial luminescence inhibition vs. electrolysis time, corresponding to the evolution of the toxicity of the formed degradation products, were investigated and tentatively interpreted.

Flow injection analysis combined with photo-induced fluorescence (FIA-PIF) has been applied for the determination of α-cypermethrin pesticide residues in Senegalese natural waters, using organic solutions and cyclodextrin (β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin) aqueous media. The α-cypermethrin insecticide has a very weak natural fluorescence, but it is converted into strongly fluorescent photoproduct(s) by UV irradiation. Cyclodextrins were found to enhance the PIF signal. FIA parameters, including mobile phase flow rate, injected volume, and reactor length, were optimized. Analytical performances of the FIA-PIF method for the determination of α-cypermethrin were satisfactory, with concentration linear dynamic ranges over one to two orders of magnitude and with rather low limits of detection and limits of quantification, in the ng mL(-1) range, and relative standard deviations comprised between 1.2% and 3.8%. Application of FIA-PIF for the analysis of fortified natural water samples collected from Senegal yielded good recovery values (84-112%). Because of its high sampling rate, the FIA-PIF method constitutes a rapid analytical tool, useful for quantification of α-cypermethrin residues in natural waters.

In this review, the recent evolution and the state of the art of photochemical reactions coupled with chemiluminescence processes are presented. Different chemiluminescence systems have been considered together with suitable photochemical derivatization processes that can affect either the analyte of interest or even the chemiluminogenic reagent, producing some derivatives able to participate more efficiently in the CL reactions and enhancing the CL emission. The on-line integration of the photochemical reactions as well as the coupling of this resulting photoinduced chemiluminescence (PICL) method with dynamic analytical systems, such as flow injection analysis, liquid or gas chromatography and capillary electrophoresis, have been discussed. Important applications of PICL have been proposed in environmental, pharmaceutical and food analysis., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The synthesis, electrochemical and optical properties of three fluorescent substituted thieno[3,2-b][1]benzothiophenes (TBT) derivatives, including 3-methoxythieno[3,2-b][1]benzothiophene (3-MeO-TBT), 2,3-dimethylthieno[3,2-b][1]benzothiophene (2,3-diMe-TBT), and 6-methoxythieno[3,2-b][1]benzothiophene-2-carboxylate (6-MeO-TBT-2-COOMe), were investigated. The oxidation potential values varied between 1.40 and 1.20 V/SCE according to the electronic substituent effect, and electropolymerization attempts, performed in 0.1 M LiClO(4) acetonitrile solution, led to the formation of very thin films of poly(3-MeO-TBT) and poly(2,3-di-Me-TBT). Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (Φ(F)) , lifetimes (τ(F)), and other photophysical parameters of the three new TBT derivatives were measured in DMSO solutions at room temperature. For the methyl-and methoxy-substituted TBT derivatives, the fluorescence emission peak were slightly red shifted relative to that of unsubstituted TBT (Δλ(em) = 1-12 nm) whereas, in the case of 6-MeO-TBT-2-COOMe, a rather strong red-shift (Δλ(em) = 73 nm) was attributed to the existence of a "push-pull" electronic interaction of the MeO and COOMe groups. All Φ(F) values were rather high, varying between 0.11 and 0.35, according to the substituent effect. Fluorescence decays were mono-exponential and τ(F) values were very short, ranging between 0.11 and 0.30 ns for the substituted TBT derivatives until study.

The photochemically induced fluorescence (PIF) spectral properties of alpha-cypermethrin in organic solvents (hexane, dichloromethane, acetonitrile, ethanol) and in cyclodextrin aqueous solutions (beta-CD and 2-hydroxypropyl-beta-CD, 2-HP-beta-CD) were investigated. The photolysis kinetics of alpha-cypermethrin were evaluated in the various media. The PIF signal was found to be significantly enhanced in the CD media relative to the organic solvents. The stoichiometry and the formation constants of the alpha-cypermethrin inclusion complexes formed with the CDs were determined. The analytical performances of the PIF method were improved in the presence of HP-beta-CD relative to the other media, and a CD-enhanced PIF analytical method was developed. The limits of detection and limits of quantification ranged, respectively, between 6 and 98 ng/mL and between 24 and 343 ng/mL, depending on the medium. Application to the analysis of tap water and Senegal natural water samples collected close to agricultural areas and spiked with alpha-cypermethrin yielded satisfactory recoveries going from about 77% to 98%. An interference study of foreign species, including pesticides and inorganic ions likely to be present in natural waters, was also carried out.

A detailed toxicological study on several pesticides, including chlorothalonil, cyprodynil, dichlobénil, pendimethaline, trifluraline, and alpha-endosulfan, present at trace levels in air and total atmospheric precipitations of Paris is presented. The pesticides contained in the atmospheric samples, collected during sampling campaigns in February-March 2007, are identified and quantified by a high-performance liquid chromatographic (HPLC)-UV detection method. The toxicity measurements are performed by means of the Microtox bioluminescence method, based on the evaluation of the bioluminescence inhibition of the Vibrio fischeri marine bacteria at two exposure times to the pesticide solutions. The specific toxicity, corresponding to the particular toxicity of the compound under study and represented by the EC(50) parameter, is determined for these pesticides. Also, the global toxicity, which is the toxicity of all micro-pollutants present in the sample under study, is estimated for the extracts of air and atmospheric precipitation (rainwater) samples. The specific toxicities strongly vary with the nature of the pesticide, the EC(50) parameter values being comprised between 0.17 and 0.83 mg/mL and 0.15 and 0.66 mg/mL, respectively, for exposure times of 5 and 15 min. The importance of the atmospheric samples' global toxicity and the respective contribution of the toxic potency of the various pesticides contained in these samples are discussed.

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.

Luminescence studies on a series of new 12H-benzo[a]phenothiazines (BPHTs), possessing potentially useful antitumor therapeutic properties, are reviewed. The electronic absorption and fluorescence spectral properties of BPHTs, as well as their triplet- and singlet-excited states luminescence quenching are reviewed. Ground-state and singlet-excited state dipole moments and solvatochromic relationships are also described for these compounds. Studies on the formation of inclusion complexes between BPHTs and cyclodextrins (CDs), including CD-enhanced fluorescence, and thermodynamic constants and molecular geometry of these complexes, are discussed. The BPHTs antitumor properties in relation to their pi-electron density, and the physico-chemical and analytical applications based on their fluorescence and photophysical properties are also presented. This review article is based on selected literature data published in the last ten years (1993-2004).

The fluorescence properties of anticancer drugs (ACDs), including steady-state native fluorescence, time-resolved fluorescence, fluorescence polarization, excimer and exciplex emission, laser-induced fluorescence (LIF) with one- or two-photon excitation are reviewed, as well as the use of fluorogenic labels and fluorescent probes for the non-fluorescent ACDs. The interest of monitoring the fluorescence spectral changes to study the interactions of ACDs with biomolecules, such as DNA, proteins, vesicles, and the formation of complexes is discussed. The fluorescence methodologies used for ACDs studies, including fluorescence with two-photon excitation, liquid chromatography and capillary electrophoresis with fluorescence and laser-induced fluorescence (LIF) detection, and fluorescence microscopy, are also surveyed. Analytical and bioanalytical applications of fluorescence, indicating good selectivity and very low limits of detection at the nanomolar and picomolar level for most ACDs, are described. Biomedical and clinical applications of the fluorescence methods, mostly oriented towards the evaluation of the cytoxicity and anti-tumor potential of ACDs in single cells as well as in biological fluids, including blood, serum, plasma, cerebrospinal fluid, urine and feces, are also discussed in detail. This review is based on selected literature published in the last decade (1994-2003).

The use of organized supramolecular systems-including micellar media and cyclodextrin inclusion complexes-combined with luminescence techniques in the study and determination of compounds and elements of environmental interest from 1990 to 2005 is reviewed. Analyses of environmental samples performed using fluorescence, photochemically induced fluorescence and phosphorescence spectroscopy as well as liquid chromatography, capillary electrophoresis and flow injection with luminescence detection in the presence of these organized media are described in detail.

A new flow injection analysis micellar-enhanced photochemically induced fluorescence (FIA-MEPIF) method was developed for the determination of four phenylurea herbicides, including isoproturon, neburon, linuron and diuron. On-line photoconversion under UV irradiation of these herbicides into strongly fluorescent photoproducts was performed in buffered aqueous solutions and in the presence of surfactants [sodium dodecyl sulphate (SDS) or cetyl trimethyl ammonium chloride (CTAC)] at micellar concentrations. The MEPIF and FIA parameters were optimized. The analytical figures of merit for the determination of the four herbicides were satisfactory, with concentration linear dynamic ranges over about one to two orders of magnitude, detection limits of 0.33-0.92 mg[sol ]L and relative standard deviations of 1.3-11%, according to the compound. Application to the analysis of fortified tap water samples yielded good recovery values (91-103%, according to the herbicide). Our results show that the on-line MEPIF-FIA method is simple, versatile, sensitive and can be easily applied to quantify pollutant residues in multiresidue systems., (Copyright 2005 John Wiley & Sons, Ltd.)

Firefly luciferase (EC 1.13.12.5) (FL) is the key enzyme in the firefly bioluminescence method (FB), which is widely used to determine the viability of living cells. The FB method can also be applied to monitoring the influence of different pollutants, such as pesticides. Firefly luciferase is a hydrophobic enzyme and its activity depends on the type of solvent, pH and substances present in the reaction mixture. The influence of three aromatic pesticides, including fenoxaprop-p-ethyl (I), diclofop-methyl (II) and metsulfuron methyl (III), on the enzyme activity was indirectly evaluated through the measurement of emitted light in the bioluminescence reaction, expressed in relative luminescence units (RLU). The reaction mixture used in the bioluminescence measurements consisted of: Tris buffer (pH 7.75), adenosine triphosphate (ATP) and ATP monitoring reagent, where FL is present. Ethanol-water solutions of each pesticide were then added at concentrations of 2.4 x 10(-4)-2.4 x 10(-8) mol/L. The FL activity inhibition factors (FL In%) were determined. The FL activity was maximally inhibited in the presence of all pesticides under study at a concentration of 2.4 x 10(-4) mol/L and was lowered by about 15-26% for pesticide I at concentrations of 2.4 x 10(-5)-2.4 x 10(-8) mol/L, whereas pesticides II and III, applied in the same concentration range, showed smaller FL inhibition values (5.3-20%). The pesticide degradation products (obtained after a 1 month period), measured in the same experimental conditions, in most cases exhibited a much less inhibitory effect on the enzyme activity than the corresponding initial pesticide.

Experimental dipole moments of curcumin (1) and of its parent compound dicinnamoylmethane (2) were determined in dioxane and benzene, respectively. Theoretical dipole moments were calculated using a combination of the PPP method (pi-moment) and a vector sum of the sigma-bond moments (sigma-moment) as well as by the ZINDO/1 method. Solvatochromic correlations were used to obtain the experimental first excited singlet-state dipole moments. The experimental electronic absorption spectra were compared with the calculated transitions.

Twenty-two pesticides and metabolites selected on the basis of a regional priority list, were surveyed in surface river waters by high performance liquid chromatography coupled in tandem with UV diode array detection and mass spectrometry, after an off-line pre-concentration step. Pesticide concentrations ranged between 0.07 and 4.8 microg/l according to the compound and sampling period. Analytical results were linked to the environmental risk of pesticides, evaluated by their system investigation of risk by integration of score (SIRIS) rank.

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m3 h(-1)) (urban site) or a low-volume pump (2.3 m3 h(-1)) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m(-3) of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19-5130 ng m(-3)) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.

In this paper a sensitive and simple method for the resolution of mixtures of chlorophenoxyacid herbicides using photochemical derivatization induced fluorescence has been described. These compounds do not show any fluorescence, hence photolysed to induce fluorescence after direct irradiation with ultraviolet light in presence of a cationic surfactant (cetyltrimethylammonium chloride). Critical variables such as the surfactant concentration and the irradiation time have been optimised for each compound using Sequential Response Surface Methodology (SRSM) by applying Doehlert designs in order to obtain maximum fluorescence intensity. The difference shown between the optimised irradiation times for the formation of the photoproducts allowed us to propose a time-resolved photoactivation method, for the simultaneous determination of binary mixtures, based on the use of different linear calibration curves established at various irradiation times depending on the mixture to be resolved. Satisfactory recoveries were obtained in the analysis of several mixtures of these herbicides at different ratios in spiked waters.

For moderately hydrophobic compounds such as most pesticides adsorption on colloids (<0.2 microm) may play a key role in pesticide mobility as well as in their degradation by chemical and microbiological processes. However, until now, pesticide-organic colloid interactions are poorly understood. Quantitative data for sorption equilibria on colloids of two series of herbicides including triazines (atrazine, simazine, terbutylazine, prometryne, desethylatrazine, and desisopropylatrazine) and phenylureas (isoproturon, linuron, neburon, and diuron) sampled in the Seine river (urban zone) and the Marne river (agricultural zone) are presented. Partition coefficient of herbicides on colloids (K(com)), were evaluated by solid-phase extraction coupled with high-performance liquid chromatography-UV diode-array detection (SPE-HPLC-UV/DAD). In the case of triazines a satisfactory log-log correlation was found between K(com) and octanol-water coefficient (K(ow)) values. Phenylureas did not obey this correlation, with K(com) values being about two times higher than those of triazines. The existence of two distinct types of adsorption behaviour on colloids partly explains the different occurrence of triazines and phenylureas in surface waters.

A study on using non-parametric statistical methods was carried out to calculate the binding constant of an inclusion complex and to estimate its associated uncertainty. First, a correct evaluation of the stoichiometry was carried out in order to ensure an accurate determination of the binding constant. For this purpose, the modified Benesi-Hildelbrand method had been previously applied. Then, four statistical methods (three non-parametric methods: two bootstrap approaches, the jackknife method and a parametric one: Fieller's theorem) were employed in order to compute the binding constant. The results obtained from applying these methods and the combination of the methods: jackknife after bootstrap and bootstrap after jackknife were compared. The best results in terms of accuracy were obtained from the application of a bootstrap method: the resampling residuals approach. These procedures were applied to the inclusion complex 2-hydroxil-propyl-beta-cyclodextrin-2,4-dichloro-phenoxyacetic, which shows photochemically-induced fluorescence.

The effects of several biologically important inorganic salts, including NaCl, NaI, NaBr, KCl, MgCl2, MgSO4 and CaCl2 on the electronic absorption and fluorescence spectra of Merocyanine 540 (MC-540) have been investigated in aqueous media at 25 degrees C. Depending on both the MC-540 concentration and the nature of salt, a new absorption band appears at about 515 nm, above the critical salt concentration (CSC), corresponding to salt-induced MC-540 aggregation. Several types of MC-540 fluorescence quenching by the salts are observed, according to their cationic charge and the nature of anion: in the case of monovalent ions (Na+, K+), a non-linear Stern-Volmer behaviour is observed, indicating variable contributions of dynamic and static quenching mechanisms, whereas for divalent alkaline-earth (Mg2+, Ca2+) ions, linear Stern-Volmer relationships are obtained. Using these results, an analytical quenchofluorimetric approach is proposed for the determination of magnesium ions.

First-derivative photochemically induced spectrofluorimetry (PIF-1D) is applied to the simultaneous determination of binary mixtures of 4 sulfonylurea herbicides in aqueous micellar samples. Synthetic binary mixtures of sulfometuronmethyl with chlorsulfuron, metsulfuron-methyl, and 3-rimsulfuron, respectively, are well resolved by using the zero-crossing point procedure. PIF-1D allows the determination of binary mixtures of these herbicides with linear dynamic ranges over about 2 orders of magnitude, limits of detection between 0.5 and 52 ng/mL, and relative standard deviations within 0.3-2.9%. Application to the determination of binary mixtures of these herbicides in spiked tap water samples yielded satisfactory recoveries (90-117%).

In this paper, a combination of a flow injection analysis (FIA) system with micellar-enhanced photochemically induced fluorescence (MEPIF) detection is presented as a powerful alternative for the rapid and sensitive analysis of chlorophenoxyacid herbicides. These compounds do not show native fluorescence but they can be photolysed into strongly fluorescence photoproducts after direct irradiation with ultraviolet light. The use of a cationic surfactant such as cetyltrimethylammonium chloride (CTAC) provides a considerable enhancement of photochemically induced fluorescence intensity and the nature of the technique allows a possible and easy adaptation to a FIA system. In this sense, parameters related to the nature of the analytical signal (pH, irradiation times, surfactant concentration) and to the FIA manifold (injection volume, flow rate and reactor length) have been optimised. Linear calibration graphs, with three replicates for each concentration value were established in the range of 0.2-5.0 mug ml(-1) for 2,4-Dichlorophenoxyacetic acid (2,4-D) and 0.1-5.0 mug ml(-1) for Mecoprop (MCPP). The IUPAC detection limits were 73.2 and 33.5 ng ml(-1) for 2,4-D and MCPP, respectively. Satisfactory recoveries were obtained in the analysis of these herbicides in spiked waters.

The electronic absorption and fluorescence excitation and emission spectra of poly(3-methoxythiophene) (PMOT), a soluble, electroactive oligomer mainly constituted of hexamer, were investigated in dimethylsulfoxide at room temperature. The study of PMOT photophysical properties suggests the existence of important pi-electronic delocalization in the oxidized and reduced form of the oligomer. A significant fluorescence quenching of PMOT takes place in the presence of various quenchers such as dimethylterephthalate, potassium iodide and thallium acetate. Quenching mechanisms implying a quencher-induced intersystem-crossing step are proposed. Modified Stern-Volmer relationships were obtained with large quenching bimolecular rate constants (2.7 x 10(9)-6.1 x 10(11) l mol(-1) s(-1)), which suggests electronic energy migration throughout the repeat units of the PMOT hexamer.

An analytical method based on the use of UV irradiation to produce fluorescent derivatives from four non-fluorescent sulfonylurea herbicides, including chlorsulfuron, metsulfuron methyl, 3-rimsulfuron and sulfometuron methyl is described. Their photochemically-induced fluorescence (PIF) properties in several solvents (water, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile, methanol, ethanol, propan-2-ol and their binary mixtures with water) and micellar solutions of sodium dodecyl sulfate (SDS), and cetyltrimethylammonium chloride (CTAC) are reported. Physicochemical variable influencing the sensitivity of the method have been optimized. A PIF method is developed for the determination of the four herbicides under study. Micellar media are found to provide the best analytical figures of merits. Linear dynamic ranges are established over about two orders of magnitude. The limit of detection (LOD) range from 0.2 to 6 ng ml(-1) according to the compound, with relative standard deviation (RSD) between 1.2 and 3.9%. Examples of applications to the analysis of these herbicides in spiked river water samples are given. The mean recoveries range from 80 to 104%.

The photochemically induced fluorescence (PIF) properties of tianeptine and some of its metabolites were investigated in acidic (pH 2.3) water-alcohol mixtures at room temperature. Two PIF methods were developed, including bulk solution and flow injection analysis (FIA). Linear calibration plots were established over a concentration range of more than one order of magnitude. Limits of detection ranged from 15 ng ml-1 for FIA-PIF to 25 ng ml-1 in bulk solution. The RSDs were between 3 and 5%. The PIF methods were applied to the determination of tianeptine in a pharmaceutical preparation with recoveries varying from 96 to 106% in bulk solutions and from 98 to 106% for FIA-PIF.