Probing the reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with metal cations and acids in acetonitrile by electrochemistry and UV-Vis spectroscopy.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is certainly one of the most widely used free radicals in several applications, because of its high stability. Unfortunately, there are few works dealing with its stability in the presence of many chemical species that coexist during chemical processes. In this work, the stability of DPPH was investigated by electrochemistry and UV-Vis spectroscopy in the presence of some metal cations (Cu2+ and Zn2+) and acids (HClO4 and HNO3) in acetonitrile. In the presence of Cu2+, DPPH was oxidized to DPPH+ with the formation of an equivalent amount of Cu+. With Zn2+, DPPH undergoes a slow disproportionation with the formation of Zn(DPPH)+ and DPPH+, certainly favored by the acidity of the metal cation. This hypothesis was subsequently confirmed by studying the stability of DPPH in the presence of HClO4. This acid of appreciable strength in acetonitrile (pKa = 1.83) causes a fast disproportionation of DPPH with the formation of DPPH-H and DPPH+. This mechanism was confirmed both by UV-Vis spectroscopy and by electrochemistry, with a stoichiometry corresponding to 2 equivalents of DPPH for about 1 equivalent of HClO4. In the presence of nitric acid, which is about 107 weaker than HClO4 in acetonitrile, the disproportionation was much slower. These preliminary results are proof that many chemical species are likely to react with DPPH and indirectly induce sources of bias during its application, especially when evaluating antioxidant properties.

Electrochemical Determination of Epinephrine in Pharmaceutical Preparation Using Laponite Clay-Modified Graphene Inkjet-Printed Electrode.

Epinephrine (EP, also called adrenaline) is a compound belonging to the catecholamine neurotransmitter family. It can cause neurodegenerative diseases, such as Alzheimer's disease, Parkinson's disease, Huntington's disease and amyotrophic lateral sclerosis. This work describes an amperometric sensor for the electroanalytical detection of EP by using an inkjet-printed graphene electrode (IPGE) that has been chemically modified by a thin layer of a laponite (La) clay mineral. The ion exchange properties and permeability of the chemically modified electrode (denoted La/IPGE) were evaluated using multi-sweep cyclic voltammetry, while its charge transfer resistance was determined by electrochemical impedance spectroscopy. The results showed that La/IPGE exhibited higher sensitivity to EP compared to the bare IPGE. The developed sensor was directly applied for the determination of EP in aqueous solution using differential pulse voltammetry. Under optimized conditions, a linear calibration graph was obtained in the concentration range between 0.8 µM and 10 µM. The anodic peak current of EP was directly proportional to its concentration, leading to detection limits of 0.34 µM and 0.26 µM with bare IPGE and La/IPGE, respectively. The sensor was successfully applied for the determination of EP in pharmaceutical preparations. Recovery rates and the effects of interfering species on the detection of EP were evaluated to highlight the selectivity of the elaborated sensor.

Amino-Functionalized Laponite Clay Material as a Sensor Modifier for the Electrochemical Detection of Quercetin.

In this work, an electrode modified with an amino-functionalized clay mineral was used for the electrochemical analysis and quantification of quercetin (QCT). The resulting amine laponite (LaNH2) was used as modifier for a glassy carbon electrode (GCE). The organic-inorganic hybrid material was structurally characterized using X-ray diffraction, Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and CHN elemental analysis. The covalent grafting of the organosilane to the clay backbone was confirmed. The charge on the aminated laponite, both without and with the protonation of NH2 groups, was evaluated via cyclic voltammetry. On the protonated amine (LaNH3+)-modified GCE, the cyclic voltammograms for QCT showed two oxidation peaks and one reduction peak in the range of -0.2 V to 1.2 V in a phosphate buffer-ethanol mixture at pH 3. By using the differential pulse voltammetry (DPV), the modification showed an increase in the electrode performance and a strong pH dependence. The experimental conditions were optimized, with the results showing that the peak current intensity of the DPV increased linearly with the QCT concentration in the range from 2 × 10-7 M to 2 × 10-6 M, leading to a detection limit of 2.63 × 10-8 M (S/N 3). The sensor selectivity was also evaluated in the presence of interfering species. Finally, the proposed aminated organoclay-modified electrode was successfully applied for the detection of QCT in human urine. The accuracy of the results achieved with the sensor was evaluated by comparing the results obtained using UV-visible spectrometry.

Dioctylsulfosuccinate Functionalized NiAl-Layered Double Hydroxide for Sensitive Fenuron Electroanalysis Using a Carbon Paste Electrode.

Environmental pollution resulting from the use of pesticides such as fenuron poses significant health risks due to the carcinogenic and teratogenic properties of these compounds. There is an urgent need to develop rapid and cost-effective detection methods for quantifying fenuron. In this study, an inorganic-organic composite material was obtained by intercalating sodium dioctylsulfosuccinate (DSS) within the interlayer space of a nickel-aluminum-layered double hydroxide (NiAl-LDH). The pristine and modified LDHs (NiAl-LDH) were characterized using Fourier transform infrared, X-ray diffraction, and thermogravimetric analysis, confirming the successful intercalation of DSS in the mineral structure. The modified LDH was used to elaborate a sensor for detecting fenuron herbicide via differential pulse voltammetry (DPV) employing a carbon paste electrode (CPE). The electrochemical procedure for fenuron analysis consisted of immersing the working electrode in an electrolytic solution containing the appropriate amount of fenuron, followed by voltammetry detection without any preconcentration step. Compared to CPE modified by pristine LDH, the peak current obtained on the organo-LDH-modified CPE was twice as high. The increase in the fenuron signal was attributed to the high organophilic feature of this composite material induced by DSS modification. To optimize the sensitivity of the organo-LDH modified electrode, the effects of several experimental parameters such as pH of the medium and proportion of the modifier in the paste on the stripping response were examined. Linear calibration curves were obtained for the fenuron concentrations ranging from 0.5 × 10-6 to 1 × 10-6 mol.L-1 and 1 × 10-6 to 5 × 10-6 mol.L-1. The limit of detection (LOD) calculated on the basis of a signal-to-noise ratio of 3 was found to be 1.8 × 10-8 mol.L-1 for the low concentration range with a limit of quantification (LOQ) which was 6 × 10-8 mol.L-1. Furthermore, the interference effect of several inorganic ions and other pesticides potentially affecting fenuron stripping was explored, and the method's applicability was confirmed by determining fenuron levels in a river sample taken from down-town Yaoundé.

Unusual reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with Fe3+ controlled by competing reactions.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is a stable organic free radical widely used in various fields as a model free radical. There is scarce information about the stability of this compound in the chemical environments in which it is used. Side reactions between DPPH and other species can alter the precision of experiments that use DPPH, such as the evaluation of antioxidant properties amongst others. Following recent investigations highlighting reactions between DPPH and metal cations or Lewis acids, a quantitative reaction between DPPH and Fe3+ in acetonitrile was studied in the present work. UV-Vis spectroscopy and electrochemistry were used to monitor the reaction. The results obtained indicate a fast and multistep reaction between Fe3+ and DPPH that can be simplified as a simple redox reaction with the formation of Fe2+ and DPPH+. The reaction mechanism proposed follows complex steps involving two competing phenomena: a disproportionation which accelerates the reaction and an oxidation process that slows it down through DPPH regeneration.

An ultra-sensitive uric acid second generation biosensor based on chemical immobilization of uricase on functionalized multiwall carbon nanotube grafted palm oil fiber in the presence of a ferrocene mediator.

In this work, palm oil fiber (POF) grafted functionalized multiwall carbon nanotube (FMWCNT) decorated ferrocene (Fc) has been drop coated on a platinum electrode (Pt), in which uricase (UOx) has been chemically immobilized for sensitive and selective biosensing of uric acid (UA). Through the use of EDC/NHS, a stable bioelectrode (UOx/Fc/FMWCNT-POF/Pt) was obtained and characterized by FTIR/ATRIR, XRD, Raman, EA/EDX, TGA, SEM, TEM, CV, EIS, CA, and DPV. Results from DPV showed the rapid response of the developed bioelectrode towards UA (0.185 V) with high sensitivity (41.14 µA mM-1) and good limit of detection (19 µM) in the linear range 10-1000 µM. The low value of Michaelis-Menten constant (km = 31.364 µM) shows high affinity of the UA towards the enzyme at the electrode surface. The developed biosensor demonstrates good reproducibility, repeatability, and stability with a deviation of less than 2.5%, and was successfully applied for human blood sample analysis. The CA study revealed a fast response time (2 s) of the sensor. The work has pioneered a new addition to the class of tailorable chemical species for biosensor development and proven to be a promising new tool for point of care testing (POCT) applications.

Surface functionalization of natural hydroxyapatite by polymerization of ß-cyclodextrin: application as electrode material for the electrochemical detection of Pb(II).

A composite material prepared by polymerization of ß-cyclodextrin (ß-CD) on the surface of natural hydroxyapatite using citric acid as cross linker, was employed as electrode material for the detection of Pb(II). Hydroxyapatite was obtained from bovine bones, following a three-step procedure including pre-calcination, chemical treatment with (NH4)2HPO4, and calcination. The structure and morphology of the pristine hydroxyapatite (NHAPP0.5) and its functionalized counterpart (NHAPp0.5-CA-ß-CD) were examined using XRD, FTIR, and SEM. Upon deposition as thin film on a glassy carbon electrode (GCE), the ion exchange ability of NHAPp0.5-CA-ß-CD was exploited to elaborate a sensitive sensor for the detection of lead. The electroanalytical procedure was based on the chemical accumulation of Pb(II) ions under open-circuit conditions, followed by the detection of the preconcentrated species using differential pulse anodic stripping voltammetry. The reproducibility of the proposed method, based on a series of 8 measurements in a solution containing 2 µM Pb(II) gave a coefficient of variation of 1.27%. Significant parameters that can affect the stripping response of Pb(II) were optimized, leading to a linear calibration curve for lead in the concentration range of 2 × 10-8 mol L-1 - 20 × 10-8 mol L-1 (R2 = 0.998). The detection limit (3S/m) and the sensitivity of the proposed sensor were 5.06 × 10-10 mol L-1 and 100.80 µA.µM-1, respectively. The interfering effect of several ions expected to affect the determination of lead was evaluated, and the proposed sensor was successfully applied in the determination of Pb(II) ions in spring water, well water, river water and tap water samples.

Fabrication of an Organofunctionalized Talc-like Magnesium Phyllosilicate for the Electrochemical Sensing of Lead Ions in Water Samples.

A talc-like magnesium phyllosilicate functionalized with amine groups (TalcNH2), useful as sensor material in voltammetry stripping analysis, was synthesized by a sol-gel-based processing method. The characterizations of the resulting synthetic organoclay by scanning electron microscopy (SEM), X-ray diffraction, N2 sorption isotherms (BET method), Fourier transform infrared spectroscopy (FTIR), CHN elemental analysis and UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS) demonstrated the effectiveness of the process used for grafting of amine functionality in the interlamellar clay. The results indicate the presence of organic moieties covalently bonded to the inorganic lattice of talc-like magnesium phyllosilicate silicon sheet, with interlayer distances of 1568.4 pm. In an effort to use a talc-like material as an electrode material without the addition of a dispersing agent and/or molecular glue, the TalcNH2 material was successfully dispersed in distilled water in contrast to natural talc. Then, it was used to modify a glassy carbon electrode (GCE) by drop coating. The characterization of the resulting modified electrode by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed its charge selectivity ability. In addition, EIS results showed low charge transfer resistance (0.32 Ω) during the electro-oxidation of [Fe(CN)6]3-. Kinetics studies were also performed by EIS, which revealed that the standard heterogeneous electron transfer rate constant was (0.019 ± 0.001) cm.s-1, indicating a fast direct electron transfer rate of [Fe(CN)6]3- to the electrode. Using anodic adsorptive stripping differential pulse voltammetry (DPV), fast and highly sensitive determination of Pb(II) ions was achieved. The peak current of Pb2+ ions on TalcNH2/GCE was about three-fold more important than that obtained on bare GCE. The calculated detection and quantification limits were respectively 7.45 × 10-8 M (S/N = 3) and 24.84 × 10-8 M (S/N 10), for the determination of Pb2+ under optimized conditions. The method was successfully used to tap water with satisfactory results. The results highlight the efficient chelation of Pb2+ ions by the grafted NH2 groups and the potential of talc-like amino-functionalized magnesium phyllosilicate for application in electrochemical sensors.

Electroanalysis of diquat using a glassy carbon electrode modified with natural hydroxyapatite and ß-cyclodextrin composite.

The present work reports the development of a low-cost and reliable differential pulse adsorptive stripping voltammetric procedure for the detection of diquat (DQ) in water, using a glassy carbon electrode (GCE) modified with ß-cyclodextrin (ß-CD)/Natural hydroxyapatite (NHAPP0.5) composite material. The structural characterization of the natural hydroxyapatite and its modified counterpart was achieved using several techniques including X-ray Diffraction, Fourier Transform Infrared Spectroscopy and Thermal Analysis. By comparing the physico-chemical characteristics of hydroxyapatite material before and after reaction with ß-CD, all of these techniques have demonstrated the successful grafting process of ß-CD on the surface hydroxyl groups of hydroxyapatite, using citric acid (CA) as cross linker. The electrochemical features and permeability properties of the obtained materials, coated as thin film onto the GCE surface were characterized using ion exchange multisweep cyclic voltammetry. The ß-cyclodextrin modified hydroxyapatite (NHAPp0.5-CA-ß-CD) was evaluated as electrode modifier for DQ sensing. The electroanalytical procedure followed two steps: the chemical preconcentration of DQ under open-circuit conditions, and the differential pulse voltammetric detection of the preconcentrated pesticide. Various experimental parameters likely to influence the sensibility of electrode were fully investigated and optimized. A linear calibration curve for DQ in the concentration range of 5 × 10-8 - 4.5 × 10-7 mol L-1 was obtained at GCE/NHAPp0.5-CA-ß-CD, with a detection limit of 4.66 × 10-10 mol L-1 (DL = 3S/M). The proposed method was successfully applied to the determination of DQ in spring water.

A Low-Cost Layered Double Hydroxide (LDH) Based Amperometric Sensor for the Detection of Isoproturon in Water Using Carbon Paste Modified Electrode.

In this work, a Layered Double Hydroxide (NiAl-LDH) was obtained by coprecipitation method and used to elaborate an electrochemical sensor for the determination of isoproturon, which is a hazardous pollutant, widely used in agriculture, and its residue is distributed into aqueous environment through run-off and leaching from the soil. Various physicochemical techniques such as FT-IR spectroscopy, X-ray diffraction, and thermal analysis were used to characterize this material. The anionic exchange capacity of NiAl-LDH on carbon paste modified electrode was investigated toward [Fe(CN)6]3- using cyclic voltammetry. Used as electrode modifier of carbon paste electrode for isoproturon detection, a remarkable increase in isoproturon signal on modified carbon paste electrode by LDH was observed. The peak current obtained after 3 min of preconcentration in 25 µM ISO on NiAl-LDH/CPE was 2.6 times higher than that exhibited by the same analyte on the unmodified CPE, thereby opening the way to the development of a sensitive method for the detection of ISO. Other parameters that can affect the stripping response (preconcentration time, pH of detection medium, and LDH loading within the paste) were investigated to optimize the proposed sensor. After optimization, a linear calibration curve was obtained in the concentration range from 2 × 10-8 to 1.8 × 10-7 M, leading to a detection limit of 1 × 10-9 M (S/N = 3). The relative standard deviation for 5 identical measurements was 2.7%. The interfering effect of some compounds and ions was examined on the stripping response of ISO. The applicability of the method was verified by the determination of ISO in spiked water sample.

Performances of Alkaloid Extract from Rauvolfia macrophylla Stapf toward Corrosion Inhibition of C38 Steel in Acidic Media.

Alkaloid extract from Rauvolfia macrophylla Stapf (AERMS) was studied as the corrosion inhibitor for C38 steel in 1 M HCl and 0.5 M H2SO4 using electrochemistry and surface analysis. The corrosion inhibition was efficient and proceeds via adsorption of AERMS on the steel surface due to the active functional groups present in the molecules. AERMS acts as a mixed inhibitor in HCl and as a cathodic inhibitor in H2SO4. In H2SO4 corrosive medium, the presence of iodides improves the adsorption of the alkaloid molecules by reducing the surface charge of the electrode and thus substantially decreases the corrosion rate. Two pure alkaloids (tetrahydroalastonine (THA) and perakine (PER)) were quantitatively isolated from AERMS, and their anticorrosive properties for C38 steel in 1 M HCl and 0.5 M H2SO4 were evaluated. THA showed the highest efficiency while the performance of PER was less important compared to the extract. This confirms that the efficiency of AERMS was the result of the complementary action of the chemical compounds present in the extract.

Preparation of Methyl Viologen-Kaolinite Intercalation Compound: Controlled Release and Electrochemical Applications.

This work reports the preparation of novel kaolinite nanohybrid material obtained by intercalation of methyl viologen (MV) in the interlayer space of kaolinite, using methoxykaolinite (K-M) as starting material. Characterization of the resulting material (K-MV) confirmed the presence of MV units in the interlayer space of K-M with lateral orientation, associated with a high amount of water molecules due to the hydrophilic nature of MV. The resulting structural formula of this organoclay based on thermogravimetric analysis was Si2Al2O5(OH)3.72(OCH3)0.28(MV)0.17(H2O)0.82. The release of MV from the K-MV composite was studied in order to evaluate the advantages of using this material for pesticide formulation with MV as active ingredient. The localization of MV in the interlayer space of K-M significantly slows its release in water. However, the interactions that retain MV in the interlayer space remain sufficiently less intense to ensure a complete release of MV in a relatively short time (2 h). On the basis of the interactions that ensure MV intercalation in methoxykaolinite, K-M was used as electrode modifier and applied for the electrochemical determination of MV. The electrochemical signal of MV on the K-M modified electrode was 2 times more intense compared to the pristine kaolinite modified electrode. After optimization of experimental parameters, a sensitivity of 3.91 µA M-1 and a detection limit of 0.14 nM were obtained at the K-M modified electrode. This performance represents one of the most important reported so far in the literature during the electrochemical determination of MV. The sensor was also found very efficient for MV determination in real water systems (well, spring, and tap water) despite the decrease of sensitivity due to the presence of interfering species.

Voltammetric behavior of Mammeisin (MA) at a glassy carbon electrode and its interaction with Bovine Serum Albumin (BSA).

The electrochemical oxidation of Mammeisin (MA) was studied in a solution containing acetone and 0.1M phosphate buffer +0.1M KCl (pH=5.3) at a glassy carbon electrode (GCE), using cyclic (CV) and square wave voltammetry (SWV). MA showed a quasi-reversible process, which is pH dependent and that involves the exchange of two electrons and two protons. The oxidation product was adsorbed by the electrode surface to form a film that blocks active sites over repetitive cyclic. Moreover, the interaction of MA and bovine serum albumin (BSA) was studied by CV and SWV at different pHs (5.4, 7.2, 9.5). As a result of the affinity binding with BSA, electrochemically inactive complex was formed. In addition, the oxidation potential of MA in the presence of BSA depends on the pH. The diffusion coefficients of both free and bound MA were estimated from the cyclic voltammetry data using the method developed by Randles-Sevich (Df=9.85×10-5cm2s-1 and Db=1.27×10-9cm2s-1) and the binding constant of MA-BSA complex, K=3.47×102Lmol-1, was obtained.

Quaternary ammonium functionalized clay film electrodes modified with polyphenol oxidase for the sensitive detection of catechol.

Naturally occurring Cameroonian smectite clay has been grafted with trimethylpropylammonium (TMPA) groups and the resulting organoclay has been deposited onto a glassy carbon electrode surface as a suitable immobilization matrix for polyphenol oxidase (PPO). High sensitivity of the electrochemical device to catechol biosensing can be achieved when the enzyme was impregnated within the organoclay film subsequent to its deposition due to favorable electrostatic interaction between PPO and the TMPA-clay layer. The bioelectrode preparation method was also compatible with the use of a mediator (i.e., ferrocene) and the best performance was obtained with a three-layer configuration made of glassy carbon coated with a first layer of ferrocene (Fc), which was then covered with the PPO-impregnated TMPA-clay layer, and finally overcoated with an enzyme-free TMPA-clay film acting as a protecting overlayer to avoid leaching of the biomolecule in solution. The electrochemical behavior of the modified film electrodes was first characterized by cyclic voltammetry and, then, they were evaluated for the amperometric biosensing of the model analyte catechol in batch conditions and in flow injection analysis. Various experimental parameters likely to influence the biosensor response have been investigated, including the electrode preparation mode (composition configuration, thickness), the usefulness of a mediator, the operating potential and pH of the medium, as well as the advantageous features of the TMPA-clay in comparison to related film electrodes based on non-functionalized clays. The organoclay was found to provide a favorable environment to enzyme activity and the multilayer configuration of the film electrode to provide a biosensor with good characteristics, such as an extended linear range for catechol detection (2 x 10(-8) to 1.2 x 10(-5)M) and a detection limit in the nanomolar range (9 x 10(-9)M).

Electrolytic arsenic removal for recycling of washing solutions in a remediation process of CCA-treated wood.

The remediation of chromated copper arsenate or CCA-treated wood is a challenging problem in many countries. In a wet remediation, the recycling of the washing solutions is the key step for a successful process. Within this goal, owing to its solubility and its toxicity, the removal of arsenic from washing solution is the most difficult process. The efficiency of arsenic removal from As(III) solutions by electrolysis was investigated in view of the recycling of acidic washing solutions usable in the remediation of CCA-treated wood. Electrochemical reduction of As(III) is irreversible and thus difficult to perform at carbon electrodes. However the electrolytic extraction of arsenic can be performed by the concomitant reduction of the cupric cation and arsenite anion. The cathodic deposits obtained by controlled potential electrolysis were analyzed by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis. XRD diffraction data indicated that these deposits were mixtures of copper and copper arsenides Cu(3)As and Cu(5)As(2). Electrolysis was carried out in an undivided cell with graphite cathode and copper anode, under a controlled nitrogen atmosphere. The evolution of arsine gas AsH(3) was not observed under these conditions.

Square wave voltammetric detection by direct electroreduction of paranitrophenol (PNP) using an organosmectite film-modified glassy carbon electrode.

This work describes the development of a low-cost and reliable adsorptive stripping voltammetric method for the detection of PNP in water. Organoclays were prepared by intercalation in various loading amounts of cetyltrimethylammonium ions (CTA(+)) in the interlayer space of a smectite-type clay mineral. Their structural characterization was achieved using several techniques including X-ray diffraction (XRD), N2 adsorption-desorption (BET method) and Fourier Transform Infrared spectroscopy (FTIR) that confirmed the intercalation process and the presence of the surfactant ions within the clay mineral layers. Using [Fe(CN)6](3-) and [Ru(NH3)6](3+) as redox probes, the surface charge and the permeability of the starting clay mineral and its modified counterparts were assessed by multisweep cyclic voltammetry, when these materials were coated on the surface of a glassy carbon electrode (GCE). In comparison with the bare GCE, the organoclay modified electrodes exhibited more sensitive response towards the reduction of paranitrophenol (PNP). Under optimized conditions, a calibration curve was obtained in the concentration range from 0.2 to 5.2µmolL(-1); leading to a detection limit of 3.75×10(-8)molL(-1) (S/N=3). After the study of some interfering species on the electrochemical response of PNP, the developed sensor was successfully applied to the electroanalytical quantification of the same pollutant in spring water.

Removal of Cd (II) from synthetic wastewater by alginate-Ayous wood sawdust (Triplochiton scleroxylon) composite material.

The biosorption characteristics of Cd (II) ions from synthetic wastewater using raw Ayous wood sawdust (Triplochiton scleroxylon), r-AS, immobilized by sodium alginate were investigated with respect to pH, biomass quantity, contact time, initial concentration of heavy metal, temperature and stirring rate. The experimental data fitted well with the Langmuir isotherm, suggesting that monolayer adsorption of the cadmium ions onto alginate-Ayous sawdust composite (a-ASC). The obtained monolayer adsorption capacity of a-ASC for Cd (II) was 6.21 mg/g. From the Dubinin-Radushkevich isotherm model, a 5.39 kJ/mol value for the mean free energy was calculated, indicating that Cd (II) biosorption could include an important physisorption stage. Thermodynamic calculations showed that the Cd (II) biosorption process was feasible, endothermic and spontaneous in nature under examined conditions. The results indicated that a-ASC could be an alternative material replacing more costly adsorbents used for the removal of heavy metals.

Electrochemical determination of mesotrione at organoclay modified glassy carbon electrodes.

A natural Cameroonian smectite-type clay (SaNa) was exchanged with cationic surfactants, namely cetyltrimethylammonium (CTA) and didodecyldimethyl ammonium (DDA) modifying its physico-chemical properties. The resulting organoclays that have higher adsorption capacity for mesotrione than the pristine SaNa clay, have been used as modifiers of glassy carbon electrode for the electrochemical detection of this herbicide by square wave voltammetry. The stripping performances of SaNa, SaCTA and SaDDA modified electrodes were therefore evaluated and the experimental parameters were optimized. SaDDA gives the best results in deoxygenated acetate buffer solution (pH 6.0) after 2 min accumulation under open circuit conditions. Under optimal conditions, the reduction current is proportional to mesotrione concentration in the range from 0.25 to 2.5 µM with a detection limit of 0.26 µM. The fabricated electrode was also applied for the commercial formulation CALLISTO, used in European maize market.

Amperometric sensors based on sawdust film modified electrodes: application to the electroanalysis of paraquat.

Natural or sodium hydroxide treated Ayous sawdusts were used to prepare thin film electrodes (denoted respectively as PSTFE and SSTFE). The sensors obtained exhibit good mechanical stability and a wide electrochemical potential range. Their electrochemical characterization revealed that they present a good capacity to accumulate cations, but are not useful for the electroanalysis of anions. In all cases, the signals were more intense and well defined on SSTFE compared to PSTFE. When applied to the electroanalysis of paraquat, a significant improvement of the current intensities was obtained on these electrodes compared to the bare glassy carbon electrode. The diffusion of this compound through the film which is the main process governing the electrochemical reaction at the electrode surface, is 2.2 times more important with SSTFE compared to PSTFE. After the optimization of the detection parameters, calibration curves were obtained in the concentration range 0.1-0.725 µmol L(-1) for PSTFE and 0.05-0.6 µmol L(-1) for SSTFE. The detection limits determined for a signal/noise ratio=3 are 5.49×10(-9) mol L(-1) for PSTFE and 3.02×10(-9) mol L(-1) for SSTFE.

Electrochemical response of ascorbic and uric acids at organoclay film modified glassy carbon electrodes and sensing applications.

A naturally occurring Cameroonian smectite clay has been grafted with trimethylpropylammonium groups and the resulting organoclay deposited as thin film onto a glassy carbon electrode (GCE) surface. It was then exploited as a suitable matrix for the accumulation and the electrochemical detection of ascorbic acid (AA) and uric acid (UA). Cyclic voltammetry revealed an increase in oxidation peak responses along with a negative shift of the corresponding anodic peak potential for both AA and UA species when using the organoclay coated GCE in comparison with the bare electrode. The electroanalytical response was improved by coating the electrode surface with a first layer of sublimed ferrocene (FC(s)), and then overcoating with the organoclay film to avoid the mediator leaching. The resulting bilayer film exhibited good characteristics such as extended linear range and high sensitivities for AA and UA, in cyclic voltammetry and amperometry. Interestingly, the redox mediator FC(s) was likely to lower overpotentials for AA oxidation (but not for UA), making possible the selective detection of these species in a mixture. The developed method could be used for the determination of AA in a pharmaceutical preparation and for UA in urine.