A diazonium-functionalized silver electrode for the sensitive amperometric detection of p-nitrophenol in water over a wide range of concentrations.

This work presents a novel approach for the electrochemical detection of p-nitrophenol (pNP) focusing on the development of a simple and efficient strategy to overcome pNP adsorption. The proposed method involves the functionalization of a silver (Ag) electrode with an electrografted, thin diazonium film. After characterization by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry, the as-functionalized electrode allowed a wide linear detection range to be established in aqueous solutions, spanning from 1 to 500 µM pNP. This outcome indicates that the diazonium film effectively addresses any issues related to adsorption with good repeatability and reproducibility. Furthermore, the sensor's analytical performances were evaluated yielding a sensitivity and a limit of detection of 0.3819 µA cm-2 µM-1 and 600 nM, respectively. The sensor was also found to exhibit a good selectivity towards pNP and phenolic compounds and was successfully tested on a real water sample.

Mercury(II) trace detection by a gold nanoparticle-modified glassy carbon electrode using square-wave anodic stripping voltammetry including a chloride desorption step.

Gold nanoparticles (AuNPs) were deposited on a glassy carbon (GC) substrate by constant potential electrolysis and characterized by cyclic voltammetry in H2SO4 and field emission gun scanning electron microscopy (FEG-SEM). The modified AuNPs-GC electrode was used for low Hg(II) concentration detection using a Square Wave Anodic Stripping Voltammetry (SWASV) procedure which included a chloride desorption step. The comparison of the obtained results with our previous work in which no desorption step was used showed that this latter step significantly improved the analytical performances, providing a three time higher sensitivity and a limit of detection of 80pM for 300s preconcentration, as well as a lower average standard deviation. The influence of chloride concentration on the AuNPs-GC electrode response to Hg(II) trace amounts was also studied and its optimal value confirmed to be in the 10(-2)M range. Finally, the AuNPs-GC electrode was used for the determination of Hg(II) in a natural groundwater sample from south of France. By using a preconcentration time of 3000s, a Hg(II) concentration of 19±3pM was found, which compared well with the result obtained by cold vapor atomic fluorescence spectroscopy (22±2pM).

Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution.

A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic "on line" monitoring devices are also evoked.

Real-time electrochemical PCR with a DNA intercalating redox probe.

The proof-of-principle of a nonoptical real-time PCR method based on the electrochemical monitoring of a DNA intercalating redox probe that becomes considerably less easily electrochemically detectable once intercalated to the amplified double-stranded DNA is demonstrated. This has been made possible thanks to the finding of a redox intercalator that (i) strongly and specifically binds to the amplified double-stranded DNA, (ii) does not significantly inhibit PCR, (iii) is chemically stable under PCR cycling, and (iv) is sensitively detected by square wave voltammetry during PCR cycling. Among the different DNA intercalating redox probes that we have investigated, namely, methylene blue, Os[(bpy)(2)phen](2+), Os[(bpy)(2)DPPZ](2+), Os[(4,4'-dimethyl-bpy)(2)DPPZ](2+) and Os[(4,4'-diamino-bpy)(2)DPPZ](2+) (with bpy = 2,2'-bipyridine, phen = phenanthroline, and DPPZ = dipyrido[3,2-a:2',3'-c]phenazine), the one and only compound with which it has been possible to demonstrate the proof-of-concept is the Os[(bpy)(2)DPPZ](2+). In terms of analytical performances, the methodology described here compares well with optical-based real-time PCRs, offering finally the same advantages than the popular and routinely used SYBR Green-based real-time fluorescent PCR, but with the additional incomes of being potentially much cheaper and easier to integrate in a hand-held miniaturized device.

Electrochemical functionalization of carbon surfaces by aromatic azide or alkyne molecules: a versatile platform for click chemistry.

The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide- or alkyne-modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3-triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.

Chemistry and electrochemistry of the heterodinuclear complex ClPd(dppm)2PtCl: a M-M' bond providing site selectivity.

The heterodinuclear d(9)-d(9) title compound 1, whose crystal structure has been solved, reacts with dppm [bis(diphenylphosphino)methane] in the presence of NaBF4 to generate the salt [ClPd(mu-dppm)2Pt(eta(1)-dppm)][BF4] (2a), which contains a Pt-bound dangling dppm ligand. 2a has been characterized by 1H and 31P NMR, Fourier transform Raman [nu(Pd-Pt) = 138 cm(-1)], and UV-vis spectroscopy [lambda(max)(dsigma-dsigma*) = 366 nm]. In a similar manner, [ClPd(mu-dppm)2Pt(eta(1)-dppm=O)][BF4] (2b), ligated with a dangling phosphine oxide, has been prepared by the addition of dppm=O. The molecular structure of 2b has been established by an X-ray diffraction study. 2a reacts with 1 equiv of NaBH4 to form the platinum hydride complex [(eta(1)-dppm)Pd(mu-dppm)2Pt(H)][BF4] (3). Both 2a and 3 react with an excess of NaBH4 to provide the mixed-metal d(10)-d(10) compound [Pd(mu-dppm)3Pt] (4). The photophysical properties of 4 were studied by UV-vis spectroscopy [lambda(max)(dsigma-dsigma*) = 460 nm] and luminescence spectroscopy (lambda(emi) = 724 nm; tau(e) = 12 +/- 1 micros, 77 K). The protonation of 1 and 4 leads to [ClPd(mu-dppm)2(mu-H)PtCl]+ (5) and 3, respectively. Stoichiometric treatment of 1 with cyclohexyl or xylyl isocyanide yields [ClPd(mu-dppm)2Pt(CNC6H11)]Cl (6a) and [ClPd(mu-dppm)2Pt(CN-xylyl)]Cl (6b) ligated by terminal-bound CNR ligands. In contrast, treatment of 1 with the phosphonium salt [C[triple bond]NCH2PPh3]Cl affords the structurally characterized A-frame compound [ClPd(mu-dppm)2(mu-C=NCH2PPh3)PtCl]Cl (6c), spanned by a bridging isocyanide ligand. The electrochemical reduction of 2a at -1.2 V vs SCE, as well as the reduction of 5 in the presence of dppm, leads to a mixture of products 3 and 4. Further reduction of 3 at -1.7 V vs SCE generates 4 quantitatively. The reoxidation at 0 V of 4 in the presence of Cl- ions produces back complex 2a. The whole mechanism of the reduction of 1 has been established.

The Pd(4)(dppm)(4)(H)(2)(2+) cluster: a precatalyst for the homogeneous hydrogenation of alkynes.

The catalytic properties of the title cluster toward the homogeneous hydrogenation of phenylacetylene, diphenylethyne and phenyl-1-propyne have been investigated as a function of temperature, pressure, solvents, substrate and cluster concentrations, and counterions. The title cluster is a precatalyst that exhibits a good catalytic activity under mild conditions (1 atm of H(2) at 20 degrees C) for the hydrogenation of alkynes and alkenes. For the alkyne substrates, the turnover frequencies (tof's) range between 200 and 500 h(-)(1), and the product distribution varies as: cis-products, 75-90%; trans-products; 0-8% after 3 h of reaction. Based on the graphs -d[substrate]/dt vs [Pd(4)](1/2), the mechanism indicates a cluster dissociation into two dimers (presumably of the type Pd(2)(dppm)(2)(H)(solvent)(+)). The variations of tof (or -d[substrate]/dt) as a function of [substrate] and pressure of H(2) are linear. At 1600 psi of H(2), the tof can reach 2500-3000 h(-)(1) (in THF). The tof also increases with temperature reaching a maximum at approximately 35 degrees C (tof: 1000-1300 h(-)(1)), but at higher temperatures cluster decomposition begins to occur, leading to a rapid decrease in rates of catalysis. At 50 degrees C, no catalysis is observed. The hydrogenation reaction can be stopped at the corresponding cis-alkenes with approximately 95% yields, depending on the substrate and experimental conditions used. The tof's also vary with the solvent, where stronger coordinating solvent molecules give higher tof's. In addition, the tof's do not change with the nature of the counterion, which acts as "spectator" in the catalysis.