Search

International audience; Waste printed circuits boards are a major source of strategic materials such as platinum group metals since they are used for the fabrication of technological devices, such as hard drive discs, capacitors, diodes, etc. Because of the high cost of platinum, palladium and gold (> 25k€ / kg), an economic and environmental challenge is their recycling from printed circuit boards, that represent around 2% weight of electronic equipment. Hydrometallurgical treatments allow to recover these metals in solution, with a high recovery rate for a leaching liquor made of thiourea in hydrochloric acid. So as to develop an efficient recycling process from this leach liquor, one requires the speciation of these strategic metals, as well as their extraction and quantitation in the mixture. For this purpose, platinum, palladium and gold were dissolved in model leach liquors made of hydrochloric acid and thiourea at low concentration. The identification of metal complexes was determined in function of thiourea concentration (between 10 µmol/L and 10 mmol/L) by the combination of UV-Visible spectrometry, cyclic voltammetry and for the first time capillary electrophoresis. The electrokinetic method was then applied for the quantitation of trace metal analyses in leach samples from waste printed circuit boards reprocessing, demonstrating its applicability for industrializable recycling applications.

Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high activation energy barrier. Of molecular catalysts, metal complexes with polypyridyl ligands are well represented, among which the [Cp*Rh(bpy)Cl] + and [M(bpy)(CO)3X] (M = Re, Mn) complexes. As redox non-innocent ligand, the bipyridine ligand is generally involved in the reduction mechanisms. It is thus tempting to replace it by other redox non-innocent ligands such as vacant polyoxometalates (POMs). We have thus prepared [α-H2PW11O39{Rh(III)Cp*(OH2}] 3-which is closely related to [Cp*Rh(III)(bpy)Cl] + by substitution of the monovacant [PW11O39] 7-Keggin-type POM for the bipyridine ligand. Its activity towards CO2 reduction has been assessed in acetonitrile in the presence of water. Compared to [Cp*Rh(bpy)Cl] + that produces formate selectively over CO and H2, the POM derived catalyst favours proton reduction over CO2 reduction.

International audience; COOH-functionalized multi-walled carbon nanotubes (f-MWCNTs) film coated on glassy carbon electrode (GCE) were prepared, and the detection of diclofenac (DCF) was investigated by cyclic voltammetry and amperometry. The results showed that the nano-structured electrodes exhibit good analytical performances towards the electrochemical oxidation of DCF with a detection limit of 0.1 μM and a sensitivity of 0.06 μA. μM−1 within a dynamic concentration range varying from 2 μM to 15 μM.

The existence of a novel double-molybdate phase with a palmierite-type structure, Cs2Ba(MoO4)2, is revealed in this work, and its structural properties at room temperature have been characterized in detail using X-ray and neutron diffraction measurements. In addition, its thermal stability and thermal expansion are investigated in the temperature range 298–673 K using high-temperature X-ray diffraction, leading to the volumetric thermal expansion coefficient αV ≈ 43.0 × 10–6 K–1. The compound’s standard enthalpy of formation at 298.15 K has been obtained using solution calorimetry, which yielded ΔfHm°(Cs2Ba(MoO4)2, cr, 298.15 K) = −3066.6 ± 3.1 kJ· mol–1, and its standard entropy at 298.15 K has been derived from low-temperature (2.1–294.3 K) thermal-relaxation calorimetry as Sm°(Cs2Ba(MoO4)2, cr, 298.15 K) = 381.2 ± 11.8 J K–1 mol–1., The existence of Cs2Ba(MoO4)2 with a palmierite structure is reported for the first time. The structure has been characterized by X-ray and neutron diffraction, and the thermal expansion has been measured by high-temperature XRD. Moreover, key thermodynamic properties (standard enthalpy of formation and standard entropy) have been derived from solution calorimetry and low-temperature thermal relaxation calorimetry.

International audience; We report here on the multiproton-multielectron electrochemical reduction of CO2 in homogeneous solution by using (TOA)6[α-SiW11O39Co(_)] (TOA = tetraoctyl ammonium; _ = vacant position in the coordination sphere of Co) as an electrocatalyst. First, the electrochemical behavior of (TOA)6[α-SiW11O39Co(_)] was analyzed in detail by cyclic voltammetry in dichloromethane, studying the influence of the presence of protons and/or CO2. These preliminary results were further used to optimize the conditions of electrolysis in terms of reduction potentials. Analysis of the electrolysis products in the gas and liquid phases show the formation of CO and HCHO without formation of H2. Our results tend to show that the (TOA)6[α-SiW11O39Co(_)] polyoxometalate is a catalyst for CO2 electroreduction, with unique selectivity.

The physicochemical properties of the potassium neptunate K2NpO4 have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L3 edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K2NpO4 have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.

Graphite rods were modified by substituted aryldiazonium salts allowing subsequent laccase immobilisation and direct electron transfer at the cathode. Two covalent enzyme immobilisation methods were performed with carboxy and amino substituted grafted groups, either via the formation of an amide bond or a Schiff base between the glycosidic groups of the enzyme and the amino groups on the electrode surface, respectively. Laccase adsorption efficiency was consistently compared to the covalent attachment method on the same carbon surface, showing that the latter method led to a higher immobilisation yield when the electrode surface was functionalised with carboxylic groups, as shown from both laccase activity measurement towards an organic reducing substrate, ABTS, and quantitative XPS analysis. Both analytical methods led to similar laccase surface coverage estimations. From activity measurements, when laccase was covalently immobilised on the electrode functionalised with carboxylic groups, the surface coverage was found to be 43 ± 2% whereas it was only 10 ± 3% when laccase was adsorbed. Biocatalysed dioxygen reduction current was also higher in the case of covalent immobilisation. For the first time, oxidised laccase performances were compared to unmodified laccase, showing significant improved efficiency when using oxidised laccase: the current obtained with oxidised laccase was 141 ± 37 μA cm− 2 compared to 28 ± 6 μA cm− 2 for unmodified laccase after covalent immobilisation of the enzyme on a graphite electrode functionalised with carboxylic groups.

International audience; The hexavalent and heptavalent sodium neptunate compounds Na$_4$NpO$_5$ and Na$_5$NpO$_6$ have been investigated using X-ray powder diffraction, Mossbauer spectroscopy, magnetic susceptibility, and specific heat measurements. Na$_4$NpO$_5$ has tetragonal symmetry in the space group 14/m, while Na$_5$NpO$_6$ adopts a monoclinic unit cell in the space group C2/m. Both structures have been refined for the first time using the Rietveld method. The valence states of neptunium in these two compounds, i.e., Np(VI) and Np(VII), respectively, have been confirmed by the isomer shift values of their Mossbauer spectra. The local structural properties obtained from the X-ray refinements have also been related to the quadrupole coupling constants and asymmetry parameters determined from the Mossbauer studies. The absence of magnetic ordering has been confirmed for Na$_4$NpO$_5$. However, specific heat measurements at low temperatures have suggested the existence of a Schottky-type anomaly at around 7 K in this Np(VI) phase.

The structure of α-Cs2Mo2O7 (monoclinic in space group P 2 1 / c ), which can form during irradiation in fast breeder reactors in the space between nuclear fuel and cladding, has been refined in this work at room temperature from neutron diffraction data. Furthermore, the compounds' thermal expansion and polymorphism have been investigated using high temperature X-ray diffraction combined with high temperature Raman spectroscopy. A phase transition has been observed at Ttr( α → β )=(621.9±0.8) K using Differential Scanning Calorimetry, and the structure of the β-Cs2Mo2O7 phase, orthorhombic in space group Pbcm, has been solved ab initio from the high temperature X-ray diffraction data. Furthermore, the low temperature heat capacity of α-Cs2Mo2O7 has been measured in the temperature range T=(1.9–313.2) K using a Quantum Design PPMS (Physical Property Measurement System) calorimeter. The heat capacity and entropy values at T=298.15 K have been derived as C p , m o ( Cs 2 Mo 2 O 7 , cr , 298.15 K ) = ( 211.9 ± 2.1 ) J K − 1 mol − 1 and S m o ( Cs 2 Mo 2 O 7 , cr , 298.15 K ) = ( 317.4 ± 4.3 ) J K − 1 mol − 1 . When combined with the enthalpy of formation reported in the literature, these data yield standard entropy and Gibbs energy of formation as Δ f S m o ( Cs 2 Mo 2 O 7 , cr , 298.15 K ) = − ( 628.2 ± 4.4 ) J K − 1 mol − 1 and Δ f G m o ( Cs 2 Mo 2 O 7 , cr , 298.15 K ) = − ( 2115.1 ± 2.5 ) kJ mol − 1 . Finally, the cesium partial pressure expected in the gap between fuel and cladding following the disproportionation reaction 2Cs2MoO4=Cs2Mo2O7+2Cs(g)+ 1/2 O2(g) has been calculated from the newly determined thermodynamic functions.

The simultaneous electrochemical quantification of oxidized (GSSG) and reduced glutathione (GSH), biomarkers of oxidative stress, is demonstrated in biological fluids. The detection was accomplished by the development of a modified carbon electrode and was applied to the analysis of fluids of model organisms under to oxidative stress caused by lead intoxication. Nanocomposite molecular material based on cobalt phthalocyanine (CoPc) and multiwalled carbon nanotubes functionalized with carboxyl groups (MWCNTf) was developed for modifying glassy carbon electrodes (GCE) for the detection of reduced and oxidized glutathione. The morphology of the nanocomposite film was characterized by scanning electron microscopy (SEM) and profilometry. The electrochemical behavior of the modified electrode was assessed by cyclic voltammetry (CV) to determine the surface coverage (Γ) by CoPc. The electrocatalytic behavior of the modified electrode towards reduced (GSH) and oxidized (GSSG) forms of glutathione was assessed by ...

The reduction of UVI uranyl halides or amides with simple LnII or UIII salts forms highly symmetric, linear, oxo-bridged trinuclear UV /LnIII /UV , LnIII /UIV /LnIII , and UIV /UIV /UIV complexes or linear LnIII /UV polymers depending on the stoichiometry and solvent. The reactions can be tuned to give the products of one- or two-electron uranyl reduction. The reactivity and magnetism of these compounds are discussed in the context of using a series of strongly oxo-coupled homo- and heterometallic poly(f-block) chains to better understand fundamental electronic structure in the f-block.

International audience; A series of [Re(N\^N)(CO)3(X)] (N\^N = diimine and X = halide) complexes based on 4-(2-pyridyl)-1,2,3-triazole (pyta) and 1-(2-pyridyl)-1,2,3-triazole (tapy) diimine ligands have been prepared and electrochemically characterized. The first ligand-based reduction process is shown to be highly sensitive to the nature of the isomer as well as to the substituents on the pyridyl ring, with the peak potential changing by up to 700 mV. The abilities of this class of complexes to catalyze the electroreduction and photoreduction of CO2 were assessed for the first time. It is found that only Re pyta complexes that have a first reduction wave with a peak potential at ca. -1.7 V vs SCE are active, producing CO as the major product, together with small amounts of H2 and formic acid. The catalytic wave that is observed in the CVs is enhanced by the addition of water or trifluoroethanol as a proton source. Long-term controlled potential electrolysis experiments gave total Faradaic yield close to 100%. In particular, functionalization of the triazolyl ring with a 2,4,6-tri-tert-butylphenyl group provided the catalyst with a remarkable stability.

We discuss here the state of the art on hybrid materials made from single (SWCNT) or multi (MWCNT) walled carbon nanotubes and MN4complexes such as metalloporphyrins and metallophthalocyanines. The hybrid materials have been characterized by several methods such as cyclic voltammetry (CV), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and scanning electrochemical microscropy (SECM). The materials are employed for electrocatalysis of reactions such as oxygen and hydrogen peroxide reduction, nitric oxide oxidation, oxidation of thiols and other pollutants.

An electrochemical sensor detects the risk of diabetes and prediabetes; low potentials are applied to nickel electrodes and electrical responses are measured. Although the contact of nickel with skin is short, the risk of allergical reactions cannot be discarded. SS 304L, with lower Ni content, was tested in carbonate buffer solutions containing chloride, lactate and urea to investigate its sensitivity to different parameters in sweat and compare it to nickel. The results show that SS 304L is a suitable material for the assessment of sudomotor dysfunction due to its high capacity to detect the deviation in Cl− concentration. Sensitivity of SS 304L to Cl− is much higher than for nickel.

We have studied the electrochemical kinetics of anodic Ni dissolution as a function of chloride ion concentration, at pH 5, 6 and 7, in order to mimic the conditions of sweat samples. Our results show that the rate-determining step for Ni dissolution in the mentioned pH range is the transfer of one first electron, as suggested by the Tafel slopes close to 0.120 V/decade. However, the reaction order in chloride ion varies from ca. 2 at pH 7 to values close to unity for pH values between 5 and 6. This finding is very important for sensor applications in sweat fluids since the sensitivity of the Ni electrode to chloride ions is higher in neutral solutions (pH ca. 7) compared to that in slightly acid solutions (pH between 5 and 6). Small variations in pH in real samples are expected so this change in sensitivity should be considered when sensing chloride ions in sweat fluids.

The control of the interface properties of titanium (Ti) and related alloys is of prime significance in dental implantology to enhance the biological compatibility of screws. In this work, we have investigated the use of electrochemical grafting of diazonium salts to modify the surface of titanium samples to propose a simple, low-cost, and reliable functionalization technique for titanium and titanium-based alloys. We have explored this electrochemical procedure by using two model salts in acidic aqueous solution, namely 4-nitrobenzenediazonium tetrafluoroborate (NBD) and 4-carboxybenzenediazonium tetrafluoroborate (CBD). A thorough chemical characterization of functionalized Ti surface enabled us to ascertain the presence of nitrophenyl or carboxyphenyl groups at titanium surfaces. The influence of the scan rate during the electrografting procedure on the properties of the modified surfaces was also analyzed by XPS. From our results, NBD is most probably electrografted according to an island-like model, as the equivalent thickness of the adsorbed layer, estimated from XPS measurements, is below one monolayer, while, CBD is electrografted in few multilayers of 2 to 3 nm thickness, depending on the scan rate used during electrografting.

The surface ageing of nickel electrodes was studied in the frame of the development of non-invasive biomedical devices, dedicated to the detection of sudomotor dysfunction manifested by an alteration of the ionic balance in human sweat. In this kind of technology, low voltage potentials with variable amplitudes are applied to nickel electrodes, placed on skin regions with a high density of sweat glands, and the electrical responses are measured. The trick is that nickel electrodes play alternately the role of anode and cathode, thus the analysis of the temporal evolution of the physico-chemical properties of nickel is of prime importance to ensure the good performance of the device. Electrochemical measurements coupled to surface chemical characterizations (X-ray photoelectron spectroscopy (XPS), Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS)) were performed on pure Ni samples, immersed in buffered chloride solutions mimicking human sweat. The shapes of voltammograms, recorded in a restricted anodic potential range, show that the nickel surface was gradually passivated as a function of the number of scans. This was confirmed by XPS data, with the formation of a 1 nm thick duplex layer composed by nickel hydroxide (outermost layer) and nickel oxide (inner layer). In a negative extended potential range, though the electrochemical behavior of electrodes was not modified upon cycling the potential, XPS data show that the inner layer was thickening, indicating a surface degradation of the nickel electrode. Below pitting potentials, adsorbed chloride was only hardly detected by XPS, and the surface composition of the nickel samples was similar after treatments in chloride or chloride-free buffered solutions. In a larger potential range enabling to reach the breakdown potential, the highly chemically sensitive ToF-SIMS characterization pointed out that the surface concentration of adsorbed chloride was higher in pits than elsewhere on the surface sample.

In this work, we report on the design, microfabrication and use of a ring disk ultramicroelectrodes array (RD-UMEs) for direct detection of nitric oxide (NO)-release from decomposition of S-Nitrosoglutathione (GSNO) catalyzed by copper species. The electrochemical device includes seven individually addressable sets of gold RD-UMEs pairs and four gold counter electrodes. For each pair of RD-UMEs, the gold ring is electrochemically modified by poly(eugenol)/poly(phenol) layers to act as NO-sensor while the gold disc electrode is electrochemically coated by a copper layer serving as Cu2+ source for the catalysis of the in situ decomposition of GSNO. The mediated decomposition of GSNO by Cu2+ is achieved in presence of ascorbate. NO released from GSNO is detected on NO ring electrode at the same potential applied to form the Cu2+-based catalyst (+0.8 V vs. Ag/AgCl) in phosphate buffer solution with or without serum. Keywords: Nitrosothiols, Nitric oxide, Electrochemical sensor, Copper catalyst

Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors.

This work describes the conditions of use of bare gold electrode to detect electrochemically the presence of peroxynitrite ONOO− in phosphate buffer solution at pH 7.1. As ONOO− is extremely unstable in neutral solution, current–potential curve was reconstructed between −0.5 and 0.7 V vs SCE by amperometry experiments at rotating disk electrode at different potentials. Comparison of this reconstructed curve with voltammograms of the common interfering species (dopamine, hydrogen peroxide, nitrite, ascorbic acid and glutamate) shows that the presence of ONOO− can be selectively determined at −0.1 V vs SCE. This detection occurs through the electrochemical reduction of peroxynitrous acid ONOOH, the conjugated acid of ONOO−. Detection of ONOO− produced in situ by the reaction of nitric oxide with superoxide was also achieved. Keywords: Peroxynitrite, Peroxynitrous acid, Neutral solution, Gold electrode, Electrochemical reduction

The adsorption of 4-nitrobenzenediazonium tetrafluoroborate (NBD) in acidic aqueous solution was investigated by scanning electrochemical microscopy (SECM) on polycrystalline gold and glassy carbon (GC) substrates. The feedback mode of SECM was used to study the local properties of each substrate before and after immersion in the aryldiazonium solution, by performing approach curves with two redox mediators, Fe ( CN ) 6 4 - and Ru ( NH 3 ) 6 3 + . The fitting of the approach curves with analytical approximate equation was used to evaluate the apparent heterogeneous rate constant k for Fe ( CN ) 6 3 - / 4 - redox system at NBD-adsorbed GC (k = 2.6 × 10−4 cm s−1).

The elaboration of hybrid materials from single-wall carbon nanotubes (SWCNT) and tetrasulfonated nickel phthalocyanine (NiTSPc) was electrochemically performed to obtain chemically modified electrodes with improved electrocatalytic activity towards the electrooxidation of nitric oxide (NO). The characterization of these hybrid electrodes was achieved by cyclic voltammetry and AFM. The electrochemical performances of the electrodes towards the oxidation of NO were then analyzed by chronoamperometry and the obtained results show that the presence of SWCNT greatly enhances the electrocatalytic performances in terms of current intensity. Additional coatings were then electrodeposited over the hybrid electrodes to act as selective membranes against four major interfering analytes: nitrite, ascorbate, hydrogen peroxide and L-arginine. Several polymer coatings were tested to achieve the best balance between sensitivity to NO and selectivity against interferents.

In this paper the preparation and characterization of modified electrodes based on carbon nanotubes / pyrrole / cobalt phthalocyanine was done to obtain hybrid materials for the electrochemical oxidation of 2-mercaptoethanol. To prepare these new electrodes, two steps were followed. First, single-walled CNT (SWNT) deposits were made in aqueous solution on glassy carbon (GC) to obtain GC/CNT electrodes. Subsequently, pyrrole (Py) was incorporated on the CNTs to produce GC/CNT/PPy electrodes by electropolymerization. Pyrrole electropolymerization was a useful method to control the film characteristics. Both deposits were studied using a redox model reaction with ferrocenemethanol (FeMeOH), enabling the determination of the stability and charge transfer characteristics of the obtained electrodes. Finally, CoPc was incorporated into the hybrid electrodes, and their response for the oxidation of 2-mercaptoethanol was investigated.

Manganese phthalocyanine MnPc(SPh)4 has been synthesized and used to form self assembled monolayers on gold electrodes. The well packed SAM monolayer was characterized by analyzing the blocking of a number of Faradic processes by cyclic voltammetry, evaluating the electrical characteristics of the modified electrode by electrochemical impedance and imaging the modified surface by electrochemical scanning microscopy. Finally, MnPc(SPh)4-SAM modified electrode displayed an electrocatalytic behavior toward the oxidation of nitrite.

Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.

International audience; Our aim was to prepare hybrid electrodes active towards the electrooxidation of thiols by the co-immobilization of native carbon nanotubes (CNTs) and cobalt phthalocyanine (CoPc) from aqueous solutions. This strategy was adopted to avoid the oxidation of CNTs that can induce a modification of their exceptional properties. To do so, a hydrosoluble pyrrole surfactant was used to get homogeneous aqueous dispersions of CNTs and CoPc and to trap both materials on the electrode via the electropolymerization of the pyrrole surfactant. The hybrid electrodes exhibit a good electrocatalytic activity towards the oxidation of L-cysteine and glutathione. Their performances in terms of limit of detection (0.01mM) are compatible with the detection of these thiols in biological samples.

We propose in this study a simple and rapid way to produce stable amino-derivatized conductive surfaces for the subsequent immobilization of (bio)molecules. This was achieved through the use of (4-aminoethyl)benzenediazonium salt (AEBD), which was immobilized on glassy carbon and gold electrodes by its electrochemical reduction. The presence of terminal grafted amino functions was evidenced with XPS by analyzing N1s core level. Besides this conventional surface characterisation, an electrochemical strategy is proposed here to evidence the presence of immobilized amines, in which the chemical reactivity of amines towards 2,4,6-trinitrobenzenesulfonic acid (TNBS) is used. Surface-bound TNBS served as an electrochemical marker and was detected by cyclic voltammetry. Additionally, pre-modified gold electrodes with amino functions can be derivatized with biomolecules such as glutathione (GSH). Glutathione attachment was evidenced by studying the electrochemical behaviour of ferri/ferrocyanide redox before and after its immobilization. The functionalized electrodes were then used for the detection of copper ions in neutral aqueous solutions. Keywords: Electrochemical surface modification, Diazonium salts, Gold electrode, Glassy carbon electrode

We have investigated in this work the kinetics of NO-release from two commercially available and commonly used diazeniumdiolates (so-called NONOates), namely diethylammonium (Z)-1-(N,N-diethylamino)-diazen-1-ium-1,2-diolate (DEA-NONOate) and (Z)-1-[N-(2-aminoepropyl)-N-(2-ammoniopropyl)amino]-diazen-1-ium-1,2-diolate (PAPA-NONOate) by electrochemical measurements. This choice was driven by the distinctive half-life of each compound (2–20 min at 37 °C for DEA- and PAPA-NONOate, respectively) that allow covering a relatively wide range of rate of NO-release. The release of NO from NONOate decomposition was followed using a home-made NO-sensitive electrochemical sensor. The electrochemical features of the starting NONOates and of the by-products of the fully decomposed molecules were also examined. Also, the electrochemical experimental results obtained under aerobic atmosphere were numerically fitted to model the production of NO and its degradation through its oxidation by molecular oxygen. All these information gathered together allows in predicting the real amount of NO released under real aerobic conditions. Keywords: Nitric oxide, Diazeniumdiolates, NONOate, Kinetics, Electrochemical sensor

We report here a fast procedure to modify glassy carbon (GC) electrode using commercially available unsubstituted cobalt phthalocyanine (CoPc) and tetrasulfonated substituted nickel phthalocyanine (NiTSPc) simply adsorbed on oxidized single walled carbon nanotubes SWCNT. The electrocatalytic activity of the resulting SWCNT-MPc nanocomposite materials was evaluated toward the oxidation of two biologically relevant molecules, namely 2-mercaptoethanol (2-ME) and nitric oxide (NO). The obtained electrodes are highly stable under hydrodynamic conditions and the tailored hybrid surfaces allow enhancing electron transfer for the electrocatalytic oxidation of 2-ME and NO. Keywords: Single walled carbon nanotube, Cobalt phthalocyanine, Nickel tetrasulfonated phthalocyanine, Electrocatalysis, 2-Mercaptoethanol, Nitric oxide

Peroxynitrite, ONOO− also so-called PON, is a very powerful oxidant and cytotoxic agent produced in biological systems by the recombination of nitric oxide and superoxide anion radical. Most of the techniques for assaying PON (chemiluminescence, fluorescence, UV-visible spectroscopy, immunochemistry and EPR ) use indirect methods relying on measurements of secondary species. We report in this study the calibration of a chemically modified Pt ultramicroelectrode by electropolymerized manganese tetraaminophthalocyanine film (MnTAPc) for the determination of PON in aqueous solution. The obtained result allows showing for the first time a real-time calibration curve of the amperometric determination of stable PON in aqueous solution. The sensitivity of the sensor is 14.6 nA mM−1 and its detection limit is 5 μM.

Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.

Cobalt(I) cobalamin and cobinamide are efficient catalysts of the hydrogenolysis of aliphatic chloro compounds. Taking chloroacetonitrile as example, the first requirement for high catalytic efficiency is fulfilled by the high reactivity of the Co(I) complex toward the substrate, leading to the alkylcobalt(III) complex. This is further reduced into the alkylcobalt(II) complex. However, the fact that these two reactions are fast is not enough to ensure an efficient catalysis: in DMF catalysis is very poor, while it is high in water. The experiments carried out in DMF with addition of an acid show that a crucial step in the catalytic process is the proton transfer decomposition of the alkylcobalt(II) complex, leading to the product, and closing the catalytic loop by regeneration of the cobalt(I) complex. Another important feature of these catalytic reactions is the role played by axial ligands present in the solution, particularly those that are produced by the catalytic reaction itself, namely, chloride ions and the counteranion of the added acid. The stronger these ligands, the more negative the potential required for the reduction of the alkylcobalt(III) complex. This amounts to a self-moderation effect: the more efficient catalysis, the slower its second step, i.e., the conversion of the alkylcobalt(III) complex into the alkylcobalt(II).

We report on the growth by flux method of large single crystals of hexagonal NpPd3. Samples with linear size up to 3 mm were obtained using lead as flux medium. Only polycrystalline samples of NpPd3 have been previously studied and in particular no information is available on the anisotropy of its physical properties. Considering the double hexagonal closely packed structure of NpPd3, important differences in the physical properties measured along the c-axis and in the basal plane can be anticipated. Preliminary magnetic susceptibility measurements performed on NpPd3 single crystal are compared to previous measurements made on polycrystalline samples. The availability of NpPd3 single crystals opens new perspectives in the understanding of the magnetic and electronic properties of this system.

We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine ( 3 ), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).

A hybrid nanocomposite based on cobalt phthalocyanine (CoPc) immobilized on nitrogen-doped graphene (N-G) (N-G/CoPc) has been developed to modify glassy carbon electrode (GCE) for the sensitive detection of thiols. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Cyclic voltammetric studies showed that cobalt phthalocyanine and nitrogen doped graphene have a synergic effect and significantly enhance the electrocatalytic activity of the modified electrode towards thiols oxidation compared with electrodes modified with solely CoPc or N-G. The electrochemical oxidation responses were studied and the reaction mechanisms were discussed. The sensors exhibited a wide linear response range from 1 μΜ to 16 mM and a low detection limit of 1 μΜ for the determination of l -cysteine, reduced l -glutathione and 2-mercaptoethanesulfonic acid in alkaline aqueous solution. The proposed N-G/CoPc hybrids contribute to the construction of rapid, convenient and low-cost electrochemical sensors for sensitive detection of thiols.

We have investigated the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the one-electron oxidation of 2-mercaptoethanol (2-ME) using adsorbed monomeric CoTAPc and electropolymerized poly-CoTAPc films of different thickness on vitreous carbon electrode. Our results show that the activity of poly-CoTAPc increases slightly with the thickness of the film, while the activity of the adsorbed monomeric CoTAPc is still greatest. The trend in activities, analysed by cyclic voltammetry, is the same for the electro-oxidation of 2-ME and for the electroreduction of the corresponding disulphide. Tafel plots obtained from rotating disk measurement for adsorbed CoTAPc and poly-CoTAPc film modified electrodes show slopes close to RT/F (ca. 70 mV) at low polarisation potentials which increase gradually with potential to values close to 2RT/F (120 mV). This suggests that at low polarisation the rate-determining step is a chemical step (formation of a metal complex–thiol adduct) preceded by a fast electron-transfer step involving the CoTAPc. At higher polarisations the one electron oxidation of the adduct to give the thiyl radical becomes rate controlling. Even though monomeric CoTAPc adsorbed on glassy carbon presents higher activity for the electro-oxidation of 2-ME, the high stability of the electropolymerized poly-CoTAPc makes them more attractive for applications in the activation and/or the amperometric detection of thiols.

A massive interest has been generated lately by the improvement of solid-state magic-angle spinning (MAS) NMR methods for the study of a broad range of paramagnetic organic and inorganic materials. The open-shell cations at the origin of this paramagnetism can be metals, transition metals, or rare-earth elements. Actinide-bearing compounds and their 5f unpaired electrons remain elusive in this intensive research area due to their well-known high radiotoxicity. A dedicated effort enabling the handling of these highly radioactive materials now allows their analysis using high-resolution MAS NMR (>55 kHz). Here, the study of the local structure of a series of actinide dioxides, namely, ThO2, UO2, NpO2, PuO2, and AmO2, using solid-state 17O MAS NMR is reported. An important increase of the spectral resolution is found due to the removal of the dipolar broadening proving the efficiency of this technique for structural analysis. The NMR parameters in these systems with numerous and unpaired 5f electrons were interpreted using an empirical approach. Single-ion model calculations were performed for the first time to determine the z component of electron spin on each of the actinide atoms, which is proportional to the shifts. A similar variation thereof was observed only for the heavier actinides of this study., JRC.E.4-Nuclear Fuel Safety

The redox potential of macrocyclic complexes is a very predictive reactivity index for the electrocatalytic activity of these molecules, and it can be easily measured under the same conditions of the catalysis experiments. It reflects directly the activity of a given complex. We have investigated the effect of the Fe(II)/(I) formal potential on the catalytic activity of a series of Fe porphyrins and Fe phthalocyanines for the electrooxidation of l-cysteine, with the complexes directly adsorbed on ordinary pyrolytic graphite or adsorbed on multi-walled carbon nanotubes (MWCNTs) deposited on graphite. A correlation of log j (at constant potential) versus the Fe(II)/(I) formal potential of the catalysts gives a volcano curve for both systems without and with MWCNTs with higher activities in the latter case. Our results clearly show that the highest catalytic activity is achieved in a rather narrow potential window of Fe(II)/(I) formal potentials of N4-macrocyclic complexes. The use of MWCNTs as supporting material for the catalysts does not change the reactivity trends of the Fe complexes.

The heterobimetallic complexes [{UO2Ln-(py)2(L)}2], combining a singly reduced uranyl cation and a rare-earth trication in a binucleating polypyrrole Schiff-base macrocycle (Pacman) and bridged through a uranyl oxo-group, have been prepared for Ln = Sc, Y, Ce, Sm, Eu, Gd, Dy, Er, Yb, and Lu. These compounds are formed by the single-electron reduction of the Pacman uranyl complex [UO2(py)(H2L)] by the rare-earth complexes LnIII(A)3 (A = N(SiMe3)2, OC6H3But2-2,6) via homolysis of a Ln-A bond. The complexes are dimeric through mutual uranyl exo-oxo coordination but can be cleaved to form the trimetallic, monouranyl "ate" complexes [(py)3LiOUO(μ-X)Ln(py)(L)] by the addition of lithium halides. X-ray crystallographic structural characterization of many examples reveals very similar features for monomeric and dimeric series, the dimers containing an asymmetric U2O2 diamond core with shorter uranyl U=O distances than in the monomeric complexes. The synthesis by LnIII-A homolysis allows [5f1-4fn]2 and Li[5f1-4fn] complexes with oxo-bridged metal cations to be made for all possible 4fn configurations. Variable-temperature SQUID magnetometry and IR, NIR, and EPR spectroscopies on the complexes are utilized to provide a basis for the better understanding of the electronic structure of f-block complexes and their f-electron exchange interactions. Furthermore, the structures, calculated by restricted-core or all-electron methods, are compared along with the proposed mechanism of formation of the complexes. A strong antiferromagnetic coupling between the metal centers, mediated by the oxo groups, exists in the UVSmIII monomer, whereas the dimeric UVDyIII complex was found to show magnetic bistability at 3 K, a property required for the development of single-molecule magnets.

Electrodes prepared from overoxidized pyrrole, multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPc) exhibit a clear catalytic activity for the electrooxidation of L-cysteine and reduced gluthatione. The electrodes are more stable than the ones modified by simple adsorption of CoPc and/or MW-CNT. Therefore, these materials offer a good alternative for the development of electrocatalytic applications and thiols detection in biological interest.

The low temperature heat capacity of UF(3) has been measured using an adiabatic low temperature calorimeter in the temperature range from 10 to 350 K. These data are complemented at the lowest temperature region with data obtained with a Quantum Design PPMS-14 device in the temperature range from 0.5 to 20 K. Good agreement between both techniques has been found, and from these experimental results the absolute entropy of UF(3) at 298.15 K has been determined as 126.8 ± 2.5 J K(-1) mol(-1). On the basis of the specific heat data and the magnetization measurements performed on a SQUID device, a transition at 1.59 K attributed to Curie temperature of a ferromagnetic transition has been found in this study. This observation makes UF(3) a unique compound with an unusually low ferromagnetic ordering temperature.

Syntheses of the bimetallic uranium(III) and neptunium(III) complexes [(Ul)2(L)], [(Npl)2(L)], and [{U(BH4)}2(L)] of the Schiff-base pyrrole macrocycles L are described. In the absence of single-crystal, structural data, fitting of the variable-temperature solid-state magnetic data allows the prediction of polymeric structures for these compounds in the solid state.

The manuscript discusses different ways of forming hybrid materials between single (SWCNT) or multi (MWCNT) walled carbon nanotubes and biomimetic compounds such as metalloporphyrins, metallophthalocyanines and other MN4 complexes. The hybrid materials are employed for electrocatalysis of reactions such as oxygen and hydrogen peroxide reduction, nitric oxide oxidation, oxidation of thiols and other pollutants. Methods of characterizing the hybrid materials such as cyclic voltammetry (CV), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) are discussed.

The grafting of 4-nitrophenyl groups on carbon or metallic surfaces without externally applied electrochemical induction is described. Clean surfaces of glassy carbon (GC), copper, nickel, iron, and zinc substrates were dipped in a solution of 4-nitrobenzene diazonium tetrafluoroborate salt in acetonitrile. After the modified surfaces were rinsed, they were analyzed by FT-IRRAS, cyclic voltammetry, XPS, and AFM. The main result of this investigation is the spontaneous formation of a multilayer coating without electrochemical induction regardless of the substrate used. Influence of immersion time and of 4-nitrobenzene diazonium tetrafluoroborate salt concentration on the grafting were also investigated.