Volcano correlations for the reactivity of surface-confined cobalt N<Subscript>4</Subscript>-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate

We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B₁₂, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin < Co–tetrasulfonatotetraphenylporphyrin < Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B₁₂ exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N₄-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site. Dedicated to Prof. Dr. Teresa Iwasita on the occasion of her 65th birthday in recognition of her numerous contributions to interfacial electrochemistry.     

Tuning the redox properties of metalloporphyrin- and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols

In this work we discuss different approaches for achieving electrodes modified with N(4) macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and E(o') of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropriate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a DeltaG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.     

Layer by Layer Electrode Surface Functionalisation Using Carbon Nanotubes,Electrochemical Grafting of Azide‐Alkyne Functions and Click Chemistry

Ferrocene was covalently bonded to a layer of adsorbed single‐walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4‐azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface‐bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3‐triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.     

Quantitation of Cu+‐catalyzed Decomposition of S‐Nitrosoglutathione Using Saville and Electrochemical Detection: a Pronounced Effect of Glutathione and Copper Concentrations

S‐nitrosothiols (RSNOs) are composed of nitric oxide (NO) bound to the sulfhydryl group of amino acids of peptides or proteins. There is a great interest for their quantitation in biological fluids as they have a crucial impact on physiological and pathophysiological events. Most analytical methodologies for quantitation of RSNOs are based on their decomposition followed by the detection of the released NO. In order to obtain the optimal sensitivity for each detection method, the total decomposition of RSNOs is highly desired. The decomposition of RSNOs can be obtained by using catalytically active metal ions, such as Cu⁺, obtained from CuSO₄ in presence of a reducing agent such as glutathione (GSH) that is naturally present in biological environment. In this work, we have re‐investigated the decomposition of S‐nitrosoglutathione (GSNO) which is the most abundant in vivo low molecular weight RSNO, with a special emphasis on the effect of CuSO₄, GSH, and GSNO concentrations and of their ratio. To this aim, GSNO decomposition optimization was performed by both indirect (Griess assay) and direct (real time electrochemical detection of NO at NO‐microsensor) quantitation methods. Our results show that the ratio between CuSO₄, GSH and GSNO should be adjusted to tune the highest decomposition rate of GSNO and the most efficient electrochemical detection of released NO; also it shows the deleterious effect of very high GSH concentration on the detection of GSNO.     

Effect of the TiC content on microstructure and thermal properties of Cu–TiC composites prepared by powder metallurgy

Copper matrix with an individual addition of TiC particles was prepared by means of powder metallurgy and hot pressing process, and the effect of TiC addition on microstructure, thermal properties, and electrical conductivity of Cu–TiC composites was investigated. The TiC quantity was changed as 1, 3, 5, 10, and 15 Cu (in mass%), and Cu–TiC powder mixtures were hot-pressed for 4 min at 700 °C under an applied pressure of 50 MPa. Microstructure studies revealed that TiC particles were distributed uniformly in the Cu matrix. Thermal Analysis result showed that there were two exothermic peaks and with rising TiC rate, oxidation amount of Cu composite decreased. With the increasing addition of TiC, hardness of composites changed between 58.6 HV_0.1 and 87.8 HV_0.1. The highest electrical conductivity for Cu–TiC composites was obtained in the Cu-1 mass% TiC composite, with approximately 81.2 % IACS.     

Estimation locale linéaire de la densité conditionnelle pour des données fonctionnelles

In this Note, we introduce the local linear estimation of the conditional density of a scalar response variable given a random variable taking values in a semi-metric space. Under some general conditions, we establish the pointwise and uniform almost complete convergences with rates of this estimator. Moreover, as an application, we use the obtained results to derive some asymptotic properties for the local linear estimator of the conditional mode.     

Corrosion Behavior of Biocompatible Stainless Steels in Physiological Medium for Non‐invasive Diagnosis of Small Fiber Neuropathies Applications

A non‐invasive device based on measurements of electrochemical skin conductance can detect small fiber neuropathy, a sweat gland dysfunction implicated in several diseases. The measurement is related to sweat composition and notably to chloride concentration. To optimize the electrode material, in vitro experiments are performed in mimetic sweat solutions. This work reports on the resistance to pitting corrosion of biocompatible stainless steels (AISI 304L, AISI 430, AISI 430T, D2205) in sweat mimicking electrolyte at pH 7 with variable chloride concentration, to determine the most sensitive material to sweat composition. AISI 430 is promising due to its high sensitivity to chloride concentration variations.     

Theoretical and numerical study of Couette-Taylor flow with an axial flow using lattice Boltzmann method

In this study, the numerical models for swirling flows developed by Li et al and Zhou for lattice Boltzmann method (LBM) are chosen. These models were firstly validated using the Couette-Taylor flow between two concentric cylinders simulations. Numerical results showed the efficiency of the Zhou's model. Numerical simulation results using LBM are in good agreement for the steady and unsteady regimes compared to the literature review. In a second step, the Zhou model was then adopted to our study to determine the Couette-Taylor instabilities with an axial flow. Two protocols are tested. The first one (direct protocol) starts with an azimuthal flow without any axial flow (Re = 0). Once the regime is established, an axial flow is then superposed to the Couette-Taylor flow (with a sudden or a progressive manner). The second protocol (inverse protocol) starts with an axial flow at a given Reynolds number (Poiseuille flow). Once the regime is established, an azimuthal flow is the executed (with a sudden or a progressive manner). The effect of various parameters controlling the physical situation is also discussed. The increase of the azimuthal velocity mainly led to the emergence and development of Taylor vortices. Its influence decreases when the axial Reynolds number increases. The relevant result for this study is the change of the critical axial Reynolds number Re_c (total disappearance of instabilities) with both protocols and both manners.