The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry preparative electrolysis. mechanisms have established, the lifetimes radical cations measured for secondary tertiary amines. These results put in parallel with attachment to glassy carbon, Au, Pt electrodes voltammetry, X-ray photoelectron spectroscopy (XPS), infrared reflection−absorption (IRRAS). It is then possible show that it not cation but obtained after...

Primary alkylamines attach spontaneously from acetonitrile (ACN) solutions onto glassy carbon and metallic surfaces (Au, Pt, Cu, Fe). The surface concentration of the organic layer measured integration cyclic voltammograms appears close to or lower than that a compact monolayer. rate attachment depends on primary amino compound; it reaches maximum after 3 h immersion for most concentrated (20 mM). modified have been characterized by voltammetry (CV), energy dispersive X-ray spectrometry...

Abstract One key challenge in inorganic mesoporous films is the development of oriented mesostructures with vertical channels, and even more challenging their functionalization while maintaining accessible selected surface groups. Combining electrochemically assisted deposition ordered azide‐functionalized silica alkyne–azide click chemistry enables such nanostructured vertically aligned hybrid to be obtained significant amounts active organic functional groups, as illustrated for ferrocene...

We report the synthesis and characterization of eight new Mo, W, or V-containing polyoxometalate (POM) bisphosphonate complexes with metal nuclearities ranging from 1 to 6. The compounds were synthesized in water by treating Mo(VI), W(VI), V(IV), V(V) precursors biologically active bisphosphonates H(2)O(3)PC(R)(OH)PO(3)H(2) (R = C(3)H(6)NH(2), Ale; R CH(2)S(CH(3))(2), Sul C(4)H(5)N(2), Zol, where Ale alendronate, (2-Hydroxy-2,2-bis-phosphono-ethyl)-dimethyl-sulfonium Zol zoledronate)....

Covalent bonding of (2,2′-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complex at the surface a carbon-based porous electrode was achieved by combining diazonium electrografting, Huisgen cycloaddition, and metal complexation. The immobilized catalyst applied to electrochemical regeneration reduced form nicotinamide adenine dinucleotide (NADH). different steps functionalization were characterized X-ray photoelectron spectroscopy electrochemistry. Faradaic efficiency NADH 87%. chemical...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTMolecular Sieving with Vertically Aligned Mesoporous Silica Films and Electronic Wiring through Isolating NanochannelsNeus Vilà†, Erwan André†, Roberto Ciganda‡, Jaime Ruiz‡, Didier Astruc*‡, Alain Walcarius*†View Author Information† Laboratoire de Chimie Physique et Microbiologie pour l'Environnement, UMR 7564, CNRS-Université Lorraine, 405 rue Vandoeuvre, 54600 Villers-les-Nancy, France‡ Institut des Sciences Moléculaires (ISM), 5255, CNRS...

Abstract This review (239 references) is dealing with the use of mesoporous materials in field electrochemical enzymatic biosensors. After a brief discussion on interest for biosensing, presentation various types inorganic and organic‐inorganic hybrid mesostructures used to date elaboration bioelectrodes given main bioelectrode configurations are described. The biosensor applications then summarized basis comprehensive table some representative illustrations. detection schemes developed...

Vertically oriented mesoporous silica has proven to be of interest for applications in a variety fields (e.g., electroanalysis, energy, and nanotechnology). Although glassy carbon is widely used as an electrode material, the adherence deposits rather poor, causing mechanical instability. A solution improve adhesion films onto electrodes without compromising vertical orientation order mesopores will greatly contribute use this kind modified electrode. We propose here electrografting...

A series of dinuclear metal terpyridine (M-tpy; M = Ru, Os, Fe, and Co) complexes with a photochromic dithienylethene bridge were designed synthesized through either convergent or divergent approach. The open forms the containing RuII FeII centers found to be inert ultraviolet photoirradiation but could cyclized electrochemically as revealed by cyclic voltammetric study. On contrary, CoII complex underwent efficient photochemical not electrochemical cyclization. corresponding OsII was...

Abstract For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As consequence, several photoinitiators are necessary to harvest all emitted photons. Herein, 2,7‐di‐ tert ‐butyldimethyldihydropyrene is used for first time as multicolor cationic polymerization epoxides. Upon addition diphenyliodonium hexafluorophosphate and optionally N‐vinylcarbazole, originality this approach allow efficient monomer conversions under various excitation...

Abstract A series of photochromic derivatives based on the trans ‐10b,10c‐dimethyl‐10b,10c‐dihydropyrene (DHP, “closed form”) skeleton has been synthesized and their photoisomerization leading to corresponding cyclophanediene (CPD, “open isomers investigated by UV/Vis 1 H NMR spectroscopies. Substitution DHP core with electron‐withdrawing pyridinium groups was found have major effects efficiency, most remarkable examples being enhance quantum yield opening reaction allow fast quantitative...

Getting oriented mesoporous thin films with functionalized pores accessible from the substrate surface remains one key challenge in materials science, and jumping step forward to multifunctional layers perpendicular nanochannels has still be achieved. Here, a general method is introduced combining electrochemically assisted deposition of ordered azide‐ thiol‐functionalized silica selective sequential azide‐alkyne thiol‐ene “click chemistry” approach prepare nanostructured vertically aligned...

There is continuing interest in the design and synthesis of functional materials for applications molecular electronics information storage. Of particular are systems that can provide multiple means controlling transport through well-defined stable electronic and/or redox states. We report herein characterization a system containing transition-metal complexes along with dithienylethene (DTE) units so as to achieve photo control transport. A facile synthetic methodology was developed assemble...

Six dinuclear cyclometalated ruthenium complexes, 1-6, based on diphenylanthracene (DPA) and anthracene (AN) as bridging ligands have been synthesized fully characterized electrochemically spectroscopically. The anodic electrochemistry of the homobinuclear has examined in three different nonaqueous solvents (ACN, DMF, CH(2)Cl(2)). ability derivatives to transmit electronic effects between two redox units demonstrated by observed splitting voltammetric signals ascribed metal centers....

Abstract Diffusion of anionic species through ordered mesoporous silica films is considerably restricted due to electrostatic repulsion by the negatively charged surface and this effect even worse in low ionic strength media (owing Donnan exclusion effects). This at origin poor electrochemical response redox probes electrodes modified with such thin films. Here, using indium–tin oxide (ITO) covered vertically aligned generated electrochemically assisted self‐assembly (EASA), we show that...

Thiol–ene click chemistry can be exploited for the immobilization of cysteine-tagged dehydrogenases in an active form onto carbon electrodes (glassy and felt). The electrode surfaces have been first modified with vinylphenyl groups by electrochemical reduction corresponding diazonium salts generated situ from 4-vinylaniline. grafting process has optimized order to not hinder regeneration NAD+/NADH cofactor soluble mediators such as ferrocenedimethanol [Cp*Rh(bpy)Cl]+. Having demonstrated...

Abstract A bioelectrode for electroenzymatic synthesis was prepared, combining a layer NADH regeneration and renewable enzymatic substrate reduction. The covalent immobilization of rhodium complex mediator ([Cp*Rh(bpy)Cl] + ) on the surface bucky paper electrode achieved by following an original protocol in two steps. bipyridine ligand first grafted electro‐reduction bipyridyl diazonium cations generated from 4‐amino‐2,2′‐bipyridine, then formed reaction with [RhCp*Cl 2 ] . turnover...

Designed prototype molecules for making a three-terminal single-molecule device, star-shaped Fe(II), Co(II), and Ru(II) tris-bipyridine complexes containing three dithienylcyclopentenes, have been synthesized characterized. All displayed reversible photochromic behavior when irradiated with UV or visible light. The open form of these could be cyclized electrochemically as revealed by cyclic voltammetric studies bulk electrolysis experiments.

Abstract A generic approach has been developed for sequential heterogeneous surface modification of electrodes. The strategy, which is applicable a wide range functional groups, involves two main steps. In the first one, azide‐alkene bifunctionalized electrodes are obtained by electrochemical reduction mixture diazonium salts generated in situ from corresponding 4‐azidoaniline and 4‐vinylaniline. that way, we provide reactive sites available further selective functionalization process based...

Organic–inorganic hybrid membranes, made of a high density redox active moieties covalently bonded to the internal surfaces vertically aligned mesoporous silica thin films, are relevant for applications in transparent energy storage devices. This is demonstrated here on basis functionalized films prepared indium–tin oxide electrode from combination an electrochemically induced self-assembly method (to generate azide-functionalized silica) and copper-catalyzed azide–alkyne click reaction...