0000000000006170
AUTHOR
Antonio Doménech
showing 95 related works from this author
Electrochemically-driven conformational shift in mono- and di-copper constrained macrotricyclic cyclen receptors
2008
International audience; An electrochemical study of mono- and di-copper constrained cyclen macrotricycles is presented. Electrochemical data in DMF solution indicate that the reduction of dinuclear complexes occurs in two steps in the -0.4 to -0.8 V vs.AgCl/Ag potential range yielding CuII CuI and CuI CuI species further reduced to Cu metal at highly negative potentials. Mononuclear complexes are reduced in two steps to CuI and Cu metal. Electrochemical data suggest that reduction of both mononuclear and dinuclear complexes approach a square scheme involving electrochemically-driven conformational shifts for metal ions. The presence of endo- and exo-forms of the complexes are revealed by ch…
Modelling electrocatalysis of hydroquinone oxidation by nicotinamide adenine dinucleaotide coenzyme encapsulated within SBA-15 and MCM-41 mesoporous …
2006
The electrochemical response of NADH associated to two mesoporous aluminosilicates, MCM-41 and SBA-15, is described upon attachment of such materials into polymer-film electrodes. The studied materials display a significant electrocatalytic activity towards the oxidation of 1,4-dihydrobenzoquinone, H2Q. Two models for describing the electrocatalytic process, based on the general theory of mediated electrocatalysis and the Lovric and Scholz formulation of the voltammetry of microparticles are discussed. Voltammetric and chronoamperometric data indicate that the electrocatalytic process involves the formation of a surface-confined NADH–H2Q adduct in the case of SBA-15, while a surface reactio…
Ship-in-a-bottle synthesis of triphenylamine inside faujasite supercages and generation of the triphenylamminium radical ion
2005
Abstract The ship-in-a-bottle synthesis of triphenylamine encapsulated within basic X zeolite has been accomplished by reacting sodium diphenylamide with bromobenzene in the presence of a bifunctional palladium (Hartwig–Buchwald conditions). The presence of incarcerated triphenylamine was demonstrated by dissolving the zeolite with concentrated HF and analyzing the organic material in the dichloromethane extract. Laser flash photolysis (266 nm) gives rise to the generation of triphenylamminium radical cation detected as a transient species decaying in hundreds of microseconds. Upon repetitive cyclic voltammograms, zeolite encapsulated triphenylamine shows a reversible oxidation–reduction pr…
Application of Modified Tafel Analysis to the Identification of Corrosion Products on Archaeological Metals Using Voltammetry of Microparticles
2011
Voltammetry of microparticles is applied to the identification of lead corrosion products by means of an essentially non-invasive 'one-touch' technique based on the use of graphite pencil. This methodology permits the mechanical attachment of few nanograms of sample from the surface of lead archaeological artefacts to a paraffin-impregnated graphite electrode, which, upon immersion in aqueous electrolytes, provides distinctive voltammetric responses for litharge and cotunnite- anglesite-, cerusite-based corrosion products. The reported method is applied to the identification of corrosion products in archaeological lead pieces from different Iberian sites in Valencia (Spain). © 2011 WILEY-VC…
Electrolyte-driven electrochemical amplification by poly(thienylacetylene) encapsulated within Zeolite Y
2006
Electrochemical oxidation and reduction of poly(thienylacetylene) encapsulated inside zeolite Y (PTA@Y) exhibit with large anodic and cathodic doping currents with a significant reversibility. Thienyl groups lower the redox potential of polyacetylene chain whereas encapsulation stabilizes the resulting charged radical species blocking undesired post electron-transfer cross-link reactions. Size-exclusion effects associated produces an electrolyte-dependent amplification of currents recorded at PTA@Y-modified electrodes for electrochemical processes involving selected substrates in solution, namely, dinitrobiphenyl and benzidine. Keywords: Poly(thienylacetylene), Zeolite Y, Electrochemistry, …
Layer-by-layer identification of copper alteration products in metallic works of art using the voltammetry of microparticles.
2010
An in situ technique for layer-by-layer electrochemical analysis of solid surfaces using the voltammetry of microparticles is presented. The method is based on the determination of several shape-dependent parameters for voltammetric curves recorded at a graphite pencil working electrode in contact with the sample, all immersed into aqueous electrolytes. Repetitive square wave voltammetry and sequential application of constant potential reductive steps and voltammetric scans yield discernible responses for the corrosion products distributed in stratified layers on metal-based surfaces. This methodology is applied to identify alteration products of copper and copper alloys distributed in diff…
A reliable procedure for the preparation of graphene-boron nitride superlattices as large area (cm x cm) films on arbitrary substrates or powders (gr…
2019
[EN] Herein, a reliable procedure for the preparation of graphene-boron nitride superlattices, either as films or powders, consisting of the pyrolysis at 900 degrees C of polystyrene embedded pre-formed boron nitride single sheets is reported. The procedure can serve to prepare large area films (cm x cm) of this superlattice on quartz, copper foil and ceramics. Selected area electron diffraction patterns at every location on the films show the occurrence of the graphene-boron nitride superlattice all over the film. The procedure can also be applied to the preparation of powdered samples on a gram scale. Comparison with other materials indicates that the superlattice appears spontaneously as…
Electrochemistry of vanadium-doped ZrSiO4Site-selective electrocatalytic effect on nitrite oxidation
2004
The electrochemistry of vanadium-doped zircon (VxZrSiO4, 0 < x < 0.10) has been studied using abrasive-conditioned paraffin-impregnated graphite electrodes. It is compared with that of ZrSiO4, ZrO2, and vanadium-doped tetragonal and monoclinic zirconias. In contact with acetic/acetate and HCl + NaCl electrolytes, zirconium materials are reduced to Zr(III) at potentials near to −0.5 versus AgCl/Ag and to Zr metal at potentials more negative than −1.2 V, via proton-assisted reductive processes, influenced by the complexing action of chloride ions. Vanadium-centred oxidation processes appear at potentials from +0.2 to +0.7 V enabling for a distinction between different coordinative arrangement…
Tramways Revisited: An analysis of the role of tramways in urban transportation during the twentieth century
2007
The structure and evolution of tramway and metro networks are studied in this article using two models involving addition/accretion and expansion/diffusion modes of growth, respectively. Data for t...
Chemical and electrochemical behaviour of 4,4’,4’’,4’’’-tetrakis(dimethylamino)-tetraphenylethylene in an oxidant environment: Toward a new sensor fo…
2020
Abstract Electrochromic compounds are suitable candidates for being used in sensor design. Here we report the use of 4,4’,4’’,4’’’-tetrakis(dimethylamino)-tetraphenylethylene for detecting both NO2 and SO2. Whereas the sensing mechanism in the case of nitrogen dioxide is a simple chemical oxidation reaction, in the case of sulfur dioxide, the mechanism is much more complex and the reaction requires the presence of t-butylhydroperoxide to take place. By modifying the detection conditions both compounds can be detected in gas phase. Additionally, a wide electrochemical study has been carried out to understand the role played by the t-butylhydroperoxide in the reaction with sulfur dioxide.
On the Existence of Different Zeolite-Associated Topological Redox Isomers. Electrochemistry of the Y Zeolite-Associated Mn(Salen)N3 Complex
2002
The electrochemical properties of Y zeolite-associated MnIII(salen)N3 (salen = trans-(R,R)-1,2-bis(salicyldeneamino)cyclohexane) has been investigated using polymer film electrodes immersed into neutral aqueous solutions. Zeolite Y-associated Mn(III)−salen complexes are reduced in one-electron reversible process at −0.25 V versus SCE. The electrochemical response is discussed in terms of the existence of two topological redox isomers: a weakly boundary-associated Mn(salen) complex, whose electrochemical response corresponds to a reversible one-electron transfer controlled by diffusion of the positive ions of the supporting electrolyte through the zeolite surface windows and channels, and a…
A Binuclear MnIII Complex of a Scorpiand-Like Ligand Displaying a Single Unsupported MnIII–O–MnIII Bridge
2012
The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.
A topological phase transition between small-worlds and fractal scaling in urban railway transportation networks?
2009
Abstract Fractal and small-worlds scaling laws are applied to study the growth of urban railway transportation networks using total length and total population as observational parameters. In spite of the variety of populations and urban structures, the variation of the total length of the railway network with the total population of conurbations follows similar patterns for large and middle metropolis. Diachronous analysis of data for urban transportation networks suggests that there is second-order phase transition from small-worlds behaviour to fractal scaling during their early stages of development.
Potential Application of Voltammetry of Microparticles for Dating Porcine Blood-based Binding Media used in Taiwanese Architectural Polychromies
2012
A method for dating Hemoglobine-containing archaeological samples using the voltammetry of microparticles is described. This is based on the record of the voltammetric response of such materials attached to paraffin-impregnated graphite electrodes in contact with aqueous acetate buffer. Signals attributable to the Fe(III)/Fe(II) iron couple and their catalytic enhancement in the presence of H(2)O(2) can be correlated, via first-order reaction kinetics, with the time of aging of the samples. The method has been applied to the study and dating of the polychromed architectural decoration of different parts of the architectural complex of the Longshan Temple in Lukang (18(th) century, Taiwan).
Mapping of corrosion products of highly altered archeological iron using voltammetry of microparticles
2013
The application of the voltammetry of microparticles to identify corrosion products on different localizations of highly altered archeological iron pieces is described. The use of graphite pencil methodology permits to mapping different corrosion products, namely, akaganeite, goethite, hematite, jarosite, magnetite, maghemite and siderite, in iron artifacts. Identification protocols are based on square wave voltammetric measurements performed at sample-modified paraffin-impregnated graphite electrodes immersed into aqueous HCl. This methodology is applied for mapping corrosion products on an Iberian Roman shield boss from the Torre la Sal archeological site (Oropesa, Spain) dated in the IVt…
Binuclear Cu2+ complex mediated discrimination between L-glutamate and L-aspartate in water.
2005
L-Glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophanetype macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes. Verdejo Viu, Begoña, Begona.Verdejo@uv.es ; Domenech Carbo, Antonio, Antonio.Domenech@uv.es ; Jimenez Garcia, Hermas Rafael, Hermas.Jimenez@uv.es ; Soriano Soto, Concepción, Concepcion.Soriano@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es
Application of solid-state electrochemistry techniques to polyfunctional organic–inorganic hybrid materials: The Maya Blue problem
2013
Abstract The time evolution of indigo plus palygorskite powdered mixtures during isothermal heating at different temperatures between 120 and 180 °C to form Maya Blue-type materials has been monitored by means of infrared spectrometry, diffuse reflectance spectrometry in the visible region and solid state electrochemical techniques. The kinetics of the formation process of such materials can be described in terms of two consecutive reactions, the first one consisting of the loss of zeolitic water of the palygorskite coupled with clay-indigo attachment and partial indigo to denydroindigo oxidation. The palygorskite dehydration acts as a rate-determining step fitting to a 3D Avrami-Erofe’ev k…
Modeling Corrosion of Archaeological Silver-Copper Coins Using the Voltammetry of Immobilized Particles
2012
Two complementary models to describe the long-term corrosion of silver-copper coins, based on potential rate laws for smooth corrosion and those combined with diffusive law, for gross corrosion, are proposed. Theoretical kinetics can be tested using signatures of copper and silver corrosion products using the voltammetry of immobilized particles technique. The method is applied to silver coins minted during the 13th–14th centuries from the Libertad street hoard in Valencia (Spain) using non-invasive one-touch graphite pencil sampling. Voltammetric features yield functional dependences in agreement with the proposed model potentially useful for distinguishing between different mints.
Synthesis and characterization of molybdenum(VI)-dioxo complexes containing both coordinated thiolate and carboxylate groups. Reactions with their ow…
1998
Abstract The synthesis, characterization and spectroscopic properties of a group of Mo(VI) complexes having thiocarboxylate ligands of type [MoVIO2(O2CC(S)MePh-X)2]2 have been reported (X = H, p-Me, p-Cl). The peak potential for the Mo(VI) reduction increasing according to the electron-donor ability of X (Me > H > Cl). Reaction of these Mo(VI) complexes with their own free ligands has been studied by ESR and UV-Vis spectroscopy, yielding the monomeric [MoVO(O2CC(S)MePh-X)2]− as unique complex products. The kinetic study of this oxidation reaction has also been investigated.
On the interpretation of the Raman spectra of Maya Blue: a review on the literature data
2011
The Raman spectroscopy of Maya Blue (MB), a nanostructured organic–inorganic hybrid material, has received considerable attention. A re-evaluation of the Raman literature data for indigo dye, genuine MB samples and model specimens obtained by the binding of indigo to phyllosilicate clays, such as palygorskite and sepiolite, using chemometric analysis of normalised spectra is reported. Available data present features in support of the following ideas: (1) dehydroindigo accompanies indigo in MB; (2) different topological isomers, i.e. dye molecules attached to different coordinative sites of the palygorskite framework, are involved in MB; and (3) different procedures were probably used for pr…
Synthesis, electrochemical and theoretical studies of the Au(i)-Cu(i) heterometallic clusters bearing ferrocenyl groups
2009
Treatment of the polymeric alkynyl compounds (AuC2R)n (R = Fc, C6H4Fc; Fc = ferrocenyl) with the diphosphine PPh2C6H4PPh2 gave complexes (RC2Au)PPh2C6H4PPh2(AuC2R) (1, R = Fc; 2, R = C6H4Fc) with end-capped ferrocenyl groups. The reactions of 1 or 2 with Cu(NCMe)4PF6 result in formation of the heterotrimetallic aggregates [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (3, R = Fc; 4, R = C6H4Fc), which consist of the alkynyl clusters [Au3Cu2(C2R)6]−“wrapped” by the cationic [Au3(PPh2C6H4PPh2)3]3+“belt”. The novel compounds were characterized by NMR spectroscopy and ESI-MS measurements. The solid state structure of 3 is reported. Electrochemical properties of the complexes 1–4 have been studied. Th…
Estimation of individual Gibbs energies of cation transfer employing the insertion electrochemistry of solid Prussian blue
2011
Abstract A novel method to determine the Gibbs energy of cation transfer between two miscible solvents is described. This method uses electrochemical data for the reversible cation-assisted solid-state reduction of Prussian blue using ferrocene as internal potential standard. Voltammetric data can be used for a direct measurement of the Gibbs energy of ion transfer from one solvent to another using midpeak potentials in solutions of suitable salts in each one of the solvents separately or mixtures of the solvents. Excess Gibbs energies of solvation in solvent mixtures can also be directly estimated. Gibbs energies of cation transfer of Li+, Na+ and K+ ions from water to MeOH, MeCN and DMSO …
Ferrocenyl-functionalized tetranuclear gold(I) and gold(I)-copper(I) complexes based on tridentate phosphanes
2013
Tetranuclear AuI–FeII dimetallic and AuI–CuI–FeII trimetallic complexes bearing ferrocenyl (Fc) groups have been assembled by using two triphosphane ligands, namely, (PPh2CH2)2PPh (dpmp) and (PPh2)3CH (tppm). The compositions and structural type of the clusters are dependent on the stereochemistry of the P donor ligands. The complexes [tppmAu3Cu(C2R)3]PF6 [R = Fc (1) and 4-C6H4-Fc (2)] adopt a trigonal pyramidal {Au3Cu} arrangement of the coordinating metal core, whereas for the compounds with the linear triphosphane [Au4(dpmp)2(C2R)2](PF6)2 [R = Fc (3) and 4-C6H4-Fc (4)], a planar rhomboidal {Au4} framework was found. Clusters 1–4 were characterized by NMR spectroscopy and ESI-MS measureme…
CO 2 Fixation and Activation by Cu II Complexes of 5,5″‐Terpyridinophane Macrocycles
2007
An aza-terpyridinophane receptor containing the polyamine 4,7,10,13-tetraazahexadecane-1,16-diamine linked through methylene groups to the 5,5″ positions of a terpyridine unit has been prepared and characterized (L). The acid-base behaviour, CuII speciation and ability to form ternary complexes (CuII-L-carbonate) have been explored by potentiometric titrations in 0.15 M NaClO4 and by UV/Vis and paramagnetic NMR spectroscopy. Comparisons are made with a previously reported terpyridinophane containing the polyamine 4,7,10-triazatridecane-1,13-diamine (L1). For this latter receptor, reductive coupling between indigo and carbon dioxide at indigo-modified electrodes produces carboxylated derivat…
Electrochemistry nanometric patterning of MOF particles: Anisotropic metal electrodeposition in Cu/MOF
2006
Abstract Electrodeposition of copper from Cu/MOF immersed into acetate buffer produces a quasi-periodic series of 10–20 nm sized laminae sandwiched within the pristine MOF lattice as monitored by voltammetry of microparticles/atomic force microscopy. This anisotropic patterning can be qualitatively described in terms of a highly orientation-dependent diffusion of electrons and charge-balancing electrolyte counterions in the MOF network.
A new macrocyclic dipyrazolate salt of diazatetraester structure able to efficiently and selectively interact with psychotropic phenethylammonium sal…
2002
Abstract The equilibrium stability constants (Ks) of a series of ammonium pyrazolate complexes [L22−]2RN(R′)H2+ (7, R′=H and 8, R′=Me) formed from a new macrocyclic disodium dipyrazolate salt of diazatetraester structure 6[L22−] 2Na+ and ammonium salts [RNH3+X− or RN(Me)H2+X−] of psychotropic drugs and neurotransmitter catecholamines has been evaluated by electrochemical methods in DMSO solution. The resulting Ks values demonstrate that in general, the diazatetraester crown-derived dipyrazolate salt 6 exerts a stronger complexing effect over phenethylammonium ions than that of the dioxatetraester crown-derived disodium dipyrazolate salt 2 previously reported. Interestingly, complexes formed…
Model for Solid State Voltammetry of Zeolite-Associated Species
2004
The electrochemical reduction/oxidation of zeolite-associated species is described from the model of Lovric and Scholz for redox conductive microcrystals and the model of Andrieux and Saveant for redox polymers. It is assumed that the reaction starts at the three-phase boundary between electrode, zeolite particle, and electrolyte. From this point, the reaction zone grows while electrons and charge-balancing cations diffuse perpendicularly along the zeolite. As a result, at short times, a Cottrell-type behavior, controlled by the diffusion of electrolyte countercations in the zeolite can be expected. At larger times, a thin-layer response in which electron hopping between adjacent redox site…
Electrochemical monitoring of the oxidative coupling of alkynes catalyzed by triphenylphosphine gold complexes
2012
Electrochemical monitoring of the oxidative coupling of alkynes in the homogeneous phase through catalytic cycles involving triphenylphosphine gold complexes and selectfluor as oxidant reveals that at least two gold species in +3 and +1 oxidation states are implicated. Electrochemically driven homocoupling of terminal alkynes using molecular oxygen as the oxidant can be performed using such catalysts. Keywords: Gold catalysis, Oxidative coupling of alkynes, Oxygen, Voltammetry
ChemInform Abstract: Maya Blue as a Nanostructured Polyfunctional Hybrid Organic-Inorganic Material: The Need to Change Paradigms.
2010
Maya Blue, an ancient nanostructured organic–inorganic hybrid material resulting from the attachment of indigo, a natural dye, to a phyllosilicate clay, palygorskite, has received considerable attention of late. Despite intensive research, several aspects remain unsolved, in particular the nature of the indigo–palygorskite association. Recent results suggest that the Maya Blue pigment is a complex system in which different topological isomers of various indigoid molecules attached to the palygorskite matrix coexist.
Molybdenum(VI)-dioxo complexes with sterically bulky thiocarboxylate ligands. Reactions with aliphatic thiols and electrochemical properties
1991
Abstract Under acid conditions, the reaction of (Bu n 4 N)2[Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] with aliphatic thiols yields the monomeric [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − as unique complex product. The experimental pseudo-first order rate constant with respect to the Mo(VI) complex was found to be K =6.1 × 10 −5 s −1 . At neutral pH, however, an unstable Mo(IV) species was formed which was also electrochemically detected in a reversible Mo(V,IV) couple. [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − appears to be obtained by the reaction of [Mo IV O(O 2 CC(S)Ph 2 ) 2 ] 2− with unreacted [Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] 2− . Steric features on the ligand (gemdiphenyl groups) explain that the latter reaction does not…
CORRELATION BETWEEN SPECTRAL, SEM/EDX AND ELECTROCHEMICAL PROPERTIES OF MAYA BLUE: A CHEMOMETRIC STUDY*
2009
Visible spectra, composition from SEM/EDX and solid-state electrochemical data are correlated for a set of 12 Maya Blue samples from different archaeological sites of Campeche and Yucatan (Mexico). In addition to indigo and dehydroindigo, indirubin and other possibly indigo-type compounds can be detected in Maya Blue samples. Application of hierarchical cluster analysis techniques allows similarity relationships to be established between samples from different sites, confirming prior results which suggest that the preparation of Maya Blue pigment evolved with time during the Maya culture following a ramified scheme.
Electrochemistry of copper complexes with polyaza[n]paracyclophanes. Influence of ATP as an exogen ligand on the relative stability of the Cu(II) and…
2000
Abstract Interaction of Cu 2+ with the macrocycle 2,6,9,13-tetraaza[14]paracyclophane (L) and ATP has been followed by pH-metric titration, cyclic voltammetry and differential pulse voltammetry (DPV). Mixed adduct species with various degrees of protonation were found to be stable for pH>4. In neutral and alkaline media reduction of mixed complexes occurs in a two-electron quasi-reversible step in contrast with binary Cu 2+ L complexes which display two successive one-electron couples. The potentiometric and voltammetric data suggest that in ternary adducts ATP binds to Cu 2+ ions through the phosphate chain and one N-site of the adenine ring system.
Enantioselective epoxidation of olefins with molecular oxygen catalyzed by gold(III): A dual pathway for oxygen transfer
2009
Abstract A chiral gold(III) complex has been prepared that performs the epoxidation of olefins in the presence of O 2 , PhIO, or bleach. Catalytic experiments with 18 O show that O 2 is activated on the catalyst and can be directly incorporated into the epoxide through a non-radical mechanism that probably involves formation of gold, oxo, or peroxo species. In addition to this, there is a parallel radical mechanism operating that yields α , β -unsaturated ketones and alcohols as subproducts. Electrochemical and UV–Vis experiments confirmed the occurrence of a Au(III)/Au(I) redox cycle during the catalytic epoxidation in a mechanism sustained by molecular oxygen.
Mn(II) complexes of scorpiand-like ligands. A model for the MnSOD active centre with high in vitro and in vivo activity
2015
Manganese complexes of polyamines consisting of an aza-pyridinophane macrocyclic core functionalised with side chains containing quinoline or pyridine units have been characterised by a variety of solution techniques and single crystal x-ray diffraction. Some of these compounds have proved to display interesting antioxidant capabilities in vitro and in vivo in prokaryotic (bacteria) and eukaryotic (yeast and fish embryo) organisms. In particular, the Mn complex of the ligand containing a 4-quinoline group in its side arm which, as it happens in the MnSOD enzymes, has a water molecule coordinated to the metal ion that shows the lowest toxicity and highest functional efficiency both in vitro …
Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic …
2011
The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (PrxZr(1−y)Si(1−z)O4; y + z = x; 0.02 < x < 0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, PrxZr(1−y)Si(1−z)O4 materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical…
Electrochemically assisted anion insertion in Au(I)–Cu(I) heterotrimetallic clusters bearing ferrocenyl groups: Application to the fluoride/chloride …
2010
The heterotrimetallic Au(I)–Cu(I) aggregate [{Au3Cu2(C2C6H4Fc)6}Au3(PPh2C6H4PPh2)3](PF6)2 exhibits a well-defined solid state electrochemistry in contact with aqueous media, based on ferrocenyl-centred oxidation processes involving anion insertion. Upon attachment of microparticulate deposits of the cluster to graphite electrodes, distinctive electrochemical responses can be obtained for fluoride and chloride ions in aqueous media. Keywords: Heterometallic clusters, Gold, Copper, Fluoride/chloride discrimination, Electrochemical anion insertion
Voltammetric behaviour of monomeric fac-trioxomolybdenum(VI) complexes with aminocarboxylic ligands in aqueous media
1992
Abstract Cyclic voltammetry, polarography and controlled-potential coulometry experiments have been used to characterize the electrochemical reduction of fac-MoO3L2− complexes (L = aspartic acid or iminodiacetic acid) in aqueous media. These complexes are reduced in two irreversible proton-assisted steps to give an oxo-bridged molybdenum(V) species and then to a molybdenum(III) dimer species. At pH 4.5, the former reduction step for the iminodiacetic acid ligand occurs at Ep = −0.75 V, while the second one appears at −1.12 V vs SCE. The overall electrochemical process can be described in terms of a homogeneous chemical reaction, coupled between two electron transfers (ECE mechanism), that i…
Tracing, authenticating and dating archaeological metal using the voltammetry of microparticles
2011
Electrochemical techniques provide information of archaeometric interest. An overview on the application and future developments of the voltammetry of microparticles to the study of archaeological metals and their alteration products is presented. A report on the state of the art and future developments of this technique with regard to identification and origin studies of materials, authentication, chronology and dating of archaeological metal is provided.
A polyazacyclophane containing two biphenyl subunits as a versatile cation and anion receptor
2002
Abstract The synthesis, protonation behaviour and coordination capabilities towards Cu 2+ , Zn 2+ and towards the nucleotides ATP and ADP of a cyclophane ditopic receptor 2,6,10,23,27,31-hexaaza[11,11](2,2′)biphenylophane containing two 2,2′-biphenylene spacers linked to the ends of 1,5,9-triazanonane chains are presented.
The catalytic reduction of nitrobenzene at the [MoVIO2(O2CC(S)(C6H5)2)2]2? complex intercalated in a Zn(II)-Al(III) layered double hydroxide host: A …
2001
The heterogeneous reduction of nitrobenzene by thiophenol catalyzed by the dianionic bis(2-sulfanyl-2,2-diphenylethanoxycarbonyl) dioxomolybdate(VI) complex, [MoVIO2(O2CC(S)(C6H5)2)2]2−, intercalated into a Zn(II)–Al(III) layered double hydroxide host [Zn3−xAlx(OH)6]x+, has been investigated under anaerobic conditions. Aniline was found to be the only product formed through a reaction consuming six moles of thiophenol for each mol of aniline produced. The kinetics of the system have been analyzed in detail. In excess of thiophenol, all reactions follow first-order kinetics (ln([PhNO2]/[PhNO2]0) = −kappt) with the apparent rate constant kapp being a complex function of both initial nitrobenz…
Determination of Individual Gibbs Energies of Anion Transfer and Excess Gibbs Energies Using an Electrochemical Method Based on Insertion Electrochem…
2011
A method is presented to determine, individually and with minimal extra-thermodynamic assumptions, the Gibbs energy for anion transfer between two solvents using solid state electrochemistry of alkynyldiphosphine dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1, R = Fc; L2, R = C6H4Fc) and the heterometallic Au(I)–Cu(I) [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3, R = Fc; L4, R = C6H4Fc) cluster complexes containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes, based on ferrocenyl-centered oxidation processes involving anion insertion. Voltammetric data can be used for a direct measurement of…
Anionic Organic Guests Incorporated in Zeolites: Adsorption and Reactivity of a Meisenheimer Complex in Faujasites
2005
Zeolites are suitable microporous hosts for positively charged organic species, but it is believed that they cannot adsorb organic anions. Pure Meisenheimer complex, derived from reduction of 2,4-dinitroaniline with NaBH4, was adsorbed inside faujasite cavities. Evidence for the internal incorporation of this negatively charged reaction intermediate comes from 1) XPS elemental analysis as a function of the depth of penetration into the particle, 2) the remarkable blue shift in lambda(max) of the Meisenheimer complex adsorbed on zeolite (ca. 470 nm) as compared to that in acetonitrile (580 nm) and 3) from the lack of reactivity with size-excluded hydride-acceptor reagents. Evidence is provid…
Gold Redox Catalytic Cycles for the Oxidative Coupling of Alkynes
2011
[EN] Au(I)/Au(III) catalytic cycles are catalytically competent to perform the oxidative coupling of alkynes in the homogeneous phase at room temperature and without any protecting atmosphere. Selectfluor as oxidant, wet acetonitrile as solvent, and sodium carbonate as base are the reagents of choice. Both aromatic and alkyl alkynes can be coupled, and mechanistic studies reveal that at least two gold species having different oxidation states are implicated in the key step of the coupling.
Cyclic voltammetric analysis of pH-dependent complex formation equilibria in anion coordination chemistry
1995
A procedure to analyze pH-dependent complex formation equilibria from cyclic voltammetry is described. Application to adduct formation equilibria between [Fe(CN)(6)](4-) and [Fe(CN)(6)](3-) with different polyammonium receptors is discussed. Extension to the interaction of substrates such as ATP, NAD(+), NADP(+), and carboxylate ions with these receptors by means of competitive interaction with hexacyanoferrate(II) ion is presented.
Steam-activated FeMFI zeolites. Evolution of iron species and activity in direct N2O decomposition
2003
Abstract In this paper the effect of the composition and steaming conditions of FeMFI catalysts on activity in direct N2O decomposition is investigated. MFI zeolites with different framework compositions (FeAlSi, FeGaSi, and FeSi) and without iron ( 100 mbar H2O in N2) favor the extraction of framework iron, enabling the application of lower activation temperatures. The optimum temperature during steam activation is that at which extraction of framework iron is complete without extensive clustering of extra-framework iron species into oxide particles, as was demonstrated by transmission electron microscopy and electrochemical characterization of the samples. Additional experiments show…
Maya Blue as a nanostructured polyfunctional hybrid organic–inorganic material: the need to change paradigms
2009
Maya Blue, an ancient nanostructured organic–inorganic hybrid material resulting from the attachment of indigo, a natural dye, to a phyllosilicate clay, palygorskite, has received considerable attention of late. Despite intensive research, several aspects remain unsolved, in particular the nature of the indigo–palygorskite association. Recent results suggest that the Maya Blue pigment is a complex system in which different topological isomers of various indigoid molecules attached to the palygorskite matrix coexist.
Vanadium‐Doped Zircon and Zirconia Materials Prepared from Gel Precursors as Site‐Selective Electrochemical Sensors
2003
Abstract Polymer film electrodes incorporating vanadium‐doped zircon (V x ZrSiO4, 0.00 < x < 0.10) and vanadium‐doped monoclinic and tetragonal zirconias (V x ZrO2, 0.00 < x < 0.15), prepared by heat treatment of gel precursors, exhibit a significant site‐selective electrocatalytic activity towards the oxidation of amino acids, polyalcohols, and polyhydroxycarboxylic acids in alkaline media. Catalysis of the oxidation of carboxylate and alcohol groups involves a relatively slow chemical reaction between the substrate and vanadium centers, while the oxidation of thiolate in cysteine can be attributed to the oxidation of an adduct formed by vanadium centers and the substrate.
Solid-state electrochemistry of LDH-supported polyaniline hybrid inorganic–organic material
2008
Abstract The solid-state electrochemistry of a Zn–Al layered double hydroxide-supported polyaniline material (LDH-PANI) in contact with aqueous electrolytes is described. Interconversion processes between different forms (emeraldine, protoemeraldine, leucoemeraldine, nigraniline and pernigraniline) of the LDH-supported polyaniline units are involved in redox processes. This material exhibits significant variations of impedance upon application of different conditioning potentials, acting as an electrochemical frequency filter. Using Fe (CN) 6 4 - as redox probe, LDH-PANI can be used as a chemical–electrochemical information processing system equivalent to different combinational logic circu…
4,4′-Substituted biphenyl coronands. Preparation of a new selective fluorescent sensor for mercury salts
2006
Six new 4,4′-substituted biphenyl coronands have been prepared. The ligands containing dimethylamino groups in the biphenyl moiety have been used in transition metal cations’ complexation and one of them (3) has demonstrated to be a selective fluorescent sensor for mercury. Stoichiometries of the formed complexes and complexation constants have been determined by titration experiments. In addition, the extractant ability of some ligands has also been studied. Finally, the electrochemical properties of some of these ligands are also described.
Ship-in-a-Bottle Synthesis of a Large Guest Occupying Two Y Zeolite Neighbour Supercages: Characterisation and Photocatalytic Activity of the Encapsu…
2003
In a series of papers we reported the ship-in-a-bottle synthesis, photochemical properties and photocatalytic applications of 2,4,6-triphenylpyrylium cation (TP ) encapsulated inside the cavities of large pore zeolites Y and Beta. 2] The identity of encapsulated TP was then confirmed spectroscopically, particularly by the match of the IR spectra of the encapsulated organic material and that of the tetrafluoroborate solid of TP (TPBF4). In addition, the electrochemical response of zeolite Y encapsulated TP (TP@Y) consisted of a reversible single reduction process taking place at the same redox potential as that measured for TPBF4 solutions. Encapsulation of TP has a dramatic influence on its…
Study of Redox Processes in Zeolite Y-Associated 2,4,6-Triphenylthiopyrylium Ion by Square Wave Voltammetry
2003
The electrochemical responses of 2,4,6-triphenylthiopyrylium ion (TTP+) in solution and attached to zeolite Y (TTP@Y) are described using cyclic and square wave voltammetries upon immersion of zeolite-modified polymer film electrodes in MeCN (LiClO4, Et4NClO4, and BuN4PF6 electrolytes) and aqueous (LiNO3, NaNO3, and KNO3 electrolytes) media. The electrochemistry of TTP@Y in contact with Bu4NPF6/MeCN is identical to that of TTP(BF4) in solution, with reduction processes at −0.25, −0.74, and −1.36 V vs SCE, and oxidation steps at +0.85 and +1.11 V. This response differs from those obtained for TTP@Y in Et4NClO4/MeCN and LiClO4/MeCN electrolytes. In contact with aqueous electrolytes, TTP@Y dis…
Study of solid state kinetics using voltammetry of immobilized particles. Application to tetragonal to monoclinic transition in nanoparticulate zirco…
2012
Abstract The voltammetry of immobilized particles methodology is applied to study solid state reaction kinetics on the basis of the electrocatalytic ability of solids toward selected electrochemical processes. Measurement of the time variation of catalytic current for oxygen evolution reaction in aqueous alkaline media provides a direct estimate of fractional conversion of the reactant in the course of the reaction for testing different reaction kinetic models. This methodology is applied to analyze the formation of monoclinic zirconia and praseodymia-doped zirconia from tetragonal precursors. Discrimination between competing and successive reactions mechanisms is obtained for reactions inv…
From Maya Blue to “Maya Yellow”: A Connection between Ancient Nanostructured Materials from the Voltammetry of Microparticles
2011
The yellow hue of a series of samples from wall paintings in several Mayan archaeological sites can be attributed to the presence of indigoid compounds, including isatin and dehydroindigo, attached to palygorskite, a local phyllosilicate clay. SEM/EDX, TEM, UV/Vis spectroscopy, and voltammetry of microparticles show that the ancient Mayas could prepare indigo, Maya Blue, and "Maya Yellow" during successive stages. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Electro- and magneto-electrochemistry of zeolite Y- and MCM-41-associated bipyrylium ion
2005
Abstract The electrochemical response of bipyrylium bication [1,4-bis(3,5-diphenyl-4-pyrylium)phenylene] associated with Y and MCM-41 aluminosilicates (BTP@Y and BTP@MCM, respectively) is described using polymer-film electrodes immersed into Et 4 N + + MeCN and Bu 4 N + + MeCN electrolytes. BTP@MCM provides a solution-like response in all electrolytes consisting in two successive strongly comproportionation mediated one-electron reduction processes near to +0.05 and −0.12 V vs. Ag|AgCl. The response of BTP@Y in Bu 4 N + + MeCN is restricted to a unique reduction process near to −0.40 V, while in Et 4 N + + MeCN, it differs significantly: here, two reduction processes at −0.22 and −0.36 …
Electrochemical determination of the stability of complexes formed by proton-ionizable ligands of 3,5-disubstituted 1H-pyrazole with phenethylamine
1999
The application of two extreme models for diffusion in two-component systems to electrochemically determine equilibrium constants is discussed. The application of cyclic voltammetric, diferential pulse and rotating-disc electrode voltammetric data to elucidate the stoichiometry and formation constant of complex species by applying a generalization of the molar-ratio method is described. Molar-ratio experiments permit the distinction between the limiting diffusive regimes. The values of the equilibrium stability constants for complexation of phenethylamine and phenethylammonium ions by a 26-membered dioxotetraester crown of 3,5-disubstituted 1H-pyrazole as free ligand 1[L] and as dipyrazolat…
Magnetoelectrochemical modulation of pre-organization processes in a 4,4′-dinitrobiphenyl azacrown macrocyclic lactam
2004
A magnetoelectrochemical effect consisting on the modulation of the reaction rate of pre-organization reactions in a 4,4′-dinitrobiphenyl azacrown lactam is described. The electrochemical response of that compound in DMSO solution at microelectrodes consists in two successive dinitrobiphenyl-centred one-electron transfer processes at −0.9 and −1.6 V vs. AgCl/Ag involving the transition from the dihedral geometry of the neutral starting compound to the planar geometry of the final dianion, resulting in an overall ECE mechanism. In the presence of moderate (0.05–0.2 T) static magnetic fields, the second electron transfer process decreases significantly, the apparent rate constant of the dihed…
Electrochemistry of copper complexes with macrocyclic polyamines containing pyrazole units.
2006
The voltammetric behaviour of bi- and mono-nuclear complexes formed in solution by Cu(2+) with three polyazacyclophanes containing pyrazole units in aqueous solution is described. Cyclic and square wave voltammetric responses at glassy carbon electrodes indicate that the reduction of copper-macrocycle complexes in solution takes place in two successive one-electron per Cu transfer processes coupled with preorganization and protonation reactions that mimic the behaviour of superoxide dismutase. The electrochemistry of ternary Cu(2+)-receptor-dopamine complexes exhibits significant differences with respect to the protection of the neurotransmitter from post-electron transfer cyclization react…
Methylation as an effective way to generate SOD-activity in copper complexes of scorpiand-like azamacrocyclic receptors
2018
Abstract Methylation of the secondary amine groups of a scorpiand-type ligand consisting of a pyridine spacer connected through methylene groups to a tris(2-aminomethyl) unit with the pendant arm further functionalised with a 3-pyridine unit leads to a ligand whose Cu(II) complex exhibits threefold enhanced SOD activity with respect to the non-methylated ligand. Potentiometric studies indicate the formation of [CuL] 2+ species with a stability three orders of magnitude lower than that formed with the related non-methylated ligand. Kinetic studies indicate that methylation of the secondary nitrogens causes a deceleration of both the complex formation and the acid-induced dissociation of the …
Cation and anion fluorescent and electrochemical sensors derived from 4,4′-substituted biphenyl
2005
Five new fluorescent macrocyclic ligands derived from biphenyl are described. These new compounds can be used in cation and anion recognition and sensing. Their fluorescent and electrochemical properties are studied and the influence of the biphenyl conformation on these properties is considered. The X-ray single crystal structure of one of the described ligands has been determined.
Synthesis and Cu(II) coordination of two new hexaamines containing alternated propylenic and ethylenic chains: Kinetic studies on pH-driven metal ion…
2006
Abstract The synthesis of the open-chain and cyclic polyamines, 1,5,8,12,15,19-hexaazaheptadecane (L1) and 2,6,9,13,16,20-hexaaza[21]-(2,6)-pyridinophane (L2), are described. The protonation constants and interaction constants with Cu(II) have been determined by potentiometric measurements carried out at 298.1 K in 0.15 mol dm −3 NaClO 4 . The values obtained are discussed as a function of the open-chain or cyclic nature of the ligands and compared with analogous polyamines containing different sets of hydrocarbon chains between the nitrogen donors. Kinetic studies on the acid-promoted dissociation of the Cu(II) complexes indicate that the mono and binuclear complexes of L1 decompose with d…
Electrochemical chiral recognition by microparticle coatings of Pd complexes with bridging cyclometalated phosphines
2008
Abstract The palladium(II) dinuclear complex with bridging cyclometalated phosphines, {Pd2[μ-(C6H4)PPh2]2(μ-O2CCH3)2} (Pd2L2), having a paddlewheel structure, is reversibly oxidized in CH2Cl2 to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd2L2 in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd2L2 produces a significant stereoselective electrocatalytic activity with respect to the oxidation of l - and d -glutamic acid in alkaline media.
Non-smooth modelling of billiard- and superbilliard-ball collisions
2008
Abstract A description of billiard-ball collisions using a ‘discontinuous’ model is presented considering a two-step situation corresponding to the ball–ball interaction followed by ball-supporting surface interaction. It is applied to the inelastic impact of a cue ball having arbitrary pivotment and ‘English’ spins against an object ball initially at rest. This formulation provides a simplified approximation to the ‘continuous’ models of impact and considers two different regimes of impact: gross slip, and slip–stick, described in terms of coefficients of friction and restitution. As a result, the angles of scattering of the balls just after the impact (post-collision angles) and when the …
Electrochemical Detection of High Oxidation States of Chromium( IV and V ) in Chromium‐Doped Cassiterite and Tin‐Sphene Ceramic Pigmenting Systems
2006
Solid-state electrochemistry is applied to detect the presence of chromium centres with high oxidation states in chromium-doped cassiterite and tin-sphene ceramic pigmenting systems. Voltammetric data indicate that CrV and CrIV centres with different coordinative arrangements exist in the studied materials, and yield proton-assisted reduction processes at +0.95, +0.42 AgCl/Ag in contact with 0.50 M H2SO4. Electrochemical measurements are correlated with spectroscopic data. The CrIV and CrV metal ions display a significant light-driven electrocatalytic effect on the oxidation of 1,4-dihydrobenzoquinone and Fe(CN)64– ions that involves the formation of surface-confined adducts. (© Wiley-VCH V…
Electrochemistry of hydrotalcite-supported bis(2-mercapto-2,2-diphenyl-ethanoate) dioxomolybdate complexes.
1998
The redox properties of the hydrotalcite-intercalated bis(2-mercapto-2,2-diphenyl-ethanoate) dioxomolybdate(VI) complex are investigated by cyclic voltammetry by using modified carbon paste electrodes and clay-modified electrodes. The electrochemical data provide evidence that boundary-associated species involving the VI, V and IV oxidation states of molybdenum are responsible for the electroactivity.
Dalton communication. Crystal structure and oxo-transfer properties of [NH4]2[WVIO2{O2CC(S)Ph2}2]
1994
The complex [NH4]2[WVIO2{O2CC(S)Ph2}2] is the first example of a non-dithiolene tungsten complex capable of oxidising benzoin to benzil in methanol; the reduced complex product formed, presumably a monomeric WVIO species, was reoxidised with nitrate ions, regenerating the starting WVIO2 complex which then acts as a true homogeneous catalyst.
Electrochemical reduction of the nitrite to ammonium ions in presence of [MoO2(O2CC(S)C6H5)2]2−
1995
Abstract Ammonia is formed during potentiostatic reduction of sodium nitrite solutions on the nafion-complex-coated electrode. When (NH4)2[MoO2(O2CC(S)(C6H5)2)2] is present in NaNO2 solutions a polarographic wave is associated to electrocatalytic reduction of nitrite ion. The wave height varies linearly on the concentration of nitrite ion, allowing a procedure for analysing this ion. This electrochemical behaviour distinguishes the nitrite from the nitrate ions. The Mo(VI), Mo(V), and Mo(IV) are involved in catalytic redox processes determining formation of NH4+ from nitrite ions.
CO2 Fixation by Cu2+ and Zn2+ complexes of a terpyridinophane aza receptor. Crystal structures of Cu2+ complexes, pH-metric, spectroscopic, and elect…
2006
The synthesis of the terpyridinophane-type polyamine 2,6,9,12,16-pentaaza[17]-(5,5' ')-cyclo-(2,2':6',2' ')-terpyridinophane heptahydrobromide tetrahydrate (L.7HBr.4H2O) is described. L presents six protonation constants with values in the range 9.21-3.27 logarithmic units. L interacts with Cu2+ and Zn2+ forming in both cases, neutral, protonated, and hydroxylated mono- and binuclear complexes whose constants have been calculated by potentiometry in 0.15 M NaClO4 at 298.1 K. The crystal structures of the compounds [Cu(HL-carb)(H2O)](ClO4)3.2H2O (1) and [Cu2(H2L)(CO3)]2(ClO4)8.9H2O (2) have been solved by X-ray diffraction. In 1, the metal center presents square pyramidal geometry. The base …
Electrochemistry of Mesoporous Organosilica of MCM-41 Type Containing 4,4′-Bipyridinium Units: Voltammetric Response and Electrocatalytic Effect on 1…
2003
The electrochemistry of a novel organic−inorganic material in which 4,4‘-bipyridinium units (BP) are covalently attached to the walls of a periodic mesoporous organisilica (PMO) of the MCM-41 type is described. The pristine material (BP@PMO), having its internal space completely filled by the cetyltrimethylammonium structure-directing agent, is almost electrochemically silent. In contrast, the extracted material obtained after removal of the structure-directing agent (BP@PMO-ex) exhibits two reduction peaks at −0.36 and −0.75 V vs AgCl/Ag in contact with aqueous electrolytes. BP@PMO-ex shows a remarkable electrocatalytic effect on the oxidation of 1,4-dihydrobenzoquinone (H2Q) that is studi…
Electrocatalysis of the oxidation of methylenedioxyamphetamines at electrodes modified with cerium-doped zirconias
2004
The catalytic effect of monoclinic and tetragonal cerium-doped zirconias (m-CexZr1−xO2 and t-CexZr1−xO2, 0<x<0.10, respectively), prepared from gel precursors, on the oxidation of methylenedioxyamphetamine (MDA) and methylenedioxymetamphetamine (MDMA) at pH 7.0 has been studied. Upon attachment of synthetic specimens to polymer film electrodes, an oxidation peak near to +1.05 V vs AgCl/Ag appears that is unaffected by chloride ions and common interfering compounds, namely, dopamine, norepinephrine and ascorbic acid. The catalytic effect appears to be strongly influenced by crystallinity of specimens and coordination of cerium, increasing from the amorphous starting material to t-CexZr1−xO2 …
2,4,6-Triphenylpyrylium Ion Encapsulated into Zeolite Y as a Selective Electrode for the Electrochemical Determination of Dopamine in the Presence of…
2002
2,4,6-Triphenylpyrylium ion immobilized inside the supercages of zeolite Y enhances by 1-2 orders of magnitude the response of electrochemical oxidation of dopamine in neutral aqueous media accompanied by a remarkable inhibition of post-electron-transfer reactions. The negative charge of the zeolite framework in which the 2,4,6-triphenylpyrylium ion is incorporated blocks the electrochemical oxidation of the negative ascorbate ion, enabling the determination of micromolar concentrations of dopamine in the presence of a large excess (10(3)-10(4) times) of ascorbate in phosphate buffer (pH 7.4). Under optimized conditions, linear calibration plots were obtained for a differential pulse detect…
Electrochemical Monitoring of Compartmentalization Effects in the Stability of Meisenheimer Anions Supported in Hydrotalcite and X and Y Zeolites
2005
Meisenheimer anions (MS - ) derived from 2,4-dinitroaniline are stabilized into Li + - and Na + -exchanged zeolites X and Y forming alkali ion-MS ion pairs. Upon attachment of the zeolites to polymer film electrodes immersedinto Et 4 N + /MeCN and Li + /MeCN electrolytes, boundary-associated MS - ions display two oxidation processes at +0.40 and +0.65 V vs. AgCl/Ag. This response sharply contrasts with that recorded for MS - in solution and incorporated within hydrotalcite, for which a unique oxidation peak at +0.35 V is recorded. The electrochemistry of zeolite-associated MS - can be described in terms of an unusual electron-transfer/ chemical reaction/electron-transfer/comproportionation …
Magnetoelectrochemistry of 4,4′-bis(dimethylamino)biphenyl and 4,4′-dinitrobiphenyl azacrown macrocyclic lactams
2005
Abstract The voltammetric behaviour at carbon fibre microelectrodes under the application of static magnetic fields of two series of macrolactams containing in their structure 4,4′-bis(dimethylamino)biphenyl or 4,4′-dinitrobiphenyl groups in MeCN solution is described. The response of 4,4′-dinitrobiphenyl receptors is dominated by two successive one-electron reduction processes at −0.9 and −1.6 V versus AgCl/Ag. 4,4′-bis(dimethylamino)biphenyl-containing receptors display two one-electron oxidations above +0.8 and +1.0 V. In both cases, a dihedral/planar interconversion precedes the second electron transfer step. Upon application of moderate (0.05–0.2 T) static magnetic fields to the electr…
Hydrophobic effects in the stabilisation of copper(I) by the macrocyclic ligands 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane and 14,1…
1996
Abstract The interaction of Cu 2+ with the para -azacychlophanes 16,17,19,20-tetramethyl-2,6,9,13-tetraazal[14]paracyclophane (L1) and 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L2) has been studied by potentiometry, and direct microcalorimetry at 298.1±0.1 K in 0.15 mol dm −3 NaClO 4 . The stability constants (log K CuLi = 13.35(3), log K CuL2 = 9.32(4)) and the thermodynamic parameters ( ΔH ° CuL1 = −47.3(8) kJ mol −1 , ΔH ° CuL2 = 20.9(8) kJ mol −1 ) evidence that not all four nitrogen atoms in the ligands are involved in the coordination to the metal centre. These results, particulary in the case of L1, are similar to those reported for the analogous cyclophanes contai…
Insights into the Maya Blue technology: greenish pellets from the ancient city of La Blanca.
2011
Financial support is gratefully acknowledged from the MEC Projects CTQ2011-28079-CO3-01 and 02 which are also supported with ERDF funds. Research was conducted within the "Grupo de anlisis cientifico de bienes culturales y patrimoniales y estudios de ciencia de la conservacion" Microcluster of the University of Valencia Excellence Campus. The authors would like to thank Dr. Isabel Solana (SCSIE, UV), Dr. Jose Luis Moya Lopez, and Manuel Planes Insausti (Microscopy Service UPV) for their technical support.
Biphenylthioureas as organocatalysts for electrochemical reductions
2007
Abstract Thioureas are able to act as organocatalysts in the electrochemical reduction of aromatic carboxylates.
Dinuclear palladium(ii) compounds with bridging cyclometalated phosphines. Synthesis, crystal structure and electrochemical study
2006
The structural characterization of bis-cyclometalated palladium(II) compounds of formula Pd2[(micro-(C6X4)PPh2]2(micro-O2CR)2 [X = H, R = CH3 (3), CF3 (4), C(CH3)3 (5) and C6F5 (6); X = F, R = CH3 (7) and CF3 (8)], has confirmed its paddle wheel structure with two palladium atoms bridged by two acetates and two metalated phosphines in a head-to-tail arrangement. The Pd...Pd distances are in the range 2.6779(16)-2.7229(8) A. Under cyclic voltammetric conditions, compounds 3-6, in CH2Cl2 solution, were found to undergo a reversible oxidation peak in the range of potential values 0.84-1.25 V. A second partially-reversible oxidation is observed at more positive potentials (1.37-1.55 V). For com…
A kinetic model for the oxidation of benzenethiol catalyzed by the [MoVIO2(O2CC(S)(C6H5)2)2]2− complex intercalated in a Zn(II)–Al(III) layered doubl…
2009
Abstract The heterogeneous oxidation of benzenethiol catalyzed by the dianionic bis(2-sulfanyl-2,2-diphenylethanoxycarbonyl) dioxomolybdate (VI) complex intercalated into a Zn(II)–Al(III) layered double hydroxide (LDH) host have been investigated under aerobic conditions. The kinetics of the system has been analysed in detail. In ethanol, the benzenethiol is cleanly oxidized to diphenyl disulfide in the acidic media provided by the protonic resin Amberlite IR-120(H). The reaction is second-order in benzenethiol, and the apparent rate coefficient has been found to be proportional to the catalyst weight and inversely proportional to the initial concentration of the substrate. A catalytic cycl…
Mononuclear mixed oxosulfidomolybdate(VI) complexes with aminodicarboxylic ligands. Synthesis and spectroscopic characterization by multinulcear magn…
1993
Addition of B2S3 to a methanolic solution of the MoVIO3L2− complex (L=N,N-bis(ethanoic acid)-1-amino-2- methylthio-ethane) results in the formation of two different monomeric oxosulfidomolybdate(VI) complexes, [MoO2SL]2− and [MoOS2L]2− as indicated by 1H, 13C, 17O and 95Mo NMR spectroscopy and by the reaction of these two sulfurated species with triphenylphosphine. The temperature dependences of the 1H NMR spectra indicate exchange processes for both sulfido complexes. Their redox properties are discussed and contrasted with those observed for the parent fac-trioxo molybdenum(VI) complex. The primary synthetic route to mixed oxosulfido [MoO3−nSnL]2− complexes described here can be extended …
Effective complexation of psychotropic phenethylammonium salts from a disodium dipyrazolate salt of macrocyclic structure
2002
The equilibrium stability constants (Ks) of ammonium pyrazolate complexes [L2−]2RN(R′)H2+ (3, R′ = H and 4, R′ = Me) formed from a macrocyclic disodium dipyrazolate salt 2[L2−] 2Na+ and ammonium salts (RNH3+X− or RN(Me)H2+X−) of psychotropic drugs and neurotransmitter catecholamines have been evaluated by electrochemical methods in DMSO solution. The resulting Ks values demonstrate that, except for (±)-amphetamine, the complexes formed by lipophilic primary [mescaline, (+)-amphetamine, (±)-p-methoxyamphetamine (PMA), (±)-3,4-methylenedioxyamphetamine (MDA)] and secondary [(±)-methamphetamine, (+)-methamphetamine and (±)-3,4-methylenedioxymethamphetamine (MDMA ‘ecstasy’)] phenethylamines are…
CO2fixation and activation by metal complexes of small polyazacyclophanes
2001
The interaction of the cyclophanes 2,6,9,13-tetraaza[14]paracyclophane (L1) and 2,6,9,13-tetraaza[14]metacyclophane (L2) and of their Zn2+ and Cu2+ complexes with CO32− and its protonated forms is described. The actuation of the Cu2+–L2 system as an electrocatalyst for the reduction of CO2 to CO in water is advanced. Copyright © 2001 John Wiley & Sons, Ltd.
Identification of Earth Pigments by Applying Hierarchical Cluster Analysis to Solid State Voltammetry. Application to Severely Damaged Frescoes
2007
Multivariate chemometric methods are applied for identifying earth pigments from square-wave voltammetric measurements performed at pigment-modified paraffin-impregnated graphite electrodes allowing for a separation between hematite-based earths, French ochres, Spanish ochres, siennas, umbers and green earths. This methodology is applied to the identification of the pigments in samples from the ceiling frescoes of Antonio Palomino (dated 1707) in the vaulted nave of the Sant Joan del Mercat church in Valencia (Spain). These frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations. Electrochemical data, support…
Selective electrochemical discrimination between dopamine and phenethylamine-derived psychotropic drugs using electrodes modified with an acyclic rec…
2010
Electrochemical discrimination between dopamine and psychotropic drugs which have in common a skeletal structure of phenethylamine, can be obtained using acyclic receptors L(1) and L(2), containing two terminal 3-alkoxy-5-nitroindazole rings. Upon attachment to graphite electrodes, L(1) and L(2) exhibit a well-defined, essentially reversible solid state electrochemistry in contact with aqueous media, based on electrolyte-assisted reduction processes involving successive cation and anion insertion/binding. As a result, a distinctive, essentially Nernstian electrochemical response is obtained for phenethylammonium ions of methamphetamine (METH), p-methoxyamphetamine (PMA), amphetamine (AMPH),…
Determination of hydrogen peroxide using glassy carbon and graphite/polyester composite electrodes modified by vanadium-doped zirconias
2002
Abstract Synthetic monoclinic and tetragonal vanadium-doped zirconias (VZrO2) with vanadium loading ranging from 0.5 to 15 mol% are used to modify glassy carbon and graphite/polyester composite electrodes able to detect oxygen and hydrogen peroxide in neutral aqueous media. Electrodes modified by monoclinic VZrO2 decrease the overpotential for the reduction of oxygen and hydrogen peroxide in neutral and alkaline media and enhance their reduction currents with respect to unmodified carbon electrodes. This is associated to seven-coordinated vanadium centers isomorphously substituting zirconium ones in the ZrO2 lattice. The catalytic effect shows site-selectivity, since it is almost entirely a…
Manganese(II) complexes of scorpiand-like azamacrocycles as MnSOD mimics.
2011
Mn(II) complexes of scorpiand-type azamacrocycles constituted by a tretrazapyridinophane core appended with an ethylamino tail including 2- or 4-quinoline functionalities show very appealing in vitro SOD activity. The observed behaviour is related to structural and electrochemical parameters.
The Maya Blue Pigment
2011
Abstract Maya blue is an artificial pigment fabricated by the Maya in the early first millennium AD. The pigment was used in Prehispanic times from the southern Maya region to most Mesoamerican cultures. Maya blue is made from indigotin mixed with palygorskite. This light blue pigment is surprisingly resistant to degradation in adverse environmental conditions, as it is unaffected by the attack of acids, alkalis, oxidants, reducing agents and organic solvents. Scientists do not fully agree in the mechanism of this organoclay interaction. The fabrication and distribution of this pigment probably required a sophisticated technical and commercial infrastructure. This chapter reviews the presen…
Imidazolate bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) complexes of a terpyridinophane azamacrocycle: a solution and solid state study.
2007
The dinuclear Cu2+ and Zn2+ as well as the mixed Cu2+-Zn2+ complexes of a 5,5''-pentaazaterpyridinophane ligand (L) are able to incorporate imidazolate (Im-) as a bridging ligand. The crystal structure of [Cu(2)L(Im)(Br)(H2O)](CF(3)SO(3))(2).3H2O (1) shows one copper coordinated by the three pyridine nitrogens of the terpyridine unit, one nitrogen of the imidazolate bridge (Im-) and one bromide anion occupying the axial position of a distorted square pyramid. The second copper atom is coordinated by the remaining imidazolate nitrogen, the three secondary nitrogens at the centre of the polyamine bridge and one water molecule that occupies the axial position. Magnetic measurements have been p…
Estimation of free energies of anion transfer from solid-state electrochemistry of alkynyl-based Au(I) dinuclear and Au(I)–Cu(I) cluster complexes co…
2011
A method is presented to determine the free energy for anion transfer between two solvents. This is based on solid-state electrochemistry of alkynyl-based dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1: R=Fc; L2: R=C6H4Fc) and heterometallic Au(I)–Cu(I) [{Au3Cu2 (C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3: R=Fc; L4: R=C6H4Fc) complexes. These compounds exhibit a reversible ferrocenyl-centred solid-state oxidation processes involving anion insertion in contact with aqueous, MeOH and MeCN electrolytes. Voltammetric data can be used for a direct measurement of the free energy of ion transfer using midpeak potentials in solutions of suitable salts in the solvents separately or in mixtures of the s…
Physicochemical Characterization of Isomorphously Substituted FeZSM-5 during Activation
2002
Physicochemical characteristics of isomorphously substituted FeZSM-5 both after preparation and after activation have been determined by gas (Ar and N2) physisorption, 27Al and 29Si magic-angle spinning–nuclear magnetic resonance, NH3 temperature-programmed desorption, transmission electron microscopy, H2 temperature-programmed reduction (TPR), 57Fe Mossbauer spectroscopy, and voltammetric response techniques. The activation of as-synthesized FeZSM-5 comprises calcination at 823 K and a subsequent steam treatment (300 mbar of H2O in N2) at 873 K. Calcination leads to complete removal of the template. During this process a significant fraction of iron is dislodged to extraframework positions…
Bis(crown ethers) derived from biphenyl: extraction and electrochemical properties
2004
Abstract Ligands derived from 4,4′-dinitrobiphenyl containing azacrown cavities in the 2,2′ position have been used in extraction and transport experiments. Control experiments with a system containing only one complexing cavity have demonstrated that the capability of forming a sandwich-type complex in the aforementioned ligand not only increases extraction but also the transport across a liquid membrane. Extraction studies have also shown that the complex present in the membrane has a 1:1 stoichiometry with regard to both ligands. Electrochemical studies have also been carried out. The ligand containing two complexing cavities is capable of giving rise to a 2:1 complex under electrochemic…
Electrochemical characterization of iron sites in ex-framework FeZSM-5
2002
Abstract The electrochemical response of FeZSM-5 prepared by an ex-framework method has been studied using Paraloid B72 polymer film electrodes immersed in aqueous media using H2SO4, HCl, Na2EDTA and NaCl electrolytes. The ex-framework method comprises the hydrothermal synthesis of isomorphously substituted FeZSM-5, followed by calcination at 823 K and subsequent steam treatment (300 mbar H2O in N2) at 873 K. During this process iron is extracted to extra-framework positions. Also partial dealumination of the zeolite framework takes place. Characteristic voltammetric responses in the +1.0 to −0.6 V versus SCE potential range have been recorded and were used to characterize the iron species …
CCDC 1559249: Experimental Crystal Structure Determination
2017
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CCDC 1559236: Experimental Crystal Structure Determination
2017
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CCDC 937899: Experimental Crystal Structure Determination
2013
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CCDC 937897: Experimental Crystal Structure Determination
2013
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CCDC 937898: Experimental Crystal Structure Determination
2013
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