Herein, a reliable procedure for the preparation of graphene-boron nitride superlattices, either as films or powders, consisting of the pyrolysis at 900 °C of polystyrene embedded pre-formed boron nitride single sheets is reported. The procedure can serve to prepare large area films (cm × 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.
View Article and Find Full Text PDFManganese 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 and in vivo.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFA 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.
View Article and Find Full Text PDFMn(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.
View Article and Find Full Text PDFThis work proposes a multi-method approach that combines advanced microscopy (SEM/EDX, AFM) and spectroscopy (UV-vis and FTIR) techniques. This approach not only characterises the behaviour of the additives of two commercial poly(vinyl acetate) (PVAc) and acrylic emulsion paints but also simultaneously characterises the changes in chemical composition and morphology observed in the paint films as a result of ageing due to the paints being exposed to an intense source of simulated daylight. In parallel, a series of mechanical tests were performed that correlate the chemical changes in composition and the changes observed in the films' mechanical properties.
View Article and Find Full Text PDFAn 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.
View Article and Find Full Text PDFElectrochemical 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), mescaline (MES), homoveratrylamine (HOM), phenethylamine (PEA) and dopamine (DA) in aqueous media.
View Article and Find Full Text PDFThe present work describes an analytical study performed on several pieces of Iranian Ilkhanate glazed ceramics from the Takht-e Soleyman palace (Iran, thirteenth century). Several advanced instrumental techniques, including pyrolysis-gas chromatography-mass spectrometry, Fourier transform IR spectroscopy, light microscopy, X-ray diffraction, scanning electron microscopy-X-ray microanalysis and voltammetry of microparticles, were used. The results obtained led to identification of the chemical and mineralogical composition of the pastes and glazes and the colouring agents.
View Article and Find Full Text PDFTreatment 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.
View Article and Find Full Text PDFThe synthesis and steady-state fluorescence studies on the interaction with AMPH, METH, MDMA, and DA of two diazatetraester pyrazole crowns containing appended N-(9H-fluoren-9-yl) and N-(naphth-2-ylmethyl) functions, in a water/ethanol 70:30 mixture at physiological pH, are described.
View Article and Find Full Text PDFAn 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.
View Article and Find Full Text PDFA novel method, using Tafel plots, for quantifying electroactive species in solid materials when their voltammetric signals are strongly overlapped is described. This is applied to the analysis of submicrosamples from the highly damaged frescoes painted by Palomino (1707) in the ceiling vault of the Sant Joan del Mercat church in Valencia, Spain. These paintings, which were fired in 1936, contained cobalt smalt plus azurite mixtures, this last being altered to tenorite (CuO).
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFSynthetic tetragonal and monoclinic vanadium-doped zirconias (t- and m-VxZr1-xO2, 0.005 < x < 0.150) exert an effective catalytic effect toward the electrochemical oxidation of glucose in aqueous alkaline media.
View Article and Find Full Text PDFThe use of the voltammetry of microparticles at paraffin-impregnated graphite electrodes allows for the characterization of different types of Maya Blue (MB) used in wall paintings from different archaeological sites of Campeche and YucatAn (Mexico). Using voltammetric signals for electron-transfer processes involving palygorskite-associated indigo and quinone functionalities generated by scratching the graphite surface, voltammograms provide information on the composition and texture of MB samples. Application of hierarchical cluster analysis and other chemometric methods allows us to characterize samples from different archaeological sites and to distinguish between samples proceeding from different chronological periods.
View Article and Find Full Text PDFThe sodium salt of the diethyl 1H-pyrazole-3,5-dicarboxylate (2) of amphiphilic character is able to interact with (+)-amphetamine, (+)-methamphetamine, and dopamine, yielding stable complexes. Crystal structure of 2 with (+)-amphetamine leads to a very nice double helical supramolecular structure.
View Article and Find Full Text PDFThe 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..
View Article and Find Full Text PDFThe 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 reactions.
View Article and Find Full Text PDFCombining a novel technique, the voltammetry of microparticles, with spectrometric, nuclear magnetic resonance, electron microscopy, and atomic force microscopy data, Maya Blue is detected in wall paintings of the Substructures A-3, A-5, and A-6, dated in the Early Classical period (440-450 a.c.), and the Substructure II-C, dated in the Late Preclassical period (150 b.
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