Phosphonic acid derivatized polythiophene: A building block for metal phosphonate and polyelectrolyte multilayers

A water-soluble polythiophene with pendant phosphonic acid groups, poly(3-(3'-thienyloxy)propane-phosphonate) (P3TOPP), has been synthesized. Matrix-assisted laser desorption ionization (MALDI) measurements showed that P3TOPP is an oligomer with an average chain length of 10 monomer units. In aqueous solutions it could be electrochemically oxidized and displayed self-acid doping at pH below 13. P3TOPP was used to prepare polyelectrolyte multilayers with poly(diallyldimethylammonium chloride) (PDADMA) and metal phosphonate multilayers with Zr4+ ions by the sequential layer-by-layer technique. The films were characterized by electrochemistry, atomic force microscopy (AFM), UV-vis, IR, and X-ray photoelectron (XPS) spectroscopy. A regular layer-by-layer growth was observed with both types of multilayers. The nature of the films was probed with XPS, which showed that the observed binding energies were characteristic for metal phosphonates and polyelectrolyte multilayers in Zr/P3TOPP and P3T0PP/PDADMA films, respectively. In the former, the Zr:P ratio showed deviation from the theoretical stoichiometry, and the reasons for the nonstoichiometry are discussed. In the latter, the N:P ratio was consistent with the partial deprotonation of the phosphonate groups. The multilayers exhibited both electrochromism and pH-induced halochromism

New insights on the interaction between thiophene derivatives and Au surfaces: the case of 3,4-ethylenedioxythiophene and the relevant polymer.

The nature of the interface between electrogenerated poly(3,4-ethylenedioxythiophene) and the Au substrate is studied in detail. In particular, the adsorption of the relevant monomer, namely, 3,4-ethylenedioxythiophene, is investigated and compared with that of other thiophene derivatives. Different deposition procedures have been adopted: very thin films of the thiophene derivatives have been obtained through chemisorption processes from vapor and liquid phases, on Au polycrystalline substrates, Au nano particles possessing different size, and a Au(111) single crystal. Different techniques, operating both in situ and ex situ, have been employed for the characterization of these deposits, that is, X-ray photoemission and surface enhanced Raman spectroscopy. The results show that the poly(3,4-ethylenedioxythiophene)/metal interface is far from being simply constituted by unreacted molecules in contact with the substrate; rather, the formation of oligothiophene species and sulfur atoms at the interface has been ascertained

Theoretical study on the electronic, structural, properties and reactivity of a series of mono-, di-, tri- and tetrachlorothiophenes as well as corresponding radical cation forms as monomers for conducting polymers

In this paper, electrical and structural properties of mono-, di-, tri- and tetrachlorothiophenes and their radical cations have been studied using the density functional theory and B3LYP method with 6-311++G** basis set. The effects of the number and position of the substituent of chlorine atoms on the properties of the thiophene ring for all chlorothiophenes and their radical cations have been studied. Vibrational frequencies, nuclear chemical shielding constants, spin-density distribution, size and direction of dipole moment vector, ionization potential, electric polarizabilities and NICS values of these compounds have been calculated as well. The analysis of these data showed that double bonds in 3-chlorothiophene are more delocalized and it is the best possible candidate monomer among all chlorothiophenes for the synthesis of corresponding conducting polymers with modified characteristics

A Facile Electrochemical Preparation of Reduced Graphene Oxide@Polydopamine Composite: A Novel Electrochemical Sensing Platform for Amperometric Detection of Chlorpromazine

© 2016 The Author(s). We report a novel and sensitive amperometric sensor for chlorpromazine (CPZ) based on reduced graphene oxide (RGO) and polydopamine (PDA) composite modified glassy carbon electrode. The RGO@PDA composite was prepared by electrochemical reduction of graphene oxide (GO) with PDA. The RGO@PDA composite modified electrode shows an excellent electro-oxidation behavior to CPZ when compared with other modified electrodes such as GO, RGO and GO@PDA. Amperometric i-t method was used for the determination of CPZ. Amperometry result shows that the RGO@PDA composite detects CPZ in a linear range from 0.03 to 967.6 μM. The sensor exhibits a low detection limit of 0.0018 μM with the analytical sensitivity of 3.63 ± 0.3 μAμM-1 cm-2. The RGO@PDA composite shows its high selectivity towards CPZ in the presence of potentially interfering drugs such as metronidazole, phenobarbital, chlorpheniramine maleate, pyridoxine and riboflavin. In addition, the fabricated RGO@PDA modified electrode showed an appropriate recovery towards CPZ in the pharmaceutical tablets

Layer-by-layer deposition of a polythiophene/Au nanoparticles multilayer with effective electrochemical properties

Multilayers consisting of a water soluble polythiophene derivative and Au nanoparticles have been deposited onto different electrode substrates by means of layer-by-layer deposition technique. The assembly of the films has been performed by taking advantage of the electrostatic interactions between the positively charged imidazolic moiety of the polythiophene chain and the negative charges of citrate ions surrounding Au nanoparticles, as well of the affinity of S to Au. The nanoparticles result stably grafted to the organic matrix. The resulting modified electrodes have been characterised through electrochemical, spectroelectrochemical and microscopic techniques. The results evidenced that a high number of individual nanoparticles is present inside the multilayer. The presence of nanoparticles is of chief importance for most effective charge percolation through the multilayer, as suggested by the responses to electroactive probe species in solution. The electrocatalytic performances of the modified electrodes have been tested with respect to the oxidation of ascorbic acid. © Springer-Verlag 2011

New Insights on the Interaction between Thiophene Derivatives and Au Surfaces. The Case of 3,4-Ethylenedioxythiophene and the Relevant Polymer

The nature of the interface between electrogen-erated poly(3,4-ethylenedioxythiophene) and the Au substrateis studied in detail. In particular, the adsorption of the relevantmonomer, namely, 3,4-ethylenedioxythiophene, is investigatedand compared with that of other thiophene derivatives. Di!er-ent deposition procedures have been adopted: very thin "lms ofthe thiophene derivatives have been obtained through chemi-sorption processes from vapor and liquid phases, on Au poly-crystalline substrates, Au nanoparticles possessing di!erent size,and a Au(111) single crystal. Di!erent techniques, operatingboth in situ and ex situ, have been employed for the characterization of these deposits, that is, X-ray photoemission and surface- enhanced Raman spectroscopy. The results show that the poly(3,4-ethylenedioxythiophene)/metal interface is far from being simply constituted by unreacted molecules in contact with the substrate; rather, the formation of oligothiophene species and sulfur atoms at the interface has been ascertained

Graphene-modified electrode. Determination of hydrogen peroxide at high concentrations.

A gold electrode partially coated by graphene multilayer is developed and tested with respect to high concentrations of hydrogen peroxide. The effective use of conventional electrode materials for the determination of such an analyte by anodic oxidation or cathodic reduction is prevented by the occurrence of adsorptions fouling the electrode surface. This prevents reliable and repeatable voltammetric curves for being recorded and serious problems arise in quantitative analysis via amperometry. The gold–graphene electrode is shown to be effective in quantitative evaluation, by cathodic reduction, of hydrogen peroxide at concentration levels that are of interest in an industrial. Acid, neutral, and basic pH values have been tested through correct adjustment of a Britton Robinson buffer. The experiment s have been performed both by cyclic voltammetry and with amperometry at constant potential in unstirred solution. The latter technique has been employed in drawing a calibration linear plot. In particular, the performances of the developed electrode system have been compared with those of both pure gold and pure graphene electrode materials. The bi-component electrode was more sensitive; co-catalytic action by the combination of the two components is hypothesised. The system is stable over many potential cycles, as checked by surface-enhanced Raman spectra recorded over time