Search results for "redox"

Redox properties of titanocene-pyrrole derivative and its electropolymerization

2001

A new titanocene dichloride derivative in which one cyclopentadienyl ligand (Cp) is functionalized with a pyrrolyl ring, Tc3Py (Cl2TiCpC5H4(CH2)3NC4H4), has been synthesized and characterized with NMR. Its redox properties have been studied by CV in acetonitrile (AN), tetrahydrofurane (THF) and dichloromethane (DCM), in comparison with unsubstituted titanocene dichloride (Tc) and pyrrole. Ti(IV/III) transition observed within the negative potential range is a quasi-reversible reaction in THF and DCM (but without a complete recuperation of the initial reagent in the back scan) while the reoxidation peak in AN is strongly shifted in the positive direction. These results are interpreted within…

Electroactivation of Transition Metal Redox Couples for the Carbonylation of Alcohols to Dialkylcarbonates

1998

Electrochemical systems which promote the carbonylation of methanol to dimethylcarbonate, based on the anodic activation of transition metal redox couples, or the Br−/Br2 couple, are poorly active for the carbonylation of ethanol to diethylcarbonate at room temperature and atmospheric pressure. Positive results have been obtained by combined addiction of PdBr2 and Bu4NBr to the system. In this way yields up to 50% in diethylcarbonate were obtained, with very good conductivities in long range electrolyses.

Anion interaction with ferrocene-functionalised cyclic and open-chain polyaza and aza-oxa cycloalkanes

2016

A family of ferrocene-functionalised receptors of different topologies have been used as receptors for anions. The compounds have been designed to contain both amine nitrogen and ether oxygen atoms and comprises from monoaza to pentaaza derivatives both open-chain (L1, L2, L3) or cyclic (L4, L5) and having from one to five ferrocenyl groups. Solution studies directed to determine the protonation constants of L1, L2 and L3 have been carried out in water (0.1 mol dm3 KNO3, 25 °C) and those of L4 and L5 in 1,4-dioxane-water (70:30 v/v, 0.1 mol dm -3 KNO 3, 25 °C). The protonation behaviour of the receptors can be explained taking into account electrostatic considerations. Speciation studies in…

Electrochemical behaviour of inorganic redox substances dispersed into Nafion® films

1999

Abstract The voltammetric response of a Nafion ® film deposited on an indium tin oxide (ITO) electrode was studied. It was observed that the response is affected by the thickness of the Nafion ® layer. Also, the voltammograms show differences depending on the concentration and composition of the supporting electrolyte solution. The ITO–Nafion ® system can be stabilised by repetitive cyclic voltammetry, and then the inner hydrogen reduction is not detected by electrochemical impedance spectroscopy. Different substances were dispersed into the Nafion ® matrix in order to study their electrochemical response.

Structure and properties of zwitterionic polysoaps: functionalization by redox-switchable moieties

2007

Redoxactive monomeric and polymeric surfactants containing viologen and N-alkylated nicotinic acid moieties were synthesized. These systems are potentially able to trigger reversible changes of self-organization by creation or removal of a charge via a redox reaction. Hence, they are investigated with respect to solubility, aggregation behavior, and their electrochemical properties in water. — All monomers, but only the viologen polymers are water-soluble and drastically decrease the surface tension of water. Critical micelle concentrations are observed for the monomers only. — The chemical reversibility of the redox reactions of the compounds in water was investigated using cyclic voltamme…

Transient Hydrogels Mediated by Redox-Switchable Supramolecular Polymerization

2017

Spatial and temporal control in multi-stimuli-responsive materials are critical properties to advance and optimize functional soft matter in order to mimic key features of living systems. In this contribution, I will discuss our methodology in developing non-equilibrium states in supramolecular materials. We have expanded our concept of charge regulated s–sheet self-assembly of alternating hydrophilic and hydrophobic amino acids in order to introduce redox-switchable properties. An interplay of pH- and oxidation-stimuli, promoted by the production of reactive oxygen species (ROS) thus leads to transient supramolecular polymerizations of methionine containing amphiphiles, with tuneable lifet…

The redox chemistry of gold with high-valence doped calcium oxide.

2012

Atmospheric Oxidation Reactions of Methyl Salicylate as Green Leaf Volatiles by OH Radical: Theoretical Kinetics and Mechanism

2020

Redox properties of nitrophenylporphyrins and electrosynthesis of nitrophenyl-linked Zn porphyrin dimers or arrays

2014

Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH 2 Cl 2 containing 0.1 M TBAP. The investigated compounds are represented as ( NO 2 Ph )x Ph 4-x PorM , where Por represents the dianion of the porphyrin macrocycle, Ph is a phenyl group on meso-position of the macrocycle, NO 2 Ph is a meso-substituted nitrophenyl group, M = 2 H , Pd II or Zn II and x = 1 or 2. Each porphyrin undergoes an initial one electron reduction at E1/2 = -1.07 to -1.12 V where the added negative charge is almost totally localized on the meso-nitrophenyl group of the compound. This reversible reduction is then followed by one or more irreversible reductions of the nitrophenyl an…

Mechanism of redox transformation of titanocene dichloride centers immobilized inside a polypyrrole matrix—EQCM and XPS evidences

2005

Abstract We report electrochemical quartz crystal microbalance (EQCM) results for electrodeposition of titanocene derivatized polypyrrole p(Tc3Py) films and redox transformation of polypyrrole matrix and titanocene centers immobilized in the film. Films of p(Tc3Py), Tc3Py = Tc(CH 2 ) 3 NC 4 H 4 (Tc = Cl 2 TiCpCp′, Cp = C 5 H 5 , Cp′ = C 5 H 4 ) were obtained from acetonitrile solutions of monomer on a Pt disc or thin Au layer evaporated on 10 MHz quartz crystals. Polymerization efficiency, derived from the slope of the change of resonant frequency as a function of the deposition charge ranged from 54% to 75%. A gradual loss of redox activity of Tc centers during consecutive redox cycles of …