Electrochemical synthesis and electrochromic application of a novel polymer based on carbazole

The compound containing carbazole and thiophene, named as B1 was synthesized with 4-(9H-carbazol-9-yl) phenol and 3,4-dibromo thiophene. Additionally, the electrochemical polymer of B1 was synthesized and coated onto an ITO-glass surface via electrochemical oxidative polymerization. The electrochemical synthesis of the polymer was performed both in 0.05 M LiClO₄ supporting electrolyte in AN/BF₃EtE (1:1, v/v) and an AN/LiClO₄ solvent/electrolyte solution. The compounds were characterized by FT-IR and NMR techniques. The spectroelectrochemical and electrochromic properties of this polymer were also investigated for two electrolyte solution systems. The switching ability of this polymer was measured as the percent transmittance (%T) at its point of maximum contrast. According to the electrochromic measurements, the synthesized polymer had a blue color when it was oxidized, and also when it was reduced, it had a transparent color. Additionally, redox stability measurements indicates that the polymer had a high stability and it could be used to produce new polymeric electrochromic devices and also, it was a good candidate for electrochromic devices (ECDs) applications.     

Preliminary Contribution to the Quantification of HMF in Honey by Electrochemical Biosensor Chips

Several hydroximethylfurfural (HMF) microbiosensors, based on a microelectrode configuration built by photolithographic techniques, have been developed. Two different biosensors based on the aldehyde dehydrogenase (ALDH) enzyme coupling with NADH oxidase (NOD) or diaphorase (Diaph) are described. Experimental variables were optimized using experimental design methodology, by central composite designs, taking the intensity registered for a given HMF solution as response. Given the reproducibility (residual standard deviation (RSD), 7.20%), repeatability (RSD=3%) and limit of detection (LOD)=1.68×10^?4 mol dm^?3 (α=β=0.05 and a replicate) reached by the ALDH‐Diaph microbiosensor under the optimum conditions, the analysis of HMF in honey was successfully accomplished.     

Mask‐free Localized Grafting of Organic Polymers at the Micrometer or Submicrometer Scale on Composite Conductors or Semiconductor Substrates

This work presents a new one‐step process enabling the mask‐free localized functionalization by organic polymers of the conducting or semiconducting parts of composite surfaces at the micrometer and submicrometer scale. The functionalization is carried out via cathodic electrografting of suitable precursors of composite cathodes, which gives an insulating polymer film strongly grafted to selected parts of the composite electrodes and guarantees that the resolution is that of the pre‐existing pattern, even when the whole surface is dipped into the reaction medium. The presumed mechanism is based on a regioselective extraction of electrons from the composite surface according to its apparent local work function in solution.     

聚天青A膜修饰电极的电化学特性及其对亚硝酸根的电催化性能

在玻碳电极上以循环伏安法制备了聚天青A膜修饰电极(PAAE) ,天青A能够在玻碳电极上形成稳定的聚合膜 ;通过正交试验确定了电聚合天青A的最佳条件 ,研究了该修饰电极的电化学特性 ,并讨论了其对亚硝酸根的电催化还原作用 ;结果表明 ,亚硝酸根在PAAE上有很好的电流响应 ,催化峰电流与亚硝酸根浓度在1.0×10-5 ～4.0×10-3 mol/L之间呈良好的线性关系     

Effect of monomer molecular flow on electrode surface on the structure of poly(α-tetrathiophene) obtained by anodic polymerization

Different structures have been found for poly(α-tetrathiophene) [poly(α-4TF)] electrosynthesized on Pt by anodic oxidation of 1.0 mM monomer solutions in media such as 45:35:20 (v/v/v) acetonitrile/THF/DMF, 45:35:20 (v/v/v) acetonitrile/ethanol/DMF and 72:28 (v/v) acetonitrile/DMF containing 0.1 M LiClO₄; as well as 72:28 (v/v) acetonitrile/DMF with 0.1 M NaClO₃, under dynamic and static conditions at 25 °C. In all cases the polymer was generated by chronoamperometry at 1.000 V vs. Ag∣AgCl, corresponding to the first oxidation peak detected by cyclic voltammetry. Uniform, adherent, insoluble and black polymer films were obtained under these conditions. The resulting structures have been elucidated by combining the information of their IR spectrum, n_ox-value and doping level of the counterion. The degree of crosslinking of every polymer has been quantified and related to the molecular flow of monomer on the Pt electrode. A monomer concentration flow between 4 × 10⁻⁶ and 5 × 10⁻⁶ mmol cm⁻² s⁻¹ was determined as the limiting value below which the polymer grows with crosslinking. This value corresponds to the electropolymerization rate of α-4TF by Pt area unit at 25 °C.     

Electrochemical synthesis, characterization and some properties of a polymer derived from thioflavin S

Polymeric films derived from thioflavin S were electrosynthesized on mild steel and silver electrodes in sulfuric acid and lithium perchlorate-containing aqueous solutions. The introduction of thioflavin S in an acidic solution protected the surface of steel from corrosion. The electrochemical behavior of the steel coated with a layer of poly(thioflavin) was examined by electrochemical impedance spectroscopy. The films exhibited a capacitive behavior and were semi-conductive in nature. Infra red reflectance measurements of the polymer films at the steel surface showed that the polymer structure retained the aromatic structure of the benzene and thiazole rings with the distinction of a nitrogen quinone vibrational band. Surface morphology of the polymer film was examined with scanning electron microscopy. The films are yellow, compact and dense when electrochemically formed onto steel surfaces when compared to a blue rather porous when formed onto silver electrode. The mechanism of electropolymerization of thioflavin is given and found similar to that of aniline with the possibility of metal chelation with the sulfur and/or nitrogen in the thiazole ring.     

Preparation and characterization of molecularly imprinted electropolymerized carbon electrodes

Molecularly imprinted polymers (MIPs) selective for fluorescein, rhodamine or 2,4-dichlorophenoxyacetic acid (2,4-D) were electropolymerized onto graphite electrodes using an aqueous solution equimolar in resorsinol/ortho-phenylenediamine and in the presence of the template molecule. For the dyes, the MIP-coated electrodes showed higher affinity for their template molecule than for a non-template dye. The 2,4-D-MIP-coated electrode showed a concentration dependent response for 2,4-D as compared to the polymer-coated electrode prepared in the absence of template molecule.     

Immobilization of invertase and glucose oxidase in poly 2-methylbutyl-2-(3-thienyl) acetate/polypyrrole matrices

Immobilization of invertase and glucose oxidase in conducting polypyrrole and copolymers of poly 2-methylbutyl-2-(3-thienyl) acetate with pyrrole were achieved via electrochemical method. Sodium dodecyl sulphate was found to be the most suitable supporting electrolyte. Maximum reaction rate, Michaelis-Menten constant and optimum temperatures were determined for native and immobilized enzymes. Storage and operational stabilities of enzyme electrodes were also investigated.     

Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

Citrate selectivity of poly(neutral red) electropolymerized films

The synthesis and the spectroscopic and potentiometric characterization of electropolymerized films obtained from neutral red (NR) on Pt surface are described. FT Raman and NMR spectroscopy were used for evaluation of the resulting poly(NR) layers. Then potentiometry was applied to study the characteristics of the complexation of carboxylates with the poly(NR) films. A potentiometric poly(NR) sensor showing high selectivity for citrate anion was employed for its determination in soft drinks.