Heterogeneous and homogeneous electrochemiluminoimmunoassays of hTSH at disposable oxide-covered aluminum electrodes

Heterogeneous and homogeneous immunoassays of human thyroid stimulating hormone (hTSH) were developed on immunometric basis using aromatic Tb(III) chelates as electrochemiluminescent labels and varied types of disposable oxide-covered aluminum electrodes as the solid phase of the immunoassays. The long luminescence lifetime of the present labels allows the use of time-resolved electrochemiluminescence detection and provide the low detection limits of these labels and, thus, sensitive immunoassays. The primary antibody of immunometric immunoassays was coated upon aluminum oxide surface by physical absorption. In homogeneous immunoassays using 66 μl cell and 15 min incubation time, a linear calibration range of 0.25-324 μU/ml was obtained by applying only a single cathodic excitation pulse in the detection step of the assay.     

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10⁻⁷ M and a sensitivity of 0.24 A M⁻¹. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia.     

Applications of Macrocyclic Polyethers in Analytical Sensors and Ion Separation

Artificial macrocyclic polyethers were synthesized and applied as neutral carriers for ion-selective PVC membrane electrodes, ion-chromatographic packing materials, extractants and adsorbents for ion separation, coating materials for piezoeletrical membrane sensors for organic species, and ion-transport carriers through liquid membranes. Ion-selective electrodes such as those for K⁺ Na⁺, UO₂²⁺, Cs⁺, Pb²⁺, Fe³⁺, Hg²⁺ and Ag⁺ ions based on crown ether-phosphotungstic acid (PW) precipitates and dithio crown ethers respectively were prepared and showed good sensitivity and selectivity. Crown ether-PW precipitates were applied as adsorbents of rare-earth ions and some common heavy-metal ions. Some rare-earth ions were easily extracted with crown ethers, especially 15-crown-5. Poly(stytene/divinyl benzene) cryptand-22 resin was synthesized and applied as a bifunctional stationary phase of ion chromatography to separate bom cations and anions, even some organic carboxylate geometric isomers. Crown ethers such as mono-benzo-15-crown-5 was successfully applied as a coating material on piezoelectric quartz membrane sensors for some organic species. The oscillation frequency of the crown-ether quartz-membrane sensor was sensitive to organic vapours such as amines and alcohols. Upon adsorption of organic species on the crown-ether quartz membrane, the oscillation frequency of the sensor decreased obviously. Special crown ether such as dibenzo-16-crown-5-oxyacetic acid, decyl-cryptand-22 and 1, 4-dihydro-pyridine-18-crown-5 were synthesized and successfully applied as ion-transport carriers (ionophores) for transport of Na⁺ K⁺ and Mg²⁺ ions through liquid membranes.     

Electrochemical Detection of Protons Produced in an Electrode Reaction Using Interdigitated Microarray Electrodes

This work describes the use of interdigitated array electrodes (IDAE) for proton detection. Methanol electrooxidation in sulfuric acid solution was exemplified. Reduction currents originating in the reaction product generated by methanol electrooxidation on a Pt generator electrode were observed at the Pt collector electrode, the potential of which was fixed in the hydrogen evolution region. In order to reduce the background current of hydrogen evolution, an Hg‐plated Pt collector electrode was fabricated. Compared to the Pt collector electrode, the reduction current observed at the Hg collector electrode was extremely small. The product detected was found to be a proton from the current responses observed at Pt and Hg collector electrodes.     

Electrocatalytic Oxidation of Amines on a Mediator‐Modified Electrode by Electrochemical Copolymerization of Nitroxyl Radical Precursor Containing Pyrrole Side Chain and Bithiophene

This paper describes the electrocatalytic oxidation of amines on TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl)‐modified electrodes prepared by electrochemical copolymerization of TEMPO precursor containing pyrrole side chain and 2,2′‐bithiophene. The modified electrode exhibits electrocatalytic activity for the oxidation of primary and secondary amines. Cyclic voltammetric studies showed that the peak current of the cyclic voltammogram increased linearly with increasing concentration of amine in the sample solution.     

Tetralactam-modified gold electrodes for amperometric detection of acrylic acid

The presence of toxic acrylamide in a wide range of food products such as potato crisps, French fries or bread has been confirmed by Swedish scientists from Stockholm University. The neurotoxicity and possible carcinogenicity of this compound and its metabolites compel us to control them by quantitative and qualitative assays. Exposing acrylamide to pH extremes results in its hydrolysis to acrylic acid or its salt. In this work, we present the use of gold electrodes coated with self-assembled monolayers (SAMs) containing tetralactam molecules and its precursor as active elements for voltammetric detection of acrylic acid in water solution. The host molecules have been immobilised on the electrode surface by covalent Au–S bond or by embedment method into the thiol layer via hydrophobic and van der Waals interactions. Interactions with analytes were confirmed by Osteryoung square-wave voltammetry.     

Photoswitchable Composite Polymer Electrolytes Using Spiropyran-Immobilized Nanoporous Templates

Composite polymer electrolytes (CPEs) with smart, stimuli-responsive characteristics have gained considerable attention owing to their noninvasive manipulation and applications in future technologies. To address this potential, in this work, we demonstrate photoresponsive composite polymer electrolytes, consisting of gel polymer electrolyte (GPE) and spiropyran-immobilized nanoporous anodic aluminum oxide (SP-AAO) templates. Under UV irradiation, the close SP form isomerizes to the open merocyanine (MC) form, creating extremely polarized AAO surfaces; whereas, under visible light irradiation, the MC form reverts to the SP form, creating neutral surface conditions. The electrostatic interactions between ions and AAO surfaces are investigated by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Moreover, the behavior of ionic conductivity of the GPE@SP-AAO is found to be consistent with the kinetics of isomerization tracked by UV-Vis spectroscopy. This work provides a promising platform for developing next-generation photoelectronic smart devices.     

Host–Guest Chemistry between Perylene Diimide (PDI) Derivatives and 18‐Crown‐6: Enhancement in Luminescence Quantum Yield and Electrical Conductivity

Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation‐induced quenching of emission from the system. Host–guest chemistry is one of the best‐known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18‐crown‐6 (18‐C‐6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18‐C‐6 formed complexes with amino‐substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI ? 18‐C‐6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60–70 %) from the PDI derivatives. More importantly, the host–guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self‐assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10^?5 S cm^?1.     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012