The photoelectrochemistry of platinum phthalocyanine films in aqueous media

Platinum phthalocyanine (PtPc) films applied to glassy carbon (GC) and platinum surfaces have been shown to exhibit complex photoelectrochemistry in aqueous media, acting as an n-type semi-conducting material. Using chopped polychromatic radiation and a lock-in amplifier to detect the modulated photocurrent, photo-responses were measured for PtPc films on GC in a variety of background electrolytes. In all instances the photo-responses were anodic over the voltage ranges used. Two peaks were seen in each sweep direction for the experiments performed in sulfuric acid and sodium hydroxide solutions. The origin of the photocurrent has been ascribed to the photo-oxidation of water in the electrolyte by positive holes produced under illumination, which accumulate at the PtPc/electrolyte interface. Photocurrent transients were also recorded and indicated some recombination of excitons within the system.     

Electrochemical impedance spectroscopy of diluted solutions of Bisphenol A

The electrochemical oxidation of bisphenol A was carried out using platinum, glassy carbon, titanium dioxide and polypyrrole modified working electrodes. Acetonitrile and water were evaluated as solvents; however, passivation could not be avoided due to the formation of insoluble oxidation products that adhere to the surface. The use of ultrasound did not show any improvement either. Finally, by using electrochemical impedance spectroscopy measurements at the open circuit potential it was possible to obtain a steady response of one of the components of the equivalent circuit proposed. This response is only dependent on the concentration of bisphenol A. At the same time it was demonstrated that the adsorption is a fundamental process that occurs more easily in water than in acetonitrile, this fact is reflected in the impedance spectra.     

A spectrophotometric study of the charge transfer complexes of [60]fullerene with different tert-butylcalix[4]crowns

Formation of the charge-transfer complexes between various calix[4]crowns (1-4) and [60]fullerene were studied in toluene solution using UV-vis spectrophotometry. The stability constants and the thermodynamic data of the resulting 1:1 complexes were determined and were found to decrease with increasing the size of the crown moiety of the calixcrown. Except the complex of 3, all the complexes were found to be enthalpy stabilized but disfavored in terms of entropy.     

Voltammetry and electrochemical impedance spectroscopy of gold electrodes modified with CdTe quantum dots and their conjugates with nickel tetraamino phthalocyanine

This work reports on the synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) caped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (NiTAPc) complex. The conjugates are characterized using cyclic (CV) and differential pulse (DPV) voltammetries, electrochemical impedance spectroscopy, X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, atomic force microscopy and time correlated single photon counting. CV and DPV show that NiTAPc stabilizes the CdTe QDs against oxidation to metallic products.     

Adsorption of concanavalin A and lentil lectin on platinum electrodes followed by electrochemical impedance spectroscopy: effect of protein state

Adsorption of concanavalin A and lentil lectin on platinum electrode was investigated through electrochemical impedance spectroscopy and cyclic voltammetry. By using ferro/ferricyanide system to probe the electrochemical interface it was possible to model the EIS data with a simple equivalent circuit. The blocking effect for electron transfer reactions observed with these proteins, indicated that they readily adsorb on platinum surface and that the degree of adsorption is related to the state of the proteins. When the proteins are in the presence of divalent cations (Ca²⁺ and Mn²⁺) they adsorb less strongly than in their absence. There is also evidence that at least convanavalin A retains its biological activity in the adsorbed state.     

Synthesis and characterization of fluorene end‐labeled polystyrene with atom transfer radical polymerization

Fluorene end‐labeled polystyrene was prepared by atom transfer radical polymerization with 9‐bromofluorene as the initiator. Reactions were carried out in bulk or tetrahydrofuran solutions at temperatures of 80 °C or above. Analysis by gel permeation chromatography indicated that the polymers formed had low polydispersities with molecular weights consistently 2–5 times higher than calculated based on monomer‐to‐initiator ratios. Coupling of two fluorenyl radicals, formed by activation of the 9‐bromofluorene, was found to compete with initiation, leading to the higher‐than‐expected molecular weight values while giving rise to a fluorene dimer. UV–vis spectrometry indicated near‐quantitative fluorene labeling of the polystyrene. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2657–2665, 2005     

Electrochemical impedance spectroscopy detection of lysozyme based on electrodeposited gold nanoparticles

A simple, highly sensitive, and label-free electrochemical impedance spectroscopy (EIS) aptasensor based on an anti-lysozyme-aptamer as a molecular recognition element, was developed for the detection of lysozyme. Improvement in sensitivity was achieved by utilizing gold nanoparticles (AuNPs), which were electrodeposited onto the surface of a gold electrode, as a platform for immobilization of the aptamer. To quantify the amount of lysozyme, changes in the interfacial electron transfer resistance (R_et) of the aptasensor were monitored using the redox couple of an [Fe(CN)₆]^3−/4− probe. The R_et increased with lysozyme concentration. The plot of R_et against the logarithm of lysozyme concentration is linear over the range from 0.1 pM to 500 pM with a detection limit of 0.01 pM. The aptasensor also showed good selectivity for lysozyme without being affected by the presence of other proteins.     

Electrochemical impedance spectroscopy of poly{pyrrole-trans-[(RuCl2(pmp)4]} copolymer films deposited on platinum electrodes

The present study focuses on the electronic and electrochemical features of a copolymer electrochemically grown from pyrrole and trans-[RuCl₂(pmp)₄] monomers, where pmp = 3-(pyrrol-1-ylmethyl)pyridine. The results from electrochemical impedance spectroscopy analyses revealed the redox behavior of the poly{pyrrole-trans-[RuCl₂(pmp)₄]} compound as well as the non-homogeneous nature of the extremely thin polymeric layers. An equivalent circuit is proposed for an optimized film produced under the scope of the work. Received: 4 May 1998 / Accepted: 24 August 1998     

The Microwave-assisted syntheses and a conductivity study of a platinum phthalocyanine and its derivatives

The parent platinum phthalocyanine (PtPc) and its derivatives with tetranitro (PtTNPc) and tetramine (PtTAPc) on the peripheral benzene were synthesized in the pure state for the first time by microwave irradiation. These complexes were characterized using physico-chemical methods like elemental, electronic absorption, IR spectral, magnetic susceptibility, thermogravimetry and X-ray powder diffraction studies. Kinetic and thermodynamic parameters associated with the thermal decomposition were calculated using the thermogravimetric analytical data. Electrical conductivity studies were carried out using the two-probe technique in the temperature range 298–473 K for each complex to study the effect of the donor and acceptor substituents on the platinum phthalocyanine macrocycle. The electrical conductivities observed at room temperature are in the order PtTAPc > PtTNPc > PtPc. The improvement in the intrinsic electrical conductivity of PtTAPc is due to the electron donating amine substituents which are expected to facilitate greater intermolecular contact and increase interactions, providing a greater pathway for charge carriers.     

Electrochemical impedance analysis of nanoporous TiO_2 electrode at low bias potential

<正>TiO_2 colloid was prepared by the sol-gel method and was bladed on transparent conduction glass to made nanoporous electrode. The impedance performance of TiO_2 electrode was studied at various bias potential.A simplified equivalent circuit was proposed to investigate the charge transport impedance of TiO_2 film and good fitting results were obtained.     

Electrochemical impedance spectroscopic studies of copper dissolution in arginine–hydrogen peroxide solutions

Anodic dissolution of copper in arginine and hydrogen peroxide-based medium suitable for chemical mechanical planarization slurry formulation was investigated using electrochemical impedance spectroscopy. Potentiodynamic polarization and impedance data were acquired for copper dissolving in hydrogen peroxide and arginine solution. Reaction mechanism analysis (RMA) was employed to determine the mechanistic pathway of copper dissolution. RMA analysis indicates that a stable passivating film does not form on the copper surface, and the direct dissolution of copper was also ruled out. A two-step mechanism involving cupric oxide as an intermediate species is proposed. The data were also fit to an electrical equivalent circuit to obtain insight into the variation of the parameters with the overpotential. The modeled data for the two-step mechanism captures the essential features of the impedance spectra at various overpotentials.     

Atom transfer radical polymerization of hexyl acrylate and preparation of its “all‐acrylate” block copolymers

This investigation reports the polymerization of hexyl acrylate (HA) using atom transfer radical polymerization technique and subsequently the preparation of its di‐ and triblock copolymers with methyl methacrylate. Atom transfer radical polymerization of HA was investigated using different initiators and CuBr or CuCl as catalyst in combination with varying ligands, e.g., 2,2′‐bipyridine and N,N,N′,N″,N″‐pentamethyl diethylenetriamine. Reaction parameters were adjusted to successfully polymerize HA with well‐defined molecular weights and narrow polydispersity indices. The polymerization was better controlled by the addition of polar solvents, which created a homogeneous catalytic system. UV–vis analysis showed that the polar solvent, acetone coordinated with copper (I), changes the nature of the copper catalyst, thereby influencing the dynamic equilibrium of activation–deactivation cycle. This resulted in improved control over polymerization as well as in lowering the polydispersity indices, but at the cost of polymerization rate compared with the bulk process. The presence of ? Br end group in the polymer chains was confirmed by ¹H NMR as well as MALDI‐TOF mass analysis. In addition, poly(hexyl acrylate) was used as macroinitiator to prepare various “all‐acrylate” block (diblock, triblock) copolymers that were characterized by GPC and ¹H NMR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3499–3511, 2008     

Electrochemical impedance spectroscopy study of cuprous oxide films formed on copper: effect of pH and sulfate and carbonate ions

The semiconducting properties of anodic passive films formed potentiostatically on polycrystalline copper in aqueous borax solutions were studied using electrochemical impedance spectroscopy, photocurrent spectroscopy and ellipsometric measurements. The semiconducting nature of the cuprous passive layer was analysed as a function of pH (9.2>pH>7.4), electrode potential and with the addition of 3.5 mM Na₂CO₃ and 8 mM Na₂SO₄. The different growth conditions change the compactness and the defect or excess of cations accumulated in the compact inner cuprous layer, leading to different semiconducting properties. Electronic Publication     

Impedance of faradeic process with partial charge transfer

The electrochemical impedance of charge-transfer reaction involving the stages of adsorption and desorption of intermediate partially charged substance is analyzed theoretically in the frequency-potential plane in order to study the possibility for measuring the partial charge transfer. The simplest case of adsorption two-electron transfer, namely, the Langmuir adsorption with liner dependence of reaction rate on the coverage, is considered. It is assumed that the partial charge transfer is independent of the electrode potential.     

交流阻抗法在细胞分析应用中的研究进展

交流阻抗法作为一种新型的无标记、全程动态、实时分析方法已在细胞研究中得到了广泛应用。本文综述了基于交流阻抗法进行细胞分析的研究新进展,重点对非法拉第阻抗谱法和法拉第阻抗谱法用于细胞分析的原理及应用进行了总结,主要包括交流阻抗法在细胞形态、细胞生长、细胞增殖、细胞凋亡以及作用于细胞的药效和毒性研究中的应用,并对其发展趋势进行了展望。     

Anthracene‐ and thiophene‐containing MEH‐PPE‐PPVs: Synthesis and study of the effect of the aromatic ring position on the photophysical and electrochemical properties

This contribution reports on the synthesis and characterization of thiophene‐ ( P1 , P2 , and P3 ) and anthracene‐ ( P4 and P5) containing PPE‐PPV copolymers. The thermostable, soluble and film‐forming polymers were fully characterized by NMR, IR and ELEM . ANAL .; they exhibit high molar masses with polydispersity indices below 2.5. The position of the thiophene in the polymeric backbone has insignificant influence on the spectroscopic properties of the polymers. In contrast, the anthracene‐containing polymers reveal position dependent optical properties. A constant bathochromic shift of 50 nm was observed going from P4 , where anthracene is surrounded by two double bonds, to P5 , where anthracene is at the bridge between a triple bond and a double bond, as well as from P5 to P6 where anthracene is surrounded by two triple bonds. This correlates to the decrease of the observed anthracene band around 255 nm going from P4 through P5 to P6 , amounting to the degree of contribution of the anthracene unit to the main chain conjugation. The phenomenon known as CN‐PPV effect was observed in the case of P4 [Φ_f (solution) = 3%, Φ_f (solid) = 13%]. Electrochemical studies carried out under absolute inert conditions revealed lower electrochemical band gap energies, E , than E . © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2243–2261, 2009     

Synthesis and unexpected electrochemical behavior of the triphenylamine‐based aramids with ortho‐ and para‐trimethyl‐protective substituents

Two series of new organosoluble polyamides with methyl‐substituted triphenylamine (MeTPA) units showing anodically electrochromic characteristic were prepared from the phosphorylation polyamidation reaction of two diamine monomers, 4,4′‐diamino‐2″,4″,6″‐trimethyltriphenylamine (Me₃TPA‐diamine; 2 ) and 4,4′‐diamino‐4″‐methyltriphenylamine (MeTPA‐diamine; 2 ′), with various dicarboxylic acids, respectively. These polymers were readily soluble in many polar solvents and showed useful levels of thermal stability associated with relatively high glass‐transition temperatures (T_g) (314–329 °C) and high char yields (higher than 62% at 800 °C in nitrogen). In addition, the polymer films showed reversible electrochemical oxidation, high coloration efficiency (CE), low switching time, and anodic green electrochromic behavior. The unexpected electrochemical behavior of higher oxidation potential and lower electrochemical stability of Me₃TPA‐polyamides I than MeTPA corresponding polymers could be attributed to the higher steric hindrance of ortho‐substituents in Me₃TPA moieties, thus made the resonance stabilization of cation radical much more difficult for the Me₃‐substituted phenyl ring. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Direct electrochemical determination of carbaryl using a multi-walled carbon nanotube/cobalt phthalocyanine modified electrode

The electrochemical detection of carbaryl at low potentials, in order to avoid matrix interferences, is an important challenge. This study describes the development, electrochemical characterization and utilization of a glassy carbon (GC) electrode modified with multi-wall carbon nanotubes (MWCNT) plus cobalt phthalocyanine (CoPc) for the quantitative determination of carbaryl in natural waters. The surface morphology was examined by scanning electron microscopy, enhanced sensitivity was observed with respect to bare glassy carbon and electrocatalytic effects reduced the oxidation potential to +0.80 V vs. SCE in acetate buffer solution at pH 4.0. Electrochemical impedance spectroscopy was used to estimate the rate constant of the oxidation process and square-wave voltammetry to investigate the effect of electrolyte pH. Square-wave voltammetry in acetate buffer solution at pH 4.0, allowed the development of a method to determine carbaryl, without any previous step of extraction, clean-up, or derivatization, in the range of 0.33-6.61 μmol L⁻¹, with a detection limit of 5.46 ± 0.02 nmol L⁻¹ (1.09 ± 0.02 μg L⁻¹) in water. Natural water samples spiked with carbaryl and without any purification step were successfully analyzed by the standard addition method using the GC/MWCNT/CoPc film electrode.     

Density functional theory studies on the electronic and vibrational spectra of octaethylporphyrin diacid

The ground-state structure and electronic and vibrational spectra of octaethylporphyrin diacid (H4OEP2+) have been studied with the density functional theory. The geometrical parameters computed with B3LYP, PBE1PBE and mPW1PW91 functionals and 6-31G* basis sets are well consistent with the experimental values. Electronic absorption spectrum of H4OEP2+ has been studied with the time-dependent DFT method, and the calculated excitation energies and oscillator strengths are compared with the experimental results. The Raman and IR spectra of H4OEP2+ and the Raman spectrum of its N-deuterated analogue (D4OEP2+) were measured. The observed Raman and IR bands have been assigned based on the frequency calculations at the B3LYP/6-31G* level of theory.     

Synthesis and characterization of soluble conjugated polymers having pyrene moiety in the main chain

Three new alternating conjugated polymers consisting of pyrene and 3‐dodecylthiophene ( PPyMT ), 4,4′‐didodecyl‐2,2′‐bithiophene ( PPyBT ), or 9,9‐didodecylfluorene ( PPyFlu ) moieties have been prepared using Suzuki coupling reaction or Sugimoto approaches. The polymers were readily soluble in common organic solvents and exhibited good thermal stability in nitrogen and air atmospheres. The structures and optical properties of the polymers were characterized by NMR, FTIR, XRD, UV–vis, and fluorescence spectroscopy. PPyMT and PPYBT showed blue‐light emission in solution, whereas PPyFlu performed blue‐light emitting in film state. The polymers exhibited an intermolecular aggregation and structural ordering due to pyrene–pyrene π–π stacking interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010