Surface behaviour and lipid interaction of Alzheimer beta-amyloid peptide 1-42: a membrane-disrupting peptide

Amyloid aggregates, found in patients that suffer from Alzheimer's disease, are composed of fibril-forming peptides in a β-sheet conformation. One of the most abundant components in amyloid aggregates is the β-amyloid peptide 1–42 (Aβ 1–42). Membrane alterations may proceed to cell death by either an oxidative stress mechanism, caused by the peptide and synergized by transition metal ions, or through formation of ion channels by peptide interfacial self-aggregation. Here we demonstrate that Langmuir films of Aβ 1–42, either in pure form or mixed with lipids, develop stable monomolecular arrays with a high surface stability. By using micropipette aspiration technique and confocal microscopy we show that Aβ 1–42 induces a strong membrane destabilization in giant unilamellar vesicles composed of palmitoyloleoyl-phosphatidylcholine, sphingomyelin, and cholesterol, lowering the critical tension of vesicle rupture. Additionally, Aβ 1–42 triggers the induction of a sequential leakage of low- and high-molecular-weight markers trapped inside the giant unilamellar vesicles, but preserving the vesicle shape. Consequently, the Aβ 1–42 sequence confers particular molecular properties to the peptide that, in turn, influence supramolecular properties associated to membranes that may result in toxicity, including: 1), an ability of the peptide to strongly associate with the membrane; 2), a reduction of lateral membrane cohesive forces; and 3), a capacity to break the transbilayer gradient and puncture sealed vesicles.

High current density and drift velocity in templated conducting polymers

Conducting polymers prepared by a templated vapour phase polymerisation process involving solid phase transition metal complexes are found to produce polymers with charge carriers that exhibit maximum drift velocity in the range of 1 m/s. This super-mobility seems to be related to a high degree of ordering in the materials as evidenced by the X-ray diffraction data. This may result from a templated polymerisation process. The high mobility manifests itself as a capacity to sustain very high current densities (>10000 A/cm2); such high current densities are of importance in thin film conductor applications.

Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid

The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf2], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu]+, which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf2] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf2] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV−vis, Raman, and 1H, 13C, and 15N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf2] can be recovered from the labile copper−water−IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu2+ from aqueous media into the [mimSBu][NTf2] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf2] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction−voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium : a thin-film rotating ring-disk electrode study

In this work, LaMO₃ and LaNi_0.5M_0.5O₃ (M = Ni, Co, Fe, Mn and Cr) perovskite oxide electrocatalysts were synthesized by a combined ethylenediaminetetraacetic acid-citrate complexation technique and subsequent calcinations at 1000 °C in air. Their powder X-ray diffraction patterns demonstrate the formation of a specific crystalline structure for each composition. The catalytic property of these materials toward the oxygen reduction reaction (ORR) was studied in alkaline potassium hydroxide solution using the rotating disk and rotating ring-disk electrode techniques. Carbon is considered to be a crucial additive component because its addition into perovskite oxide leads to optimized ORR current density. For LaMO₃ (M = Ni, Co, Fe, Mn and Cr)), in terms of the ORR current densities, the performance is enhanced in the order of LaCrO₃, LaFeO₃, LaNiO₃, LaMnO₃, and LaCoO3. For LaNi_0.5M_0.5O₃, the ORR current performance is enhanced in the order of LaNi_0.5Fe_0.5O₃, LaNi_0.5Co_0.5O₃, LaNi_0.5Cr_0.5O₃, and LaNi_0.5Mn_0.5O₃. Overall, LaCoO₃ demonstrates the best performance. Most notably, substituting half of the nickel with cobalt, iron, manganese, or chromium translates the ORR to a more positive onset potential, suggesting the beneficial catalytic effect of two transition metal cations with Mn as the most promising candidate. Koutecky–Levich analysis on the ORR current densities of all compositions indicates that the four-electron pathway is favored on these oxides, which are consistent with hydroperoxide ion formation of <2%.

Reduction of the photocatalytic activity of ZnO nanoparticles for UV protection applications

The detrimental effects of UV radiation are having a significant impact on our life and environment. The development of effective UV shielding agents is therefore of great importance to our society. ZnO nanoparticles are considered to be one of the most effective UV blocking agents. However, the development of ZnO-based UV shielding products is currently hindered due to the adverse effects of the inherent photocatalytic activity exhibited by ZnO. This paper reports our recent study on the possibility of reducing the photoactivity of ZnO nanoparticles via surface modification and impurity doping. It was found that the photoactivity was drastically reduced by SiO2-coatings that were applied to ZnO quantum dots using the Stöber method and a microemulsion technique. The effect of transition metal doping on the photoactivity was also studied using mechanochemical processing and a co-precipitation method. Cobalt doping reduced the photoactivity, while manganese doping led to mixed results, possibly due to the difference in the location of dopant ions derived from the difference in the synthesis methods.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

A self-supported, flexible, binder-free pseudo-supercapacitor electrode material with high capacitance and cycling stability from hollow, capsular polypyrrole fibers

Flexible energy devices with high performance and long-term stability are highly promising for applications in portable electronics, but remain challenging to develop. As an electrode material for pseudo-supercapacitors, conducting polymers typically show higher energy storage ability over carbon materials and larger conductivity than transition-metal oxides. However, conducting polymer-based supercapacitors often have poor cycling stability, attributable to the structural rupture caused by the large volume contrast between doping and de-doping states, which has been the main obstacle to their practical applications. Herein, we report a simple method to prepare a flexible, binder-free, self-supported polypyrrole (PPy) supercapacitor electrode with high cycling stability through using novel, hollow PPy nanofibers with porous capsular walls as a film-forming material. The unique fiber structure and capsular walls provide the PPy film with enough free-space to adapt to volume variation during doping/de-doping, leading to super-high cycling stability (capacitance retention > 90% after 11000 charge-discharge cycles at a high current density of 10 A g^-1) and high rate capability (capacitance retention ∼ 82.1% at a current density in the range of 0.25-10 A g^-1).

Understanding structure-function relationship in hybrid Co3O4-Fe2O3/C lithium-ion battery electrodes

A range of high-capacity Li-ion anode materials (conversion reactions with lithium) suffer from poor cycling stability and limited high-rate performance. These issues can be addressed through hybridization of multiple nanostructured components in an electrode. Using a Co3O4-Fe2O3/C system as an example, we demonstrate that the cycling stability and rate performance are improved in a hybrid electrode. The hybrid Co3O4-Fe2O3/C electrode exhibits long-term cycling stability (300 cycles) at a moderate current rate with a retained capacity of approximately 700 mAh g(-1). The reversible capacity of the Co3O4-Fe2O3/C electrode is still about 400 mAh g(-1) (above the theoretical capacity of graphite) at a high current rate of ca. 3 A g(-1), whereas Co3O4-Fe2O3, Fe2O3/C, and Co3O4/C electrodes (used as controls) are unable to operate as effectively under identical testing conditions. To understand the structure-function relationship in the hybrid electrode and the reasons for the enhanced cycling stability, we employed a combination of ex situ and in situ techniques. Our results indicate that the improvements in the hybrid electrode originate from the combination of sequential electrochemical activity of the transition metal oxides with an enhanced electronic conductivity provided by percolating carbon chains.

Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

Four cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.

Potential-resolved electrogenerated chemiluminescence for the selective detection of multiple luminophores

Electrogenerated chemiluminescence (ECL) is fundamentally dependent on the applied electrode potential, and measuring ECL intensity over a range of different potentials is commonly used to examine the underlying chemical reaction pathways responsible for the emission of light. Several research groups have now demonstrated that the applied potential can be exploited to selectively elicit ECL from: 1) multiple excited states within a single chemical species; 2) multiple emitters sharing a common co-reactant; or 3) distinct ECL systems. This new generation of multiplexed ECL processes has been facilitated by the extensive development of novel electrochemiluminophores and instrumental approaches such as the near-continuous collection of ECL spectra with CCD detectors during voltammetry or chronoamperometry experiments. New dimensions: In electrogenerated chemiluminescence experiments the applied potential can be exploited to selectively elicit light from: multiple excited states within a single chemical species, multiple emitters sharing a common co-reactant, and distinct electrogenerated chemiluminescence systems. These findings may be used to develop low-cost portable analytical devices.

Brønsted acid-mediated radical processes in organic synthesis

This highlight focuses on recent applications of Brønsted acid-mediated radical processes across a range of reaction manifolds, including transition metal-based catalysis, photochemistry, and polymer science. A brief overview of significant research developments in the area and a discussion of the key mechanistic features of notable transformations are provided.

Síntese e caracterização de espinélios a base de Cu, Fe e Cr para pigmentos cerâmicos

Inorganic pigment comprises a host lattice, which is part of the chromophore component (usually a transition metal cation) and possible components modifiers, which stabilize, add or restate the properties pigments. Among the materials with spinel, ferrites, and the chromite stand out, because they have broad technological importance in the area of materials, applicability, pigments, catalytic hydrogenation, thin film, ceramic tiles, among others. The present work, pigments containing CuFe2O4, CuCr2O4,e CuFeCrO4, were synthesized by a method that makes use of gelatin as organic precursor using their application to ceramic pigments. The pigments were characterized by X-ray diffraction (XRD), Infrared spectroscopy, scanning electron microscopy (SEM) spectroscopy in the UV-visible and Colorimetry. The results confirmed the feasibility of the synthetic route used, with respect to powders synthesized, there is the formation of spinel phase from 500°C, with an increase in crystallinity and the formation of other phases. The pigments were shown to be crystalline and the desired phases were obtained. The copper chromite have hues ranging from green to black according to the calcination temperature, while the copper chromite doped with iron had brownish. The ferrites showed copper color and darker brown to black, which may indicate an interesting factor because of the importance of black pigment

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

Magnetic interactions and spin-reversal mechanism in ErMn1-xCoxO3-delta samples

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)