Surface and grain‐boundary excess of ZnO‐doped SnO2 nanopowders by the selective lixiviation method

The primary characteristic of nanopowders is the high surface area and consequently high fraction of atoms on the interfaces, which changes the energy of the system. The additive distribution in the nanopowder interfaces is a fundamental aspect to control the energy, particle size, and final properties of nanopowders. In this work, the surface excess was determined using a selective lixiviation method, where a low‐water‐soluble oxide, SnO₂, was used as the matrix, and a high‐water‐soluble oxide, ZnO, was used as the additive. The X‐ray photoelectron spectroscopy (XPS) analysis confirmed that ZnO segregated on SnO₂ surfaces. However, after acid lixiviation the same analysis showed an undetectable surface concentration of ZnO. The evaluation of the nanostructure change and surface composition enables us to calculate the heat of segregation for the grain boundary and surface and the interface energy reduction because of segregation. At low‐ZnO concentrations, the additive solubilizes in the bulk and promotes particle growth. However, the segregation to the grain boundary and surface determines the relative stability of each interface, which promotes hard agglomeration and particle size stabilization at intermediated ZnO amounts. At high‐ZnO concentrations, the surface segregation stabilizes the solid‐gas interface and decreases the agglomeration and final particle size.     

Industrial Home Laundry Closed Loop Cleaning Process

This study presents a method to develop an efficient and economical system for cleaning home laundry on a commercial scale with both water and chemical (detergent) reuse. The experiments were done using an industrial-type horizontal-axis machine, two leading consumer heavy-duty liquid laundry detergents, one I&I detergent formulation, and chlorine bleach. The technical feasibility of reusing laundry water at high levels without significant deterioration in detergency was established in this study. Warm water (40 °C) was used in the wash cycle, and cold water (29 °C) was used for three rinse cycles. In the integrated process, waters from wash and rinse steps were treated using tubular microfiltration units with 0.1 μm pore size to remove particles and emulsion droplets. These recovered waters were recycled to be reused. In addition, water recycled from the wash step contains surfactants that can be reused. In order to simulate a large-scale industrial laundry operation at steady-state, the batch process used here was operated six times in sequence; wash and rinse waters were filtered after each cycle and reused in the next wash cycle. The surfactant recovery is over 40%. Soiled test strips were used to measure the percentage of soil removal after the wash/filtration sequence for stains and various liquid or particulate soils. The soil removal remained practically constant under simulated steady-state conditions even with water recoveries of nearly 90%. Softness of towels remained unchanged when recycled water was used in this process. Chlorine carry-over from white laundry to the wash process was shown to be minimal. This is important to avoid color fading in mixed loads upon reuse since water is not segregated for colored laundry versus white laundry. Hardness ions can precipitate fatty acids which reduce flux during filtration and decrease surfactant recovery. Preliminary analysis of the different formulations used indicates that an all-nonionic formulation may be best suited to this recycling process.

Drug-Induced Lysosomal Impairment Is Associated with the Release of Extracellular Vesicles Carrying Autophagy Markers

Amiodarone is a cationic amphiphilic drug used as an antiarrhythmic agent. It induces phospholipidosis, i.e., the accumulation of phospholipids within organelles of the endosomal–lysosomal system. Extracellular vesicles (EVs) are membrane-enclosed structures released by any type of cell and retrieved in every fluid of the body. EVs have been initially identified as a system to dispose cell waste, but they are also considered to be an additional manner to transmit intercellular signals. To understand the role of EVs in drug-induced phospholipidosis, we investigated EVs release in amiodarone-treated HEK-293 cells engineered to produce fluorescently labelled EVs. We observed that amiodarone induces the release of a higher number of EVs, mostly of a large/medium size. EVs released upon amiodarone treatment do not display significant morphological changes or altered size distribution, but they show a dose-dependent increase in autophagy associated markers, indicating a higher release of EVs with an autophagosome-like phenotype. Large/medium EVs also show a higher content of phospholipids. Drugs inducing lysosomal impairment such as chloroquine and bafilomycin A1 similarly prompt a higher release of EVs enriched in autophagy markers. This result suggests a mechanism associated with amiodarone-induced lysosomal impairment more than a connection with the accumulation of specific undigested substrates. Moreover, the implementation of the lysosomal function by overexpressing TFEB, a master gene regulator of lysosomal biogenesis, prevents the amiodarone-induced release of EVs, suggesting that this could be a feasible target to attenuate drug-induced abnormalities.     

Peptides Derived from Angiogenin Regulate Cellular Copper Uptake

The angiogenin protein (ANG) is one of the most potent endogenous angiogenic factors. In this work we characterized by means of potentiometric, spectroscopic and voltammetric techniques, the copper complex species formed with peptide fragments derived from the N-terminal domain of the protein, encompassing the sequence 1-17 and having free amino, Ang1-17, or acetylated N-terminus group, AcAng1-17, so to explore the role of amino group in metal binding and cellular copper uptake. The obtained data show that amino group is the main copper anchoring site for Ang1-17. The affinity constant values, metal coordination geometry and complexes redox-potentials strongly depend, for both peptides, on the number of copper equivalents added. Confocal laser scanning microscope analysis on neuroblastoma cells showed that in the presence of one equivalent of copper ion, the free amino Ang1-17 increases cellular copper uptake while the acetylated AcAng1-17 strongly decreases the intracellular metal level. The activity of peptides was also compared to that of the protein normally present in the plasma (wtANG) as well as to the recombinant form (rANG) most commonly used in literature experiments. The two protein isoforms bind copper ions but with a different coordination environment. Confocal laser scanning microscope data showed that the wtANG induces a strong increase in intracellular copper compared to control while the rANG decreases the copper signal inside cells. These data demonstrate the relevance of copper complexes’ geometry to modulate peptides’ activity and show that wtANG, normally present in the plasma, can affect cellular copper uptake.     

Characterisation of the phenolic and flavonoid fractions and antioxidant power of Italian honeys of different botanical origin

BACKGROUND: Twenty‐seven Italian honey samples of different floral origin were analysed for total phenolic and flavonoid contents by a spectrophotometric method and for antioxidant power and radical‐scavenging activity by the ferric‐reducing/antioxidant power (FRAP) and 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) assays respectively. In addition, the phenolic and flavonoid profiles were analysed using high‐performance liquid chromatography with UV detection (HPLC‐UV). RESULTS: The results of this study showed that honey contains copious amounts of phenolics and flavonoids. HPLC‐UV analysis showed a similar qualitative polyphenolic profile for all honey samples analysed. The main difference among samples was in the contribution of individual analytes, which was affected by floral origin. Total phenolic and flavonoid contents varied from 60.50 to 276.04 mg gallic acid equivalent kg^?1 and from 41.88 to 211.68 mg quercetin equivalent kg^?1 respectively. The antioxidant capacity was high and differed widely among samples. The FRAP value varied from 1.265 to 4.396 mmol Fe²⁺ kg^?1, while the radical‐scavenging activity expressed as DPPH‐IC₅₀ varied from 7.08 to 64.09 mg mL^?1. Correlations between the parameters analysed were found to be statistically significant (P < 0.05). CONCLUSION: The present study shows that honey contains high levels of phenolics and flavonoids and that the distribution of these compounds is influenced by the honey's floral origin. Copyright © 2009 Society of Chemical Industry     

Study of the mechanical,electrical and morphological properties of PU/MWCNT composites obtained by two different processing routes

A comparative study of the influence of processing route on polyurethanes (PUs)/multiwalled carbon nanotube (MWCNT) composites mechanical and electrical properties and also morphology was undergone employing two differentiated processing methods, solvent casting and buckypaper infiltration, for producing PU composites with low, medium and high mass fractions of acid treated MWCNT, and with no covalent linkages between the matrix and the nanotubes. As for example, with a MWCNT mass fraction of ∼18 wt.% the second method produced stiffer (270 MPa), lighter (948 kg m⁻³) and more electrically conductive (1.8 S cm⁻¹) composite while the first one gave softer (111 MPa) and more ductile (141%) materials. These properties differences are related to the different PU/MWCNT dispositions obtained through each synthesis route. Nanotubes percolating concentration is found to be crucial on composite properties evolution and a preferential interaction of MWCNT with PU hard segments is observed for solvent cast composites.     

Microdomain composition and properties differences of biodegradable polyurethanes based on MDI and HDI

The study of the effect of the diisocyanate structure on the microstructure and macroscopic properties of polyurethanes was the main aim of this work. Biodegradable segmented thermoplastic elastomeric polyurethanes based on a poly(hexamethylene carbonate‐co‐caprolactone)diol (PHM‐co‐PCL) as soft segment were synthesized using 1,4‐butanediol (BD) as chain extender and both 4,4′‐diphenylmethane diisocyanate (MDI) and 1,6‐hexamethylene diisocyanate (HDI) as components of the hard segment by the two shoot synthesis procedure. Microphase structure and properties were analyzed using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) as complementary techniques, used to characterize thermal transitions of the polyurethanes and to assign them to determinate functional groups interactions. Gaussian deconvolution technique was used to decompose carbonyl region in four peaks and to study the hydrogen bonding within the different polyurethanes. Both DSC and FTIR showed that MDI‐based biodegradable polyurethanes were less phase segregated than to those based on HDI, and thus that diisocyanate structure has an important role on microdomain composition and polyurethanes properties. Macroscopic properties as hardness and water‐polymer contact angles are related to polyurethanes microphase compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

The distribution of lithium intercalated in V2O5 thin films studied by XPS and ToF-SIMS

The distribution of lithium in V₂O₅/V lower oxide duplex thin films prepared by thermal oxidation of V metal was analysed by XPS and ToF-SIMS after intercalation at 2.8 V versus Li/Li⁺ and de-intercalation at 3.8 V following cycling between 3.8 and 2.8 V in 1 M LiClO₄-PC. XPS analysis of the intercalated thin film evidenced a partial reduction (43 at.% V⁴⁺) of the V₂O₅ surface, the modification of its electronic structure and the presence of Li, consistent with the formation of the δ-Li_xV₂O₅ (0.9 ≤ x ≤ 1) phase. The Li in-depth distribution measured by ToF-SIMS shows a maximum in the outer layer of V₂O₅, but Li is also found at the oxide film/metal substrate interface indicating its diffusion across the inner layer of V lower oxides. The analyses performed after de-intercalation on the samples cycled 12, 120 and 300 times reveal the effect of aging on the trapping of lithium. A significant reduction (17-22 at.% V⁴⁺) of the V₂O₅ surface was measured after 300 cycles. The Li in-depth distribution shows a maximum at the interface between the outer layer of V₂O₅ and the inner layer of lower oxides. Aging favours the accumulation of lithium at this interface with a resulting enlarged distribution enriching the sub-surface of the outer layer of V₂O₅ and the inner layer of lower oxides after 300 cycles. Lithium is also found, but in smaller quantities, at the oxide film/metal substrate interface. Measurements performed in the non-electrochemically treated surface areas of the de-intercalated samples revealed the same type of modifications, evidencing the diffusion of lithium along the interfaces where it is trapped.