Prussian blue analogues of reduced dimensionality

Mixed-valence polycyanides (Prussian Blue analogues) possess a rich palette of properties spanning from room-temperature ferromagnetism to zero thermal expansion, which can be tuned by chemical modifications or the application of external stimuli (temperature, pressure, light irradiation). While molecule-based materials can combine physical and chemical properties associated with molecular-scale building blocks, their successful integration into real devices depends primarily on higher-order properties such as crystal size, shape, morphology, and organization. Herein a study of a new reduced-dimensionality system based on Prussian Blue analogues (PBAs) is presented. The system is built up by means of a modified Langmuir-Blodgett technique, where the PBA is synthesized from precursors in a self-limited reaction on a clay mineral surface. The focus of this work is understanding the magnetic properties of the PBAs in different periodic, low-dimensional arrangements, and the influence of the "on surface" synthesis on the final properties and dimensionality of the system.     

Electrical Detection of Spin Precession in Freely Suspended Graphene Spin Valves on Cross‐Linked Poly(methyl methacrylate)

Spin injection and detection is achieved in freely suspended graphene using cobalt electrodes and a nonlocal spin‐valve geometry. The devices are fabricated with a single electron‐beam‐resist poly(methyl methacrylate) process that minimizes both the fabrication steps and the number of (aggressive) chemicals used, greatly reducing contamination and increasing the yield of high‐quality, mechanically stable devices. As‐grown devices can present mobilities exceeding 10⁴ cm² V^?1 s^?1 at room temperature and, because the contacts deposited on graphene are only exposed to acetone and isopropanol, the method is compatible with almost any contacting material. Spin accumulation and spin precession are studied in these nonlocal spin valves. Fitting of Hanle spin precession data in bilayer and multilayer graphene yields a spin relaxation time of ～125‐250 ps and a spin diffusion length of 1.7‐1.9 μm at room temperature.     

Fenton and photo‐Fenton oxidation of a model mixture of dyes – overall kinetic analysis

The decolorisation and mineralisation of a model mixture of reactive dyes, under Fenton and photo‐Fenton conditions, have been investigated. A kinetic study was performed and rate constants and half‐life times determined from batch experimental data according to a pseudo‐first‐order degradation kinetic model. Moreover, the use of natural or artificial light, as well as the effect of temperature, was evaluated with the aim of finding the best Fenton process to promote the efficient degradation of the standard trichromatic system. The experimental results showed that the Fenton process run under solar light was the most effective. It is suggested that Fenton‐ and photo‐Fenton‐type reactions are viable techniques for the treatment of these types of dye mixtures, according to the high levels of colour, chemical oxygen demand and total organic carbon removal.     

Mineralization of flumequine in acidic medium by electro-Fenton and photoelectro-Fenton processes

The mineralization of flumequine, an antimicrobial agent belonging to the first generation of synthetic fluoroquinolones which is detected in natural waters, has been studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton (EF) and photoelectro-Fenton (PEF) with UVA light. The experiments were performed in a cell containing a boron-doped diamond (BDD) anode and an air-diffusion cathode to generate H₂O₂ at constant current. The Fe²⁺ ion added to the medium increased the solubility of the drug by the formation of a complex of intense orange colour and also reacted with electrogenerated H₂O₂ to form hydroxyl radical from Fenton reaction. Oxidant hydroxyl radicals at the BDD surface were produced from water oxidation. A partial mineralization of flumequine in a solution near to saturation with optimum 2.0 mM Fe²⁺ at pH 3.0 was achieved by EF. The PEF process was more powerful, giving an almost total mineralization with 94-96% total organic carbon removal. Increasing current accelerated both treatments, but with decreasing mineralization current efficiency. Comparative treatments using a real wastewater matrix led to similar degradation degrees. The kinetics for flumequine decay always followed a pseudo-first-order reaction and its rate constant, similar for both EAOPs, raised with increasing current. Generated carboxylic acids like malonic, formic, oxalic and oxamic acids were quantified by ion-exclusion HPLC. Fe(III)-oxalate and Fe(III)-oxamate complexes were the most persistent by-products under EF conditions and their quicker photolysis by UVA light explains the higher oxidation power of PEF. The release of inorganic ions such as F⁻, NO₃⁻ and in lesser extent NH₄⁺ was followed by ionic chromatography.     

New chlorinated amphetamine-type-stimulants disinfection-by-products formed during drinking water treatment

Previous studies have demonstrated high removal rates of amphetamine-type-stimulants (ATSs) through conventional drinking water treatments; however the behaviour of these compounds through disinfection steps and their transformation into disinfection-by-products (DBPs) is still unknown. In this work, for the first time, the reactivity of some ATSs such as amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA) and 3,4-methylenedioxyethylamphetamine (MDEA) with chlorine has been investigated under simulated and real drinking water treatment conditions in order to evaluate their ability to give rise to transformation products. Two new DBPs from these illicit drugs have been found. A common chlorinated-by-product (3-chlorobenzo)-1,3-dioxole, was identified for both MDA and MDEA while for MDMA, 3-chlorocatechol was found. The presence of these DBPs in water samples collected through drinking water treatment was studied in order to evaluate their formation under real conditions. Both compounds were generated through treatment from raw river water samples containing ATSs at concentration levels ranging from 1 to 15 ng/L for MDA and from 2.3 to 78 ng/L for MDMA. One of them, (3-chlorobenzo)-1,3-dioxole, found after the first chlorination step, was eliminated after ozone and GAC treatment while the MDMA DBP mainly generated after the postchlorination step, showed to be recalcitrant and it was found in final treated waters at concentrations ranging from 0.5 to 5.8 ng/L.     

Interface sensor based on computer vision: Fine tuning using a fluidized bed

The fine tuning of a sensor designed to locate interfaces using a two‐dimensional gas–solid fluidized bed (FB) as reference is described. The sensor works through computer vision and consists of a charge coupled device camera that is placed alongside the bed and, as the human eye would do, first establishes a straight segment of the bed's top surface to define the phase boundary and then through pattern recognition continuously scans the interface in search of a similar pattern. The field of view is 582 × 752 pixels². The experimentally measured Pixel size is 216 × 208 μm². The device allows for experimentally obtaining the position of the probe with a resolution of ± 0.01 pixels at 25 Hz. We also describe its use to measure the height of the FB and observe a linear relationship with fluidization velocity. © 2012 American Institute of Chemical Engineers AIChE J, 2012     

Scanning order strategies for bitplane image coding

Scanning orders of bitplane image coding engines are commonly envisaged from theoretical or experimental insights and assessed in practice in terms of coding performance. This paper evaluates classic scanning strategies of modern bitplane image codecs using several theoretical-practical mechanisms conceived from rate-distortion theory. The use of these mechanisms allows distinguishing those features of the bitplane coder that are essential from those that are not. This discernment can aid the design of new bitplane coding engines with some special purposes and/or requirements. To emphasize this point, a low-complexity scanning strategy is proposed. Experimental evidence illustrates, assesses, and validates the proposed mechanisms and scanning orders.     

Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles

Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.     

Flavour index and aroma profiles of fresh and processed honeys

This paper discusses the importance of flavour profiling in detecting indicative parameters for quality control of fresh and heated honey. Flavour compounds of six unifloral honeys (Lavandula stoechas, Castanea sativa, Dorycnium pentaphyllum, Rosmarinus officinalis, Eucalyptus sp and Robinia pseudoacacia) were investigated. The aroma extracts were obtained by a two‐step procedure involving (i) preliminary steam distillation under reduced pressure to evaluate the methylpyrazines generated in heated honeys by spectrophotometry (flavour index) and (ii) Likens–Nickerson's simultaneous steam distillation and solvent extraction (SDE) method with added NaCl. A combined total of 64 compounds were detected by gas chromatography/mass spectrometry (GC/MS), 58 of which were identified. Some compounds appeared to be characteristic of the floral source, particularly in Spanish lavender (methylated aliphatic acids and aromatic esters), eucalyptus (2,3‐pentanedione, acetoin, 1‐hexyl alcohol, 2‐acetyl‐5‐methylfuran, furfuryl propionate, 2‐phenylacetaldehyde and nerolidol), chestnut (acetophenone and 2‐aminoacetophenone), rosemary and D pentaphyllum (aromatic acids and esters, 2‐phenylacetaldehyde, farnesol and thymol) honeys. Robinia honey samples were characterised by very low levels of aromatic compounds. Twenty‐six flavour compounds were statistically closely related to the floral origin of the honeys (P ≤ 0.05). The flavour index was evaluated progressively in heated honeys, whereas in fresh honeys it showed a minimal value. © 2003 Society of Chemical Industry