Electrochemical reactions of catechol, methylcatechol and dopamine at tetrahedral amorphous carbon (ta-C) thin film electrodes

The electrochemical reactions of dopamine, catechol and methylcatechol were investigated at tetrahedral amorphous carbon (ta-C) thin film electrodes. In order to better understand the reaction mechanisms of these molecules, cyclic voltammetry with varying scan rates was carried out at different pH values in H2SO4 and PBS solutions. The results were compared to the same redox reactions taking place at glassy carbon (GC) electrodes. All three catechols exhibited quasi-reversible behavior with sluggish electron transfer kinetics at the ta-C electrode. At neutral and alkaline pH, rapid coupled homogeneous reactions followed the oxidation of the catechols to the corresponding o-quinones and led to significant deterioration of the electrode response. At acidic pH, the extent of deterioration was considerably lower. All the redox reactions showed significantly faster electron transfer kinetics at the GC electrode and it was less susceptible toward surface passivation. An EC mechanism was observed for the oxidation of dopamine at both ta-C and GC electrodes and the formation of polydopamine was suspected to cause the passivation of the electrodes.

Robust solutions to multi-objective linear programs with uncertain data

In this paper we examine multi-objective linear programming problems in the face of data uncertainty both in the objective function and the constraints. First, we derive a formula for the radius of robust feasibility guaranteeing constraint feasibility for all possible scenarios within a specified uncertainty set under affine data parametrization. We then present numerically tractable optimality conditions for minmax robust weakly efficient solutions, i.e., the weakly efficient solutions of the robust counterpart. We also consider highly robust weakly efficient solutions, i.e., robust feasible solutions which are weakly efficient for any possible instance of the objective matrix within a specified uncertainty set, providing lower bounds for the radius of highly robust efficiency guaranteeing the existence of this type of solutions under affine and rank-1 objective data uncertainty. Finally, we provide numerically tractable optimality conditions for highly robust weakly efficient solutions.

Blending in English Charactoons

This article deals with both the word-formation mechanism of blending and the creative process involved in providing characters with proper names in cartoons or TV series for children in English. The study addresses the nature and features of proper and common names, two apparently well-distinguished categories, as well as, and basically fictional proper names, by suggesting differences between fictional proper names and other types of proper and common names. Furthermore, it discusses the presence of blending in fiction and in fictional proper names, with special reference to charactonyms. The main focus of this work is on blended charactonyms in cartoons addressed to children, which for the purposes of this study will be called cartoonyms or charactoons. Questions such as the following are addressed: the formation or creation of cartoonyms or charactoons from pre-existing material; the semantic motivations behind their formation; their resulting structural complexity; their particularly descriptive, expressive and meaningful nature; as well as how suitable they are to the genre in which they are used.

The activating role of phospho-(Tyr)-calmodulin on the epidermal growth factor receptor

The activity of calmodulin (CaM) is modulated not only by oscillations in the cytosolic concentration of free Ca2+, but also by its phosphorylation status. In the present study, the role of tyrosine-phosphorylated CaM [P-(Tyr)-CaM] on the regulation of the epidermal growth factor receptor (EGFR) has been examined using in vitro assay systems. We show that phosphorylation of CaM by rat liver solubilized EGFR leads to a dramatic increase in the subsequent phosphorylation of poly-L-(Glu:Tyr) (PGT) by the receptor in the presence of ligand, both in the absence and in the presence of Ca2+. This occurred in contrast with assays where P-(Tyr)-CaM accumulation was prevented by the presence of Ca2+, absence of a basic cofactor required for CaM phosphorylation and/or absence of CaM itself. Moreover, an antibody against CaM, which inhibits its phosphorylation, prevented the extra ligand-dependent EGFR activation. Addition of purified P-(Tyr)-CaM, phosphorylated by recombinant c-Src (cellular sarcoma kinase) and free of non-phosphorylated CaM, obtained by affinity-chromatography using an immobilized anti-phospho-(Tyr)-antibody, also increased the ligand-dependent tyrosine kinase activity of the isolated EGFR toward PGT. Also a CaM(Y99D/Y138D) mutant mimicked the effect of P-(Tyr)-CaM on ligand-dependent EGFR activation. Finally, we demonstrate that P-(Tyr)-CaM binds to the same site (645R-R-R-H-I-V-R-K-R-T-L-R-R-L-L-Q660) as non-phosphorylated CaM, located at the cytosolic juxtamembrane region of the EGFR. These results show that P-(Tyr)-CaM is an activator of the EGFR and suggest that it could contribute to the CaM-mediated ligand-dependent activation of the receptor that we previously reported in living cells.

Silica Microparticles Supported Gold and Copper Ferrite Nanoparticles: A Magnetically Recyclable Bimetallic Catalyst for Sonogashira Reaction

Novel silica supported gold and copper ferrite nanoparticles (NPs) have been synthesized, characterized and used as a separable dual catalyst in Sonogashira type reaction. These Au.CuFe2O4@Silica NPs show a high efficiency as catalyst in the alkynylation not only of aryl iodides but also aryl bromides. By using only 0.5 mol% loading and t-BuOK as base in N,N-dimethylacetamide as solvent, aryl iodides react at 115 ºC in 1 d, whereas for aryl bromides the cross-coupling takes place at 130 ºC in 2 d. The catalyst can be successfully recycled using an external magnet for four consecutive runs.

Gold Nanoparticles Supported on Polyacrylamide Containing a Phosphorus Ligand as an Efficient Heterogeneous Catalyst for Three-Component Synthesis of Propargylamines in Water

Gold nanoparticles supported on a polyacrylamide containing a phosphinite ligand have been synthesized and characterized using different techniques such as TEM, SEM, EDX, XPS, and solid UV analyses. The new material was successfully applied as a heterogeneous catalyst for the three-component A3 coupling of amines, aldehydes, and alkynes to give propargylamines. Reactions are performed in neat water at 80 °C with only 0.05 mol% catalyst loading. The heterogeneous catalyst is recyclable during seven consecutive runs with small decrease in activity.

Paving the way for methane hydrate formation on metal–organic frameworks (MOFs)

The presence of a highly tunable porous structure and surface chemistry makes metal–organic framework (MOF) materials excellent candidates for artificial methane hydrate formation under mild temperature and pressure conditions (2 °C and 3–5 MPa). Experimental results using MOFs with a different pore structure and chemical nature (MIL-100 (Fe) and ZIF-8) clearly show that the water–framework interactions play a crucial role in defining the extent and nature of the gas hydrates formed. Whereas the hydrophobic MOF promotes methane hydrate formation with a high yield, the hydrophilic one does not. The formation of these methane hydrates on MOFs has been identified for the first time using inelastic neutron scattering (INS) and synchrotron X-ray powder diffraction (SXRPD). The results described in this work pave the way towards the design of new MOF structures able to promote artificial methane hydrate formation upon request (confined or non-confined) and under milder conditions than in nature.

Colour changes by laser irradiation of reddish building limestones

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm−2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm−2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm−2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

Delineating zones to increase geographical detail in individual response data files: An application to the Spanish 2011 Census of population

Due to confidentiality considerations, the microdata available from the 2011 Spanish Census have been codified at a provincial (NUTS 3) level except when the municipal (LAU 2) population exceeds 20,000 inhabitants (a requirement that is met by less than 5% of all municipalities). For the remainder of the municipalities within a given province, information is only provided for their classification in wide population intervals. These limitations, hampering territorially-focused socio-economic analyses, and more specifically, those related to the labour market, are observed in many other countries. This article proposes and demonstrates an automatic procedure aimed at delineating a set of areas that meet such population requirements and that may be used to re-codify the geographic reference in these cases, thereby increasing the territorial detail at which individual information is available. The method aggregates municipalities into clusters based on the optimisation of a relevant objective function subject to a number of statistical constraints, and is implemented using evolutionary computation techniques. Clusters are defined to fit outer boundaries at the level of labour market areas.

ViDRILO: The Visual and Depth Robot Indoor Localization with Objects information dataset

In this article we describe a semantic localization dataset for indoor environments named ViDRILO. The dataset provides five sequences of frames acquired with a mobile robot in two similar office buildings under different lighting conditions. Each frame consists of a point cloud representation of the scene and a perspective image. The frames in the dataset are annotated with the semantic category of the scene, but also with the presence or absence of a list of predefined objects appearing in the scene. In addition to the frames and annotations, the dataset is distributed with a set of tools for its use in both place classification and object recognition tasks. The large number of labeled frames in conjunction with the annotation scheme make this dataset different from existing ones. The ViDRILO dataset is released for use as a benchmark for different problems such as multimodal place classification and object recognition, 3D reconstruction or point cloud data compression.

Synthesis of 5-Carbapterocarpens by α-Arylation of Tetralones Followed by One-Pot Demethylation/Cyclization with BBr3

5-Carbapterocarpens, one of them displaying estrogenic activity, were prepared from α-aryltetralones in high yields through a one-pot, BBr3-promoted O-demethylation and cyclization sequence. The key α-aryltetralone intermediates were obtained by direct α-arylation of tetralones with o-alkoxybromoarenes in the presence of Pd2(dba)3 (2.5 mol-%) and tBu3PHBF4 (10 mol-%) as catalysts, together with 2.5 equiv. of KOH in dioxane/H2O (4:1), under microwave irradiation conditions (80 W, 100 °C, 40 min), leading to α-monoaryltetralones in good yields.

Number of discernible colors for color-deficient observers estimated from the MacAdam limits

We estimated the number of colors perceived by color normal and color-deficient observers when looking at the theoretic limits of object-color stimuli. These limits, the optimal color stimuli, were computed for a color normal observer and CIE standard illuminant D65, and the resultant colors were expressed in the CIELAB and DIN99d color spaces. The corresponding color volumes for abnormal color vision were computed using models simulating for normal trichromatic observers the appearance for dichromats and anomalous trichomats. The number of colors perceived in each case was then computed from the color volumes enclosed by the optimal colors also known as MacAdam limits. It was estimated that dichromats perceive less than 1% of the colors perceived by normal trichromats and that anomalous trichromats perceive 50%–60% for anomalies in the medium-wavelength-sensitive and 60%–70% for anomalies in the long-wavelength-sensitive cones. Complementary estimates obtained similarly for the spectral locus of monochromatic stimuli suggest less impairment for color-deficient observers, a fact that is explained by the two-dimensional nature of the locus.

The minimum number of measurements for colour, sparkle, and graininess characterisation in gonio-apparent panels

Materials with new visual appearances have emerged over the last few years. In the automotive industry in particular there is a growing interest in materials with new effect finishes, such as metallic, pearlescent, sparkle, and graininess effects. Typically, for solid colours the mean of three measurements with repetitions is sufficient to obtain a representative measurement for colour characterisation. However, gonio-apparent panels have non-homogeneous colours, and there are no studies that recommend the minimum number of repetitions for colour, sparkle, and graininess characterisation of this type of panel. We assume that colour panels incorporating special-effect pigments in their colour recipes will require a higher minimum number of measurements than solid colour panels. Therefore, the purpose of this study is to verify this assumption by using a multiangle BYK-mac spectrophotometer, given that it is currently the only commercial device that can measure colour, sparkle, and graininess values simultaneously. In addition, a possible methodology is given for establishing the minimum number of measurements when characterising gonio-apparent materials using a specific instrument, able to be implemented in future instruments when determining multiple appearance attributes (colour, gloss, sparkle, etc.) for many coloration technologies. Thus, we studied the minimum number of measurements needed to characterise the colour, sparkle, and graininess of three types of sample with solid, metallic, and pearlescent coatings respectively. Twenty measurements were made at twenty random positions (different target areas) of 90 samples. The minimum number of measurements for all these variables was determined on the basis of the point at which the cumulative mean value became constant. Thus, applying new statistical tools, it is clearly shown that metallic and pearlescent panels require more colour measurements than solid panels, in particular when geometries are being measured in a specular direction. As regards texture (sparkle and graininess), more measurements are needed for graininess than for sparkle, and more for metallic panels than for pearlescent panels.