Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.

Specific and reversible immobilization of proteins tagged to the affinity polypeptide C-LytA on functionalized graphite electrodes

We have developed a general method for the specific and reversible immobilization of proteins fused to the choline-binding module C-LytA on functionalized graphite electrodes. Graphite electrode surfaces were modified by diazonium chemistry to introduce carboxylic groups that were subsequently used to anchor mixed self-assembled monolayers consisting of N,N-diethylethylenediamine groups, acting as choline analogs, and ethanolamine groups as spacers. The ability of the prepared electrodes to specifically bind C-LytA-tagged recombinant proteins was tested with a C-LytA-β-galactosidase fusion protein. The binding, activity and stability of the immobilized protein was evaluated by electrochemically monitoring the formation of an electroactive product in the enzymatic hydrolysis of the synthetic substrate 4-aminophenyl β-D-galactopyranoside. The hybrid protein was immobilized in an specific and reversible way, while retaining the catalytic activity. Moreover, these functionalized electrodes were shown to be highly stable and reusable. The method developed here can be envisaged as a general, immobilization procedure on the protein biosensor field.

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Spectroelectrochemical Study of the Photoinduced Catalytic Formation of 4,4′-Dimercaptoazobenzene from 4-Aminobenzenethiol Adsorbed on Nanostructured Copper

Surface-enhanced raman scattering (SERS) spectra of self-assembled monolayers of 4-aminobenzenethiol (4-ABT) on copper (Cu) and silver (Ag) surfaces decorated with Cu and Ag nanostructures, respectively, have been obtained with lasers at 532, 632.8, 785, and 1064 nm. Density functional theory (DFT) has been used to obtain calculated vibrational frequencies of the 4-ABT and 4,4′-dimercaptoazobenzene (4,4′-DMAB) molecules adsorbed on model Cu surfaces. The features of the SERS spectra depend on the electrode potential and the type and power density of the laser. SERS spectra showed the formation of the 4,4′-DMAB on the nanostructured Cu surface independently of the laser employed. For the sake of comparison SERS spectra of a self-assembled monolayer of the 4-ABT on Ag surfaces decorated with Ag nanostructures have been also obtained with the same four lasers. When using the 532 and 632.8 nm lasers, the 4,4′-DMAB is formed on Cu surface at electrode potentials as low as −1.0 V (AgCl/Ag) showing a different behavior with respect to Ag (and others metals such as Au and Pt). On the other hand, the surface-enhanced infrared reflection absorption (SEIRA) spectra showed that in the absence of the laser excitation the 4,4′-DMAB is not produced from the adsorbed 4-ABT on nanostructured Cu in the whole range of potentials studied. These results point out the prevalence of the role of electron–hole pairs through surface plasmon activity to explain the obtained SERS spectra.

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.

A proposal of algorithm for solving definite descriptions through dialogue structure

En este trabajo proponemos un algoritmo para la resolución de las descripciones definidas en español a través de la estructura del diálogo, mediante la definición de un espacio de accesibilidad anafórico. Este algoritmo está basado en la hipótesis de que la resolución de la anáfora está relacionada con la estructura del diálogo. Así, la resolución de la anáfora mejora si se especifica un espacio de accesibilidad para cada tipo descripción definida según la estructura del diálogo. La utilización de este espacio de accesibilidad anafóico reduce tanto el tiempo de procesamiento como la posibilidad de obtener un antecedente erróneo. Además, la definición de este espacio de accesibilidad depende únicamente de la propia estructura textual del diálogo.

Electronic structure of gated graphene and graphene ribbons

We study the electronic structure of gated graphene sheets. We consider both infinite graphene and finite width ribbons. The effect of Coulomb interactions between the electrically injected carriers and the coupling to the external gate are computed self-consistently in the Hartree approximation. We compute the average density of extra carriers n2D, the number of occupied subbands, and the density profiles as a function of the gate potential Vg. We discuss quantum corrections to the classical capacitance and we calculate the threshold Vg above which semiconducting armchair ribbons conduct. We find that the ideal conductance of perfectly transmitting wide ribbons is proportional to the square root of the gate voltage.

The Spanish version of the Prenatal Breast-feeding Self-efficacy Scale: Reliability and validity assessment

Background: Only a minority of infants are exclusively breastfed for the recommended 6 months postpartum. Breast-feeding self-efficacy is a mother's confidence in her ability to breastfeed and is predictive of breastfeeding behaviors. The Prenatal Breast-feeding Self-efficacy Scale (PBSES) was developed among English-speaking mothers to measure breastfeeding self-efficacy before delivery. Objectives: To translate the PBSES into Spanish and assess its psychometric properties. Design: Reliability and validity assessment. Setting: A public hospital in Yecla, Spain. Participants: A convenience sample of 234 pregnant women in their third trimester of pregnancy. Methods: The PBSES was translated into Spanish using forward and back translation. A battery of self-administered questionnaires was completed by participants, including a questionnaire on sociodemographic variables, breastfeeding experience and intention, as well as the Spanish version of the PBSES. Also, data on exclusive breastfeeding at discharge were collected from hospital database. Dimensional structure, internal consistency and construct validity of the Spanish version of PBSES were assessed. Results: Confirmatory factor analysis suggested the presence of one construct, self-efficacy, with four dimensions or latent variables. Cronbach's alpha coefficient for internal consistency was 0.91. Response patterns based on decision to breastfeed during pregnancy provided evidence of construct validity. In addition, the scores of the Spanish version of the PBSES significantly predicted exclusive breastfeeding at discharge. Conclusions: The Spanish version of PBSES shows evidences of reliability, and contrasting group and predictive validity. Confirmatory factor analysis indicated marginal fit and further studies are needed to provide new evidence on the structure of the scale. The Spanish version of the PBSES can be considered a reliable measure and shows validity evidences.

Constrained self-organizing feature map to preserve feature extraction topology

In many classification problems, it is necessary to consider the specific location of an n-dimensional space from which features have been calculated. For example, considering the location of features extracted from specific areas of a two-dimensional space, as an image, could improve the understanding of a scene for a video surveillance system. In the same way, the same features extracted from different locations could mean different actions for a 3D HCI system. In this paper, we present a self-organizing feature map able to preserve the topology of locations of an n-dimensional space in which the vector of features have been extracted. The main contribution is to implicitly preserving the topology of the original space because considering the locations of the extracted features and their topology could ease the solution to certain problems. Specifically, the paper proposes the n-dimensional constrained self-organizing map preserving the input topology (nD-SOM-PINT). Features in adjacent areas of the n-dimensional space, used to extract the feature vectors, are explicitly in adjacent areas of the nD-SOM-PINT constraining the neural network structure and learning. As a study case, the neural network has been instantiate to represent and classify features as trajectories extracted from a sequence of images into a high level of semantic understanding. Experiments have been thoroughly carried out using the CAVIAR datasets (Corridor, Frontal and Inria) taken into account the global behaviour of an individual in order to validate the ability to preserve the topology of the two-dimensional space to obtain high-performance classification for trajectory classification in contrast of non-considering the location of features. Moreover, a brief example has been included to focus on validate the nD-SOM-PINT proposal in other domain than the individual trajectory. Results confirm the high accuracy of the nD-SOM-PINT outperforming previous methods aimed to classify the same datasets.

Self-Description Questionnaire II (versión breve): evidencia de fiabilidad y validez en una muestra de adolescentes chilenos

El objetivo de este estudio fue analizar la fiabilidad y validez de las puntuaciones de la versión breve del Self-Description Questionnaire II (SDQ-II-S) en población chilena. La muestra se compuso de 1255 adolescentes chilenos, con un rango de edad de 13 a 17 años (M = 15.10; DT = 1.30). El análisis factorial confirmatorio corroboró la estructura original de 11 factores correlacionados del SDQ-II-S. La multidimensionalidad del cuestionario también fue avalada por la pequeña magnitud de las correlaciones entre los 11 factores (M = 0.26). Los coeficientes alfa de Cronbach variaron desde 0.70 hasta 0.84, y se destacó una adecuada fiabilidad. Para profundizar en el análisis de la validez de constructo del SDQ-II-S, se relacionaron las puntuaciones de las diferentes escalas con puntuaciones en medidas de ansiedad (Inventario de Ansiedad Estado-Rasgo) y autoeficacia (Escala de Autoeficacia Percibida Específica de Situaciones Académicas). Los resultados pusieron de manifiesto que estos cuestionarios permiten analizar constructos diferenciados aunque relacionados. Los datos de este trabajo destacan que el SDQ-II-S presenta adecuadas propiedades psicométricas en población chilena, contrarrestando las carencias existentes en lo que respecta a la evaluación del autoconcepto, y resaltan interesantes aplicaciones tanto en el ámbito aplicado como en el de la investigación.