Electrocatalytic self-assembled multilayer structures based on thiolated Fc-DAB dendrimers: Determination of heavy metal ions by enzymatic inhibition

The development of sensitive and rapid inhibition-based biosensors for monitoring trace levels of heavy metals such as lead and copper ions in environmental samples is of high interest. In this work, we describe the fabrication of HRP sensitive peroxide biosensors based on ferrocenyl thiolated DAB dendrimers as bonding-layer between electrodeposited and colloidal gold nanoparticles and compare their electrocatalytic properties with those of thiolated DAB homologues. The complete electrochemical, kinetic and analytical characterization of these new heavy metals’ inhibition-biosensors are investigate

Priorities and strategies for improving Roma women’s access to primary health care services in cases on intimate partner violence: a concept mapping study

Background: With an explicit focus on Roma women in Spain (Kale/Spanish Gypsies), this study aims to integrate key informants’ opinions about the main actions needed to improve primary health care services’ and professionals’ responses to Roma women in an Intimate Partner Violence (IPV) situation. Methods: Concept mapping study. A total of 50 (brainstorming phase), 36 (sorting and rating phase) and 16 (interpretation phase) participants from Roma civil society groups, primary health care professionals and other related stakeholders (social services, academic experts and other IPV NGOs representatives) from different cities in Spain were involved in the different study phases. Results: Among the 55 action proposals generated, ten priority actions were identified through consensus as most important for improving primary health care’s response to Romani women in an IPV situation, and these included primary, secondary and tertiary prevention activities. Conclusion: Results indicated that efforts to address this challenge should take an integrated approach that reinforces the primary health care response to IPV in general, while also promoting more specific actions to address barriers to access that affect all Roma women and those who experience IPV in particular.The material and analysis of this study is part of the larger research project titled “Violence against women and the responses of primary health professionals in Spain”, financed by the Ministry of Economy and Competitiveness of the Government of Spain, Carlos III Institute and Fondos FEDER (Ref.PI13/00874), directed by the professor Carmen Vives-Cases

Health education in primary school: Alicante city (Spain) teachers’ opinions

Objetivo: Explorar la opinión del profesorado de educación primaria de la ciudad de Alicante sobre las actividades de salud realizadas en la escuela. Método: Estudio exploratorio mediante análisis de contenido cualitativo. Se formaron tres grupos de discusión (8-9 participantes) con profesorado de educación primaria (14 mujeres y 11 hombres) procedentes de 14 escuelas públicas y 7 concertadas de la ciudad de Alicante. La información se obtuvo preguntando a los/las participantes sobre las actividades de salud realizadas en el aula o en el centro escolar. Resultados: El profesorado diferenció las actividades que forman parte de las programaciones escolares de educación para la salud de las que proceden de programas de otras instituciones públicas o privadas. Consideró que los programas externos son impuestos, no tienen continuidad y responden a modas pasajeras. Aunque mostró una actitud más favorable y comprometida con las actividades y programaciones escolares, identificó la educación para la salud como una tarea secundaria. En su opinión, incrementar su formación en salud, implicar a los padres y las madres, profesionales sanitarios y la administración educativa fomentaría la educación para la salud en la escuela. Conclusiones: El profesorado muestra una opinión más favorable y un mayor compromiso hacia las actividades de salud que complementan y facilitan su tarea educativa. Su programación docente y opinión deben tenerse en cuenta para maximizar la eficiencia de las actividades de promoción y educación para la salud promovidas por instituciones, compañías y fundaciones externas a la escuela.Objective: This study explores the opinions of primary school teachers about health activities carried out in schools in Alicante city (Spain). Methods: An exploratory study was conducted through qualitative content analysis. Three focus groups were conducted with 25 primary school teachers (14 women and 11 men) working in 14 public and 7 private schools in the city of Alicante. Participants were asked about the health activities carried on in their schools. Results: Teachers distinguished between health education activities promoted by the school and those included in external programmes promoted by public and private institutions. External programmes were considered as impositions, lacking continuity and chosen according to passing fads. Although teachers demonstrated a more positive attitude towards activities arising from their own initiative, they identified health education as a secondary task. Teachers considered that improving their own health education training and promoting the involvement of parents, health professionals and public institutions were the most appropriate ways to promote health education in the school. Conclusion: Teachers showed a more positive opinion and greater commitment towards health activities that complement and facilitate their teaching tasks. Their didactic programme and opinion should be taken into account to maximise the efficiency of the health promotion and education activities promoted by external organisations.Este trabajo ha sido financiado por la Escuela Valenciana de Estudios en Salud (EVES) de la Generalitat Valenciana nº 044/2006

Theoretical understanding of the increment of upon protonation of pyridine peripheral octupolar molecules: Toward nonlinear optical sensors

6 pages, 6 tables, 4 figures.In this article, we present a computational study of the nonlinear optical properties of pyridine-based octupolar molecules in their neutral and fully triprotonated states. The effect of the core substitution and the degree of conjugation with the periphery has been also established and confirms the possibility of fine-tuning the nonlinear optical response. Computations involving the time-dependent density-functional theory approach serve to further explore the existence of excited states with nonzero dipole moment. From these results, the origin of the high second-order nonlinear optical activity upon protonation is addressed.The present work was supported in part by the Dirección General de Enseñanza Superior DGES, MEC, Spain through research Project Nos. CTQ2006-14987-C02-01 and CTQ2005-01368. The authors are also indebted to Junta de Andalucía and Gobierno de Aragón Spain for funding their research groups FQM-0159 and E39. M.C.R.D. is grateful to the MEC/Fulbright for her Postdoctoral Fellowship at the Georgia Institute of Techology. J.C. is grateful to the MEC of Spain for an I3 professorship position of Chemistry at the University of Málaga and M.M.O. acknowledges the MEC for a personal grant.Peer reviewe

Synthesis of titanium and zirconium complexes with 2-pyridonate and 2, 6-pyridinedithiolate ligands

Special Issue: Dedicated to Professor F. Ekkehardt Hahn on the Occasion of His 60th Birthday with our most Sincere Congratulations for his Outstanding Contributions to Chemistry and Best Wishes.Treatment of complex [Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex [Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound [Cp2ZrCl2] did not worked. However, the use of the metallocene [Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted [Cptt 2ZrMe2] with methanol affording complex [Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of [Cptt 2ZrMe2] with 2-hydroxypyridine gave complex [Cptt 2Zr(Me)(Opy)] (3); forcing the conditions of this reaction did not lead to the expected complex [Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine [py(SH)2] a double protonation of the methyl ligands in [Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex [Cptt 2Zr(κS,κS,κN-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement; structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions.Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER, Projects CTQ2012-35665 and CTQ2013-42532-P), MICINN (Project Consolider Ingenio 2010, CSD2009-00050) and Diputación General de Aragón (DGA/ FSE-E07 and E70) is gratefully acknowledged.Peer Reviewe

Electrochemical and bioelectrocatalytical properties of novel block-copolymers containing interacting ferrocenyl units

The electrochemical characterization of three different polystyrene-b-polybutadiene block copolymers functionalized with ferrocenyl units electronically communicated, PSm-PBn(HSiMeFc2)p where m=615, n=53, p=39 (1), m=375, n=92, p=76 (2) and m=455, n=204, p=170 (3), has been carried out both in solution and electrochemically deposited onto platinum electrodes. The bioelectrocatalytical properties of electrodes modified with the polymers in the nicotinamide dinucleotide (NADH) and glucose oxidase (GOx) oxidations have been investigated as a function of the constitution and structure of the polymers. The analytical properties of electrodes modified with these polymers as sensors of NADH and GOx are described. In addition, an amperometric biosensor for glucose, prepared by electrostatic immobilization of glucose oxidase onto a platinum electrode modified with one of the ferrocenyl block copolymers as an example, has been developed. The results confirm that electrodes modified with the examined copolymers act as efficient redox mediators for the electrocatalytic oxidation of both reduced nicotinamide dinucleotide cofactor and glucose oxidase. The reaction with NADH proceeds via formation of a charge-transfer intermediate before yielding the reaction products. This is a novel example of electrodes modified with ferrocene derivatives that can be applied to the determination of NADH without the use of diaphorase. The redox copolymers co-immobilized with glucose-oxidase have been successfully used as amperometric biosensors for glucose determinations. As expected these compounds allow using lower working potentials. The sensitivities and detection limits obtained are comparable or even better than those of other ferrocene-modified polymers mediator electrodes

Quantum chemical DFT and spectroscopic UV-Vis-NIR analysis of a series of push-pull oligothiophenes end capped by amino-cyanovinyl groups

A series of push-pull chromophores built around thiophene-based -conjugating spacers and bearing various types of amino-donors and cyanovinyl-acceptors have been analyzed by means of UV-Vis- NIR spectroscopic measurements. Density functional theory (DFT) calculations have also been performed to help the assignment of the most relevant electronic features and to derive useful information about the molecular structure of these NLO-phores. The effects of the donor/acceptor substitution in the electronic and molecular properties of the -conjugated spacer have been addressed. The effectiveness of the intramolecular charge transfer (ICT) has also been tested as a function of the nature of the end groups (i.e., electron-donating or electron-withdrawing capabilities).Research at the University of Málaga was supported by the Ministerio de Educación y Ciencia (MEC) of Spain through project CTQ2006-14987-C02-01, and by the Junta de Andalucía for funding our FQM- 0159 scientific group. J.C. is grateful to the Ministerio de Ciencia y Tecnología of Spain for a Ramón y Cajal position of Chemistry at the University of Málaga. M.C.R.D. is also grateful to the Ministerio de Educación y Ciencia of Spain for a personal grant. The group at the University of Minho acknowledges the Foundation for Science and Technology (Portugal) for financial support through Centro de Química (UM) and through POCTI, FEDER (ref. POCTI/QUI/37816/2001). M. Manuela M. Raposo and A. Maurício C. Fonseca are also grateful to Professor G. Kirsch from University of Metz (France) for his collaboration

U-Pb SHRIMP zircon dating of Grenvillian metamorphism in Western Sierras Pampeanas (Argentina) : correlation with the Arequipa-Antofalla craton and constraints on the extent of the Precordillera Terrane

The Sierras Pampeanas of Argentina, the largest outcrop of pre-Andean crystalline basement in southern South America, resulted from plate interactions along the proto-Andean margin of Gondwana, from as early as Mesoproterozoic to Late Paleozoic times (e.g., Ramos, 2004, and references therein). Two discrete Paleozoic orogenic belts have been recognized: the Early Cambrian Pampean belt in the eastern sierras, and the Ordovician Famatinian belt, which partially overprints it to the west (e.g., Rapela et al., 1998). In the Western Sierras Pampeanas, Mesoproterozoic igneous rocks (ca. 1.0–1.2 Ga) have been recognized in the Sierra de Pie de Palo (Fig. 1) (McDonough et al., 1993 M.R. McDonough, V.A. Ramos, C.E. Isachsen, S.A. Bowring and G.I. Vujovich, Edades preliminares de circones del basamento de la Sierra de Pie de Palo, Sierras Pampeanas occidentales de San Juán: sus implicancias para el supercontinente proterozoico de Rodinia, 12° Cong. Geol. Argentino, Actas vol. 3 (1993), pp. 340–342.McDonough et al., 1993, Pankhurst and Rapela, 1998 and Vujovich et al., 2004) that are time-coincident with the Grenvillian orogeny of eastern and northeastern North America (e.g., Rivers, 1997 and Corrievau and van Breemen, 2000). These Grenvillian-age rocks have been considered to be the easternmost exposure of basement to the Precordillera Terrane, a supposed Laurentian continental block accreted to Gondwana during the Famatinian orogeny (Thomas and Astini, 2003, and references therein). However, the boundaries of this Grenvillian belt are still poorly defined, and its alleged allochthoneity has been challenged (Galindo et al., 2004). Moreover, most of the Grenvillian ages so far determined relate to igneous protoliths, and there is no conclusive evidence for a Grenvillian orogenic belt, other than inferred from petrographic evidence alone (Casquet et al., 2001). We provide here the first evidence, based on U–Pb SHRIMP zircon dating at Sierra de Maz, for a Grenville-age granulite facies metamorphism, leading to the conclusion that a continuous mobile belt existed throughout the proto-Andean margin of Gondwana in Grenvillian times

Chondroid Tumors: Review of Salient Imaging Features and Update on the WHO Classification

Chondrogenic tumors are typically well recognized on radiographs, but differentiation between benign and malignant cartilaginous lesions can be difficult both for the radiologist and for the pathologist. Diagnosis is based on a combination of clinical, radiological and histological findings. While treatment of benign lesions does not require surgery, the only curative treatment for chondrosarcoma is resection. This article (1) emphasizes the update of the WHO classification and its diagnostic and clinical effects; (2) describes the imaging features of the various types of cartilaginous tumors, highlighting findings that can help differentiate benign from malignant lesions; (3) presents differential diagnoses; and (4) provides pathologic correlation. We attempt to offer valuable clues in the approach to this vast entit