Microwave Hydrothermal Synthesis and Photocatalytic Performance of ZnO and M:ZnO Nanostructures (M = V, Fe, Co)

ZnO and doped M:ZnO (M = V, Fe and Co) nanostructures were synthesized by microwave hydrothermal synthesis using a low temperature route without addition of any surfactant. The transition metal ions were successfully doped in small amount (3% mol) into ZnO structure. Analysis by X-ray diffraction reveals the formation of ZnO with the hexagonal (wurtzite-type) crystal structure for all the samples. The as-obtained samples showed a similar flower-like morphology except for Fe:ZnO samples, which presented a plate-like morphology. The photocatalytic performance for Rhodamine B (RhB) degradation confirmed that the photoactivity of M:ZnO nanostructures decreased for all dopants in structure, according to their eletronegativity. Photoluminescence spectroscopy was employed to correlate M:ZnO structure with its photocatalytical properties. It was suggested that transition metal ions in ZnO lattice introduce defects that act as trapping or recombination centers for photogenerated electrons and holes, making it impossible for them reach the surface and promote the photocatalytical process.

Epidemiological, parasitological and molecular aspects of Giardia duodenalis infection in children attending public daycare centers in southeastern Brazil

The purpose of this study was to determine the prevalence, associated risk factors and genotype of Giardia duodenalis infection in children attending public daycare centers in the city of Araguari, state of Minas Gerais, Brazil. Fecal samples were collected from 245 children aged 0-5 years, and questionnaires were asked about sociodemographic and hygiene-related characteristics. At the daycare centers where children tested positive, fecal samples were collected from the staff handling food, and from family members and domestic animals. Positive samples were analyzed at the dehydrogenase glutamate (gdh) locus to determine the genotype. The prevalence of G. duodenalis was 51.8%, and drinking unfiltered and unboiled water (OR 2.12, CI 1.26-3.69, p<0.001) and washing hands only with water (OR 2.14, Cl 1.19-4.04, p<0.001) were related risk factors. No association was found between test-positive children anti their family members, domestic animals and food handlers. An analysis of the sequences of 30 samples revealed that they all belonged to genotype B. (C) 2012 Royal Society of Tropical Medicine and Hygiene. Published by Elsevier Ltd. All rights reserved.

RHYTHM-AF: design of an international registry on cardioversion of atrial fibrillation and characteristics of participating centers

Background: Atrial fibrillation is a serious public health problem posing a considerable burden to not only patients, but the healthcare environment due to high rates of morbidity, mortality, and medical resource utilization. There are limited data on the variation in treatment practice patterns across different countries, healthcare settings and the associated health outcomes. Methods/design: RHYTHM-AF was a prospective observational multinational study of management of recent onset atrial fibrillation patients considered for cardioversion designed to collect data on international treatment patterns and short term outcomes related to cardioversion. We present data collected in 10 countries between May 2010 and June 2011. Enrollment was ongoing in Italy and Brazil at the time of data analysis. Data were collected at the time of atrial fibrillation episode in all countries (Australia, Brazil, France, Germany, Italy, Netherlands, Poland, Spain, Sweden, United Kingdom), and cumulative follow-up data were collected at day 60 (+/- 10) in all but Spain. Information on center characteristics, enrollment data, patient demographics, detail of atrial fibrillation episode, medical history, diagnostic procedures, acute treatment of atrial fibrillation, discharge information and the follow-up data on major events and rehospitalizations up to day 60 were collected. Discussion: A total of 3940 patients were enrolled from 175 acute care centers. 70.5% of the centers were either academic (44%) or teaching (26%) hospitals with an overall median capacity of 510 beds. The sites were mostly specialized with anticoagulation clinics (65.9%), heart failure (75.1%) and hypertension clinics (60.1%) available. The RHYTHM-AF registry will provide insight into regional variability of antiarrhythmic and antithrombotic treatment of atrial fibrillation, the appropriateness of such treatments with respect to outcomes, and their cost-efficacy. Observations will help inform strategies to improve cardiovascular outcomes in patients with atrial fibrillation.

Guidelines for the Development of Comprehensive Care Centers for Congenital Adrenal Hyperplasia: Guidance from the CARES Foundation Initiative

Patients with rare and complex diseases such as congenital adrenal hyperplasia (CAH) often receive fragmented and inadequate care unless efforts are coordinated among providers. Translating the concepts of the medical home and comprehensive health care for individuals with CAH offers many benefits for the affected individuals and their families. This manuscript represents the recommendations of a 1.5 day meeting held in September 2009 to discuss the ideal goals for comprehensive care centers for newborns, infants, children, adolescents, and adults with CAH. Participants included pediatric endocrinologists, internal medicine and reproductive endocrinologists, pediatric urologists, pediatric surgeons, psychologists, and pediatric endocrine nurse educators. One unique aspect of this meeting was the active participation of individuals personally affected by CAH as patients or parents of patients. Representatives of Health Research and Services Administration (HRSA), New York-Mid-Atlantic Consortium for Genetics and Newborn Screening Services (NYMAC), and National Newborn Screening and Genetics Resource Center (NNSGRC) also participated. Thus, this document should serve as a "roadmap" for the development phases of comprehensive care centers (CCC) for individuals and families affected by CAH.

Ravenna e i piu' significativi centri dell'Impero. Il mosaico parietale tra V e VI secolo: Revisione critica

Tra il V ed il VI secolo, la città di Ravenna, per tre volte capitale, emerge fra i più significativi centri dell’impero, fungendo da cerniera tra Oriente e Occidente, soprattutto grazie ai mosaici parietali degli edifici di culto, perfettamente inseriti in una koinè culturale e artistica che ha come comune denominatore il Mar Mediterraneo, nel contesto di parallele vicende storiche e politiche. Rispetto ai ben noti e splendidi mosaici ravennati, che insieme costituiscono senza dubbio un unicum nel panorama artistico dell’età tardoantica e altomedievale, nelle decorazioni musive parietali dei coevi edifici di culto dei diversi centri dell’impero d’Occidente e d’Oriente, e in particolare in quelli localizzati nelle aree costiere, si possono cogliere divergenze, ma anche simmetrie dal punto di vista iconografico, iconologico e stilistico. Sulla base della letteratura scientifica e attraverso un poliedrico esame delle superfici musive parietali, basato su una metodologia interdisciplinare, si è cercato di chiarire l’articolato quadro di relazioni culturali, ideologiche ed artistiche che hanno interessato e interessano tuttora Ravenna e i vari centri della tarda antichità, insistendo sulla pluralità, sulla complessità e sulla confluenza di diverse esperienze artistiche sui mosaici di Ravenna. A tale scopo, i dati archeologici e artistici sono stati integrati con quelli storici, agiografici ed epigrafici, con opportuni collegamenti all’architettura, alla scultura, alle arti decorative e alle miniature, a testimonianza dell’unità di intenti di differenti media artistici, orientati, pur nella diversità, verso le medesime finalità dogmatiche, politiche e celebrative. Si tratta dunque di uno studio di revisione e di sintesi sui mosaici parietali mediterranei di V e VI secolo, allo scopo di aggiungere un nuovo tassello alla già pur vasta letteratura dedicata all’argomento.

Bio-inspired polymer-supported nitrido molybdenum(VI) complexes for ammonia synthesis − reactivity towards protons and electrons : EPR investigations on paramagnetic molybdenum(V) and copper(II) complexes

Die biologische Stickstofffixierung durch Molybdän-haltige Nitrogenasen sowie die Erforschung des zugrundeliegenden komplexen Mechanismus (N2-Aktivierung an Metall-Zentren, 6-fache Protonierung und Reduktion, N–N Bindungsspaltung unter Bildung von Ammoniak) ist von erheblichem Interesse. Insbesondere Molybdän-Komplexe wurden bereits erfolgreich als Modellverbindungen für die Untersuchung elementarer Einzelschritte der N2-Aktivierung eingesetzt. Durch die Verwendung von Triamidoamin-Liganden ist es Schrock et al. sogar gelungen mehrere Katalysezyklen zu durchlaufen und einen Mechanismus zu formulieren. Trotz der sterisch anspruchsvollen Substituenten in den Schrock-Komplexen ist die Umsatzrate dieses homogenen Katalysators, aufgrund Komplex-Deaktivierung infolge intermolekularer Reaktionen wie Dimerisierung und Disproportionierung, limitiert. In der vorliegenden Arbeit wurden einige dieser Herausforderungen angegangen und die aktiven Spezies auf einer Festphase immobilisiert, um intermolekulare Reaktionen durch räumliche Isolierung der Komplexe zu unterdrücken.rnEin Polymer-verankertes Analogon des Schrock Nitrido-Molybdän(VI)-Komplexes wurde auf einem neuen Reaktionsweg synthetisiert. Dieser beinhaltet nur einen einzigen Reaktionsschritt, um die funktionelle Gruppe „MoN“ einzuführen. Protonierung des immobilisierten Nitrido-Molybdän(VI)-Komplexes LMoVIN (L = Polymer-verankerter Triamidoamin-Ligand) mit 2,6-Lutidinium liefert den entsprechenden Imido-Molybdän(VI)-Komplex. Durch anschließende Ein-Elektronen-Reduktion mit Cobaltocen wird der Polymer-angebundene Imido-Molybdän(V)-Komplex erhalten, bewiesen durch EPR-Spektroskopie (g1,2,3 = 1.989, 1.929, 1.902). Durch die Immobilisierung und die effektive räumliche Separation der Reaktionszentren auf der Festphase werden bimolekulare Nebenreaktionen, die oft in homogenen Systemen auftreten, unterdrückt. Dies ermöglicht zum ersten Mal die Darstellung des Imido-Molybdän(V)-Intermediates des Schrock-Zyklus.rnEPR-Spektren des als Spin-Label eingeführten immobilisierten Nitrato-Kupfer(II)-Komplexes wurden unter verschiedenen Bedingungen (Lösungsmittel, Temperatur) aufgenommen, wobei sich eine starke Abhängigkeit zwischen der Zugänglichkeit und Reaktivität der immobilisierten Reaktionszentren und der Art des Lösungsmittels zeigte. Somit wurde die Reaktivität von LMoVIN gegenüber Protonen und Elektronen, welches zur Bildung von NH3 führt, unter Verwendung verschiedener Lösungsmittel untersucht und optimiert. Innerhalb des kugelförmigen Polymers verläuft die Protonierung und Reduktion von LMoVIN stufenweise. Aktive Zentren, die sich an der „äußeren Schale“ des Polymers befinden, sind gut zugänglich und reagieren schnell nach H+/e− Zugabe. Aktive Zentren im „Inneren des Polymers“ hingegen sind schlechter zugänglich und zeigen langsame diffusions-kontrollierte Reaktionen, wobei drei H+/e− Schritte gefolgt von einer Ligandenaustausch-Reaktion erforderlich sind, um NH3 freizusetzen: LMoVIN  LMoVNH  LMoIVNH2  LMoIIINH3 und anschließender Ligandenaustausch führt zur Freisetzung von NH3.rnIn einem weiteren Projekt wurde der Bis(ddpd)-Kupfer(II)-Komplex EPR-spektroskopisch in Hinblick auf Jahn−Teller-Verzerrung und -Dynamik untersucht. Dabei wurden die EPR-Spektren bei variabler Temperatur (70−293 K) aufgenommen. Im Festkörperspektrum bei T &lt; 100 K erscheint der Kupfer(II)-Komplex als gestreckter Oktaeder, wohingegen das EPR-Spektrum bei höheren Temperaturen g-Werte aufzeigt, die einer pseudo-gestauchten oktaedrischen Kupfer(II)-Spezies zuzuordnen sind. Diese Tatsache wird einem intramolekularen dynamischen Jahn−Teller Phänomen zugeschrieben, welcher bei 100 K eingefroren wird.

Luz industrial e imagen tecnificada: de Moholy Nagy al C.A.V.S. (Center for Advanced Visual Studies)

El desarrollo de la tecnología de la luz implicará la transformación de la vida social, cultural y económica. Tanto las consideraciones espaciales del Movimiento Moderno, como los efectos producidos por la segunda Guerra Mundial, tendrán efectos visibles en las nuevas configuraciones espaciales y en la relación simbiótica y recíproca que se dará entre ideología y tecnología. La transformación en la comprensión de la articulación espacial, asociada al desarrollo tecnológico, afectará al modo en que este espacio es experimentado y percibido. El espacio expositivo y el espacio escénico se convertirán en laboratorio práctico donde desarrollar y hacer comprensible todo el potencial ilusorio de la luz, la proyección y la imagen, como parámetros modificadores y dinamizadores del espacio arquitectónico. Esta experimentación espacial estará precedida por la investigación y creación conceptual en el mundo plástico, donde los nuevos medios mecánicos serán responsables de la construcción de una nueva mirada moderna mediatizada por los elementos técnicos. La experimentación óptica, a través de la fotografía, el cine, o el movimiento de la luz y su percepción, vinculada a nuevos modos de representación y comunicación, se convertirá en elemento fundamental en la configuración espacial. Este ámbito de experimentación se hará patente en la Escuela de la Bauhaus, de la mano de Gropius, Schlemmer o Moholy Nagy entre otros; tanto en reflexiones teóricas como en el desarrollo de proyectos expositivos, arquitectónicos o teatrales, que evolucionarán en base a la tecnología y la modificación de la relación con el espectador. El espacio expositivo y el espacio escénico se tomarán como oportunidad de investigación espacial y de análisis de los modos de percepción, convirtiéndose en lugares de experimentación básicos para el aprendizaje. El teatro se postula como punto de encuentro entre el arte y la técnica, cobrando especial importancia la intersección con otras disciplinas en la definición espacial. Las múltiples innovaciones técnicas ligadas a los nuevos fundamentos teatrales en la modificación de la relación con la escena, que se producen a principios del siglo XX, tendrán como consecuencia la transformación del espacio en un espacio dinámico, tanto física como perceptivamente, que dará lugar a nuevas concepciones espaciales, muchas de ellas utópicas. La luz, la proyección y la creación de ilusión en base a estímulos visuales y sonoros, aparecen como elementos proyectuales efímeros e inmateriales, que tendrán una gran incidencia en el espacio y su modo de ser experimentado. La implicación de la tecnología en el arte conllevará modificaciones en la visualización, así como en la configuración espacial de los espacios destinados a esta. Destacaremos como propuesta el Teatro Total de Walter Gropius, en cuyo desarrollo se recogen de algún modo las experiencias espaciales y las investigaciones desarrolladas sobre la estructura formal de la percepción realizadas por Moholy Nagy, además de los conceptos acerca del espacio escénico desarrollados en el taller de Teatro de la Bauhaus por Oskar Schlemmer. En el Teatro Total, Gropius incorporará su propia visión de cuestiones que pertenecen a la tradición de la arquitectura teatral y las innovaciones conceptuales que estaban teniendo lugar desde finales del s.XIX, tales como la participación activa del público o la superación entre escena y auditorio, estableciendo en el proyecto una nueva relación perceptual entre sala, espectáculo y espectador; aumentando la sensación de inmersión, a través del uso de la física, la óptica, y la acústica, creando una energía concéntrica capaz de extenderse en todas direcciones. El Teatro Total será uno de los primeros ejemplos en los que desde el punto de partida del proyecto, se conjuga la imagen como elemento comunicativo con la configuración espacial. Las nuevas configuraciones escénicas tendrán como premisa de desarrollo la capacidad de transformación tanto perceptiva, como física. En la segunda mitad del s.XX, la creación de centros de investigación como el CAVS (The Center for Advanced Visual Studies,1967), o el EAT (Experiments in Art and Technology, 1966), favorecerán la colaboración interdisciplinar entre arte y ciencia, implicando a empresas de carácter tecnológico, como Siemens, HP, IBM o Philips, facilitando soporte técnico y económico para el desarrollo de nuevos sistemas. Esta colaboración interdisciplinar dará lugar a una serie de intervenciones espaciales que tendrán su mayor visibilidad en algunas Exposiciones Universales. El resultado será, en la mayoría de los casos, la creación de espacios de carácter inmersivo, donde se establecerá una relación simbiótica entre espacio, imagen, sonido, y espectador. La colocación del espectador en el centro de la escena y la disposición dinámica de imagen y sonido, crearán una particular narrativa espacial no lineal, concebida para la experiencia. Desde las primeras proyecciones de cine a la pantalla múltiple de los Eames, las técnicas espaciales de difusión del sonido en Stockhausen, o los experimentos con el movimiento físico interactivo, la imagen, la luz en movimiento y el sonido, quedan inevitablemente convertidos en material arquitectónico. ABSTRACT. Light technology development would lead to a social, cultural and economic transformation. Both spatial consideration of “Modern Movement” and Second World War effects on technology, would have a visible aftereffect on spatial configuration and on the symbiotic and mutual relationship between ideology & technology. Comprehension adjustment on the articulation of space together with technology development, would impact on how space is perceived and felt. Exhibition space and scenic space would turn into a laboratory where developing and making comprehensive all illusory potential of light, projection and image. These new parameters would modify and revitalize the architectonic space. as modifying and revitalizing parameters of architectonic space. Spatial experimentation would be preceded by conceptual creation and investigation on the sculptural field, where new mechanic media would be responsible for a fresh and modern look influenced by technical elements. Optical experimentation, through photography, cinema or light movement and its perception, would turn into essential components for spatial arrangement linked to new ways of performance and communication. This experimentation sphere would be clear at The Bauhaus School, by the hand of Gropius, Schlemmer or Moholy Nag among others; in theoretical, theatrical or architectural performance’s projects, that would evolve based on technology and also based on the transformation of the relationship with the observer. Exhibition and perfor-mance areas would be taken as opportunities of spatial investigation and for the analysis of the different ways of perception, thus becoming key places for learning. Theater is postulated as a meeting point between art and technique, taking on a new significance at its intersection with other disciplines working with spatial definition too. The multiple innovation techniques linked to the new foundations for the theater regarding stage relation, would have as a consequence the regeneration of the space. Space would turn dynamic, both physically and perceptibly, bringing innovative spatial conceptions, many of them unrealistic. Light, projection and illusory creation based on sound and visual stimulus would appear as intangible and momentary design components, which would have a great impact on the space and on the way it is experienced. Implication of technology in art would bring changes on the observer as well as on the spatial configuration of the art spaces2. It would stand out as a proposal Walter Groupis Total Theater, whose development would include somehow the spatial experiments and studies about formal structure of perception accomplished by Moholy Nagy besides the concepts regarding stage space enhanced at the Bauhaus Theater Studio by Oskar Schlemmer. Within Total Theater, Groupis would incorporate his own view about traditional theatric architecture and conceptual innovations that were taking place since the end of the nineteenth century, such as active audience participation or the diffusing limits between scene and audience, establishing a new perception relationship between auditorium, performance and audience, improving the feeling of immersion through the use of physics, optics and acoustics, creating a concentric energy capable of spreading in all directions. Total Theater would be one of the first example in which, from the beginning of the Project, image is combined as a communicating element with the spatial configuration. As a premise of development, new stage arrangement would have the capacity of transformation, both perceptive and physically. During the second half or the twentieth century, the creation of investigation centers such as CAVS (Center for Advanced Visual Studies, 1967) or EAT (Experiments in Art and Technology, 1966), would help to the interdisciplinary collaboration between art and science, involving technology companies like Siemens, HP, IBM or Philips, providing technical and economic support to the development of new systems. This interdisciplinary collaboration would give room to a series of spatial interventions which would have visibility in some Universal Exhibitions. The result would be, in most cases, the creation of immersive character spaces, where a symbiotic relationship would be stablished between space, image, sound and audience. The new location of the audience in the middle of the display, together with the dynamic arrangement of sound and image would create a particular, no lineal narrative conceived to be experienced. Since the first cinema projections, the multiple screen of Eames, the spatial techniques for sound dissemination at Stockhausen or the interactive physical movement experimentation, image, motion light and sound would turn inevitably into architectural material.

The extended environment of mononuclear metal centers in protein structures

The objectives of this and the following paper are to identify commonalities and disparities of the extended environment of mononuclear metal sites centering on Cu, Fe, Mn, and Zn. The extended environment of a metal site within a protein embodies at least three layers: the metal core, the ligand group, and the second shell, which is defined here to consist of all residues distant less than 3.5 Å from some ligand of the metal core. The ligands and second-shell residues can be characterized in terms of polarity, hydrophobicity, secondary structures, solvent accessibility, hydrogen-bonding interactions, and membership in statistically significant residue clusters of different kinds. Findings include the following: (i) Both histidine ligands of type I copper ions exclusively attach the Nδ1 nitrogen of the histidine imidazole ring to the metal, whereas histidine ligands for all mononuclear iron ions and nearly all type II copper ions are ligated via the Nɛ2 nitrogen. By contrast, multinuclear copper centers are coordinated predominantly by histidine Nɛ2, whereas diiron histidine contacts are predominantly Nδ1. Explanations in terms of steric differences between Nδ1 and Nɛ2 are considered. (ii) Except for blue copper (type I), the second-shell composition favors polar residues. (iii) For blue copper, the second shell generally contains multiple methionine residues, which are elements of a statistically significant histidine–cysteine–methionine cluster. Almost half of the second shell of blue copper consists of solvent-accessible residues, putatively facilitating electron transfer. (iv) Mononuclear copper atoms are never found with acidic carboxylate ligands, whereas single Mn2+ ion ligands are predominantly acidic and the second shell tends to be mostly buried. (v) The extended environment of mononuclear Fe sites often is associated with histidine–tyrosine or histidine–acidic clusters.

Photochemically induced nuclear spin polarization in reaction centers of photosystem II observed by 13C-solid-state NMR reveals a strongly asymmetric electronic structure of the P680.+ primary donor chlorophyll

We report 13C magic angle spinning NMR observation of photochemically induced dynamic nuclear spin polarization (photo- CIDNP) in the reaction center (RC) of photosystem II (PS2). The light-enhanced NMR signals of the natural abundance 13C provide information on the electronic structure of the primary electron donor P680 (chlorophyll a molecules absorbing around 680 nm) and on the pz spin density pattern in its oxidized form, P680⨥. Most centerband signals can be attributed to a single chlorophyll a (Chl a) cofactor that has little interaction with other pigments. The chemical shift anisotropy of the most intense signals is characteristic for aromatic carbon atoms. The data reveal a pronounced asymmetry of the electronic spin density distribution within the P680⨥. PS2 shows only a single broad and intense emissive signal, which is assigned to both the C-10 and C-15 methine carbon atoms. The spin density appears shifted toward ring III. This shift is remarkable, because, for monomeric Chl a radical cations in solution, the region of highest spin density is around ring II. It leads to a first hypothesis as to how the planet can provide itself with the chemical potential to split water and generate an oxygen atmosphere using the Chl a macroaromatic cycle. A local electrostatic field close to ring III can polarize the electronic charge and associated spin density and increase the redox potential of P680 by stabilizing the highest occupied molecular orbital, without a major change of color. This field could be produced, e.g., by protonation of the keto group of ring V. Finally, the radical cation electronic structure in PS2 is different from that in the bacterial RC, which shows at least four emissive centerbands, indicating a symmetric spin density distribution over the entire bacteriochlorophyll macrocycle.

Smart Monitoring Embedded Service for Energy-Efficient and Sustainable Management in Data Centers

Information technologies (IT) currently represent 2% of CO2 emissions. In recent years, a wide variety of IT solutions have been proposed, focused on increasing the energy efficiency of network data centers. Monitoring is one of the fundamental pillars of these systems, providing the information necessary for adequate decision making. However, today’s monitoring systems (MSs) are partial, specific and highly coupled solutions. This study proposes a model for monitoring data centers that serves as a basis for energy saving systems, offered as a value-added service embedded in a device with low cost and power consumption. The proposal is general in nature, comprehensive, scalable and focused on heterogeneous environments, and it allows quick adaptation to the needs of changing and dynamic environments. Further, a prototype of the system has been implemented in several devices, which has allowed validation of the proposal in addition to identification of the minimum hardware profile required to support the model.