CO2 and vitamin B12 interactions determine bioactive trace metal requirements of a subarctic Pacific diatom

Phytoplankton growth can be limited by numerous inorganic nutrients and organic growth factors. Using the subarctic diatom Attheya sp. in culture studies, we examined how the availability of vitamin B(12) and carbon dioxide partial pressure (pCO(2)) influences growth rate, primary productivity, cellular iron (Fe), cobalt (Co), zinc (Zn) and cadmium (Cd) quotas, and the net use efficiencies (NUEs) of these bioactive trace metals (mol C fixed per mol cellular trace metal per day). Under B(12)-replete conditions, cells grown at high pCO(2) had lower Fe, Zn and Cd quotas, and used those trace metals more efficiently in comparison with cells grown at low pCO(2). At high pCO(2), B(12)-limited cells had ~50% lower specific growth and carbon fixation rates, and used Fe ~15-fold less efficiently, and Zn and Cd ~3-fold less efficiently, in comparison with B(12)-replete cells. The observed higher Fe, Zn and Cd NUE under high pCO(2)/B(12)-replete conditions are consistent with predicted downregulation of carbon-concentrating mechanisms. Co quotas of B(12)-replete cells were 5- to 14-fold higher in comparison with B(12)-limited cells, suggesting that >80% of cellular Co of B(12)-limited cells was likely from B(12). Our results demonstrate that CO(2) and vitamin B(12) interactively influence growth, carbon fixation, trace metal requirements and trace metal NUE of this diatom. This suggests the need to consider complex feedback interactions between multiple environmental factors for this biogeochemically critical group of phytoplankton in the last glacial maximum as well as the current and future changing ocean.

Conceptual design of the liquid metal laboratory of the TECHNOFUSION facility

The application of liquid metal technology in fusion devices requires R&D related to many phenomena: interaction between liquid metals and structural material as corrosion, erosion and passivation techniques; magneto-hydrodynamics; free surface fluid-dynamics and any other physical aspect that will be needed for their safe reliable operation. In particular, there is a significant shortage of experimental facilities dedicated to the development of the lithium technology. In the framework of the TECHNOFUSION project, an experimental laboratory devoted to the lithium technology development is proposed, in order to shed some light in the path to IFMIF and the design of chamber's first wall and divertors. The conceptual design foresee a development in two stages, the first one consisting on a material testing loop. The second stage proposes the construction of a mock-up of the IFMIF target that will allow to assess the behaviour of a free-surface lithium target under vacuum conditions. In this paper, such conceptual design is addressed.

Effects of sheep and horse manure and pine bark amendments on metal distribution and chemical properties of contaminated mine soils.

Mine soils usually contain large levels of heavy metals and poor fertility conditions which limit their reclamation and the application of phyto-remediation technologies. Two organic waste materials (pine bark compost and sheep and horse manure compost), with different pHs and varying degrees of humification and nutrient contents, were applied as amendments to assess their effects on copper (Cu) and zinc (Zn) bioavailability and on fertility conditions of mine soils. Soil samples collected from two abandoned mining areas near Madrid (Spain) were mixed with 0, 30 and 60 t ha?1 of the organic amendments. The concentrations of metals among the different mineral and organic fractions of soil were determined by several extraction procedures to study the metal distribution in the solid phase of the soil affected by the organic amendments. The results showed that the manure amendment increased the soil pH and the cation exchange capacity and enhanced the nutrient levels of these soils. The pine bark amendment decreased the soil pH and did not significantly change the nutrient status of soil. Soil pH, organic matter content and its degree of humification, which were altered by the amendments, were the main factors affecting Cu fractionation. Zn fractionation was mainly affected by soil pH. The addition of manure not only improved soil fertility, but also decreased metal bioavailability resulting in a reduction of metal toxicity. Conversely, pine bark amendment increased metal ioavailability. The use of sheep and horse manure could be a cost-effective practice for the restoration of contaminated mine soils.

Phytostabilization of metals in mine soils using Brassica juncea in combination with organic amendments

Background and aims The high metal bioavailability and the poor conditions of mine soils yield a low plant biomass, limiting the application of phytoremediation techniques. A greenhouse experiment was performed to evaluate the effects of organic amendments on metal stabilization and the potential of Brassica juncea L. for phytostabilization in mine soils. Methods Plants were grown in pots filled with soils collected from two mine sites located in Central Spain mixed with 0, 30 and 60 tha?1 of pine bark compost and horse- and sheep-manure compost. Plant biomass and metal concentrations in roots and shoots were measured. Metal bioavailability was assessed using a rhizosphere-based method (rhizo), which consists of a mixture of low-molecular-weight organic acids to simulate root exudates. Results Manure reduced metal concentrations in shoots (10?50 % reduction of Cu and 40?80 % of Zn in comparison with non-amended soils), bioconcentration factor (10?50 % of Cu and 40?80 % of Zn) and metal bioavailability in soil (40?50 % of Cu and 10?30 % of Zn) due to the high pH and the contribution of organic matter. Manure improved soil fertility and was also able to increase plant biomass (5?20 times in shoots and 3?30 times in roots), which resulted in a greater amount of metals removed from soil and accumulated in roots (increase of 2?7 times of Cu and Zn). Plants grown in pine bark treatments and in non-amended soils showed a limited biomass and high metal concentrations in shoots. Conclusions The addition of manure could be effective for the stabilization of metals and for enhancing the phytostabilization ability of B. juncea in mine soils. In this study, this species resulted to be a potential candidate for phytostabilization in combination with manure, differing from previous results, in which B. juncea had been recognized as a phytoextraction plant.

Intermediate band solar cells. The transition metal supersaturated Silicon approach

Within the framework of the third solar cell generation some new ideas to enlarge the spectral response of the solar cells toward the infrared have been proposed. Among them the inclusion of an Intermediate Band (IB) seems to be very promising. This paper will deal with one of the ways to generate the IB namely the deep level center approach. We will discuss not only its existence but also the carriers lifetime recovery which is necessary to obtain the expected increase of the solar cell efficiency.

Análisis de la geometría de Pablo Palazuelo desde la visión del arquitecto

Esta investigación indaga sobre la relación entre el método geométrico empleado por Pablo Palazuelo y el proceso del proyecto arquitectónico. La elección de este pintor y escultor madrileño como hilo conductor de esta tesis no es fortuita, puesto que la arquitectura desempeña una influencia esencial sobre su obra. Un influjo que le llega en parte a través de su formación académica, dado que cursó estudios de arquitectura en la School of Arts and Crafts de la ciudad de Oxford (1933-1936). Así mismo diseñó propuestas estrechamente vinculadas a un lugar construido, con el consiguiente condicionante de las trazas del mismo. La hipótesis de trabajo formulada a partir de textos elaborados por autores como Víctor Nieto Alcaide y Juan Daniel Fullaondo sugería una interconexión con la arquitectura orgánica. Como comprobación del grado de profundidad en otros análisis publicados, se han seleccionado los textos que indagan en el proceso que el artista desarrollaba durante la producción de su obra, y se adentran en cuestiones estructurales que trascienden el ámbito formal. Siguiendo esta pauta, además de una acotación temporal, se han escogido los realizados por Santiago Amón, Carme Bonell, Valerio Bozal, Manuel J. Borja-Villel, Francisco Calvo Serraller, Claude Esteban, Julián Gállego, Teresa Grandas, Max Hölzer, George Limbour, Kevin Power y Carlos Rodríguez-Spiteri. A estos autores se suman las fuentes orales consultadas dentro de un entorno intrínsecamente próximo a sus realizaciones, procedentes de Pere Casanovas y Soledad Lorenzo. Además de personas que en diferentes etapas de su vida coincidieron por distintos motivos con sus realizaciones, como son Ramón Ayerza, Mariano Bayón, José Antonio Corrales, Luis Gordillo, Rafael Moneo, José Rodríguez-Spiteri y Antonio Tornero. A partir del acceso obtenido a los escritos, libros, bocetos y abundante obra gráfica y escultórica que atesora la Fundación del pintor, se ha podido elaborar un andamiaje tanto teórico como geométrico que ha servido de base para confrontar estas premisas. Esta empresa se ha estructurado en una narración que, además de los estudios precedentes citados, comienza con los cimientos del pensamiento de Palazuelo. Elaborada a partir de sus escritos, donde defendía un sincretismo que concilia las visiones de las culturas occidental y oriental. En los siguientes apartados, se han analizado las principales obras gráficas y escultóricas del autor haciendo un especial hincapié en el método productivo. Una gestación que se resiste a una mera enumeración cronológica, por lo que la clasificación que se propone en este trabajo trata de ser lo más fiel posible al espíritu expresado por Palazuelo basado en linajes y coherencias, para desvelar las herramientas empleadas y poder compararlas con el proceso del proyectual. Este recorrido se completa con una última sección se reúnen por primera vez las dieciséis obras y los dieciséis proyectos más representativos que ilustran la aproximación más directa que obró Palazuelo entre sus investigaciones geométricas y un locus determinado. Durante casi cuatro años se desarrolló un inventariado y catalogación pormenorizada de la documentación y piezas sobre papel, lienzo y metal realizadas por Palazuelo. Esta indagación saca a la luz un conjunto constituido por casi cuatro mil obras, en su mayoría inéditas, que constituyen el archivo de la citada institución. En definitiva, esta investigación construye un tejido gráfico y geométrico referido a uno de los artistas españoles más importantes del siglo XX, entreverado por su pensamiento teórico y realizaciones en dibujos, maquetas, esculturas y propuestas arquitectónicas. Las cuales permiten establecer los acuerdos y desacuerdos con el proceso de la arquitectura para proponer una nueva aproximación geométrica interdisciplinar. ABSTRACT This research investigates the relationship between the geometric method used by Palazuelo and the architectural design’s process. Choosing this Spanish painter and sculptor as thread of this thesis is not fortuitous, since the architecture has an essential influence on his work. An influx that arrives in part through his academic training, as he was an architecture student at the School of Arts and Crafts of the city of Oxford (1933-1936). Furthermore his proposals designed closely linked to a built place, therefore conditioned by its traces. The working hypothesis formulated from texts written by authors like Victor Nieto Alcaide and Juan Daniel Fullaondo suggested an interconnection with organic architecture. As a check on the degree of depth in other published reviews, articles that explore the process that the artist developed during the production of his work, and penetrate into structural issues beyond formal domain have been selected. Following this pattern, along with a temporal dimension, assays by Santiago Amón, Carme Bonell, Valerio Bozal, Manuel J. Borja-Villel, Francisco Calvo Serraller, Claude Esteban, Julián Gállego, Teresa Grandas, Max Hölzer, George Limbour, Kevin Power and Carlos Rodriguez-Spiteri have been selected. Oral sources within an inherently environment close to his achievements, as Pere Casanovas and Soledad Lorenzo, are also added. In addition to people coincided with his accomplishments, such as Ramón Ayerza, Mariano Bayón, José Antonio Corrales, Luis Gordillo, Rafael Moneo, José Rodríguez-Spiteri and Antonio Tornero. From obtained access to the writings, books, sketches and abundant graphic and sculptural work that holds the Foundation painter, it has been able to develop a theoretical and geometric framework that have served as the basis for confronting these premises. This dissertation has been structured in a narrative that ⎯in addition to the previously mentioned studies⎯, begins with the foundations of Palazuelo thought. A structure built from his writings, where he defended a syncretism that reconciles the views of Western and Eastern cultures. In the following sections, his main graphic and sculptural works have been analyzed with particular emphasis on the productive method. A process that resists mere chronological enumeration, so the classification proposed in this investigation tries to be as faithful as possible to the spirit expressed by Palazuelo, based on bloodlines and coherences, to uncover the tools he used and to compare them with the architectural design process. This tour is completed with a final chapter that gathers the sixteen proposals and sixteen works most representative projects that illustrate the more direct approach that Palazuelo worked between geometric investigations and a given locus. For nearly four years, a detailed inventory and cataloguing of documents and works on paper, canvas and metal made by Palazuelo was developed. This research brings to light a set consisting of nearly four thousand works, mostly unpublished, that constitute the current archive of the aforementioned institution. Ultimately, this research builds a graph and geometric fabric referred to one of the most important Spanish artists of the twentieth century, interspersed by his theoretical thinking and achievements in drawings, models, sculptures and architectural proposals. Which allow establishing agreements and disagreements with the process of architecture to propose a new geometric interdisciplinary approach.

Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra

A family of nanoscale-sized supramolecular cage compounds with a polyhedral framework is prepared by self-assembly from tritopic building blocks and rectangular corner units via noncovalent coordination interactions. These highly symmetrical cage compounds are described as face-directed, self-assembled truncated tetrahedra with Td symmetry.

Double-level “orthogonal” dynamic combinatorial libraries on transition metal template

Dynamic combinatorial libraries are mixtures of compounds that exist in a dynamic equilibrium and can be driven to compositional self adaptation via selective binding of a specific assembly of certain components to a molecular target. We present here an extension of this initial concept to dynamic libraries that consists of two levels, the first formed by the coordination of terpyridine-based ligands to the transition metal template, and the second, by the imine formation with the aldehyde substituents on the terpyridine moieties. Dialdehyde 7 has been synthesized, converted into a variety of ligands, oxime ethers L11–L33 and acyl hydrazones L44–L77, and subsequently into corresponding cobalt complexes. A typical complex, Co(L22)22+ is shown to engage in rapid exchange with a competing ligand L11 and with another complex, Co(L22)22+ in 30% acetonitrile/water at pH 7.0 and 25°C. The exchange in the corresponding Co(III) complexes is shown to be much slower. Imine exchange in the acyl hydrazone complexes (L44–L77) is strongly controlled by pH and temperature. The two types of exchange, ligand and imine, can thus be used as independent equilibrium processes controlled by different types of external intervention, i.e., via oxidation/reduction of the metal template and/or change in the pH/temperature of the medium. The resulting double-level dynamic libraries are therefore named orthogonal, in similarity with the orthogonal protecting groups in organic synthesis. Sample libraries of this type have been synthesized and showed the complete expected set of components in electrospray ionization MS.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Electrocatalytic reduction of CO2 to formate using particulate Sn electrodes: Effect of metal loading and particle size

The development of electrochemical processes for the conversion of CO2 into value-added products allows innovative carbon capture & utilization (CCU) instead of carbon capture & storage (CCS). In addition, coupling this conversion with renewable energy sources would make it possible to chemically store electricity from these intermittent renewable sources. The electroreduction of CO2 to formate in aqueous solution has been performed using Sn particles deposited over a carbon support. The effect of the particle size and Sn metal loading has been evaluated using cyclic voltammetry and chronoamperometry. The selected electrode has been tested on an experimental filter-press type cell system for continuous and single pass CO2 electroreduction to obtain formate as main product at ambient pressure and temperature. Experimental results show that using electrodes with 0.75 mg Sn cm−2, 150 nm Sn particles, and working at a current density of 90 mA cm−2, it is possible to achieve rates of formate production over 3.2 mmol m−2 s−1 and faradaic efficiencies around 70% for 90 min of continuous operation. These experimental conditions allow formate concentrations of about 1.5 g L−1 to be obtained on a continuous mode and with a single pass of catholyte through the cell.

Mesoporous Metal Complex–Silica Aerogels for Environmentally Friendly Amination of Allylic Alcohols

Two series of mesoporous hybrid iron(III) complex–silica aerogels were prepared in one-pot synthesis by using the sol–gel coordination chemistry approach. The use of the ligands 3-(2-aminoethylamino)propyltrimethoxysilane and 2-(diphenylphosphino)ethyltriethoxysilane, both with terminal triethoxysilyl groups, were used to incorporate metal complexes in situ into the framework of silica, through their co-condensation with a silicon alkoxide during the aerogel formation. This methodology yielded optically translucent hybrid mesoporous gels with homogeneous metal incorporation and excellent textural properties. The catalytic performance of these materials was tested in the direct amination of allylic alcohols in water as a target reaction, with activities comparable or even higher than those corresponding to the homogeneous iron(III) complex. Furthermore, these catalysts were stable and maintained their catalytic activity after six reaction cycles.