Modelling the effects of salt solutions on the hydration of calcium ions

Classical molecular dynamics simulations of several aqueous alkali halide salt solutions have been used to determine the effect of electrolytes on the structure of water and the hydration properties of calcium ions. Compared with the simulations of Ca2+ ions in pure liquid water, the frequency of water exchange in the first hydration shell of calcium, which is a fundamental process in controlling the reactivity of calcium(II) aqua-ions, is drastically reduced in the presence of other electrolytes in solution. The strong stabilization of the hydration shell of Ca2+ occurs not only when the halide anions are directly coordinated to calcium, but also when the alkali and halide ions are placed at or outside the second coordination shell of Ca2+, suggesting that the reactivity of the first solvation shell of the calcium ion can be influenced by the specific affinity of other ions in solution for the water molecules coordinated to Ca2+. Analysis of the hydrogen-bonded structure of water in the vicinity of the calcium ion shows that the average number of hydrogen bonds per water molecules, which is 1.8 in pure liquid water, decreases as the concentration of alkali–halide salts in solution increases, and that the temporal fluctuations of hydrogen bonds are significantly larger than those obtained for Ca2+ in pure liquid water. This effect has been explained in terms of the dynamics of reorganization of the O–H X (X = F, Cl and Br) hydrogen bond. This work shows the importance of solution composition in determining the hydrogen-bonding network and ligand-exchange dynamics around metal ions, both in solution and at the mineral–water interfaces, which in turn has implications for interactions occurring at the mineral–water interface, ultimately controlling the mobilization of ions in the environment as well as in industrial processes

El proyecto de vivienda como laboratorio de estrategias para Sejima y Nishizawa de 1987 a 2010

Como indica el título, esta tesis plantea el estudio de la arquitectura doméstica elaborada por los arquitectos japoneses Kazuyo Sejima y Ryue Nishizawa. Más concretamente, la investigación se ciñe a un conjunto integrado por veinticinco casas que los arquitectos proyectaron entre 1987, momento en el que Sejima establece su propia oficina, y 2010, fecha en la que el reconocimiento del trabajo que ambos venían desarrollando queda certificado a nivel internacional, ya que ese año son galardonados con el premio Pritzker y comisarían la Bienal deVenecia. Del estudio conjunto y sistemático de estos proyectos, y de sus distintas versiones se espera poder obtener una serie de criterios exegéticos que permitan comprenderlos y explicarlos mejor, relacionándolos entre sí de manera coherente. A estos criterios es a lo que hemos denominado estrategias. En el momento en el que se inicia esta investigación se detectó un vacío editorial respecto al tema tratado, apenas había textos, propios o ajenos que abordaran esta faceta de la obra de Sejima y Nishizawa en profundidad. No en vano, algunos críticos han acuñado el apelativo de "arquitectos sin palabras" para referirse, tanto a ellos como a la generación de arquitectos que la pareja encabeza, dando a entender que se trata de una arquitectura carente de explicación.1 Sin embargo, esta investigación sostiene que el hecho de que los arquitectos no hablen en exceso de su obra y mantengan una actitud centrada en desarrollar de forma práctica su trabajo no quiere decir que prescindan de realizar operaciones compositivas altamente idealizadas y abstractas, refrendadas por un marco cultural y teórico que se pueda describir. Tras recopilar, ordenar y analizar un número lo suficientemente amplio como para ser significativo de las manifestaciones verbales que los arquitectos han realizado a lo largo del periodo estudiado, se ha observado que de entre todos los términos que los dos socios que integran SANAA emplean para describir sus proyectos, uno de los más relevantes y quizás también el más general resulta la palabra “sistema”.2 El modo en el que ambos describen los principios de su arquitectura, diferenciando entre los componentes del programa, y las relaciones que se establecen entre éstos, y entre ellos y el exterior permiten sostener que no se trata de un uso accidental término. Paralelamente, al mismo tiempo que se indaga sobre el corpus intelectual de esta teoría se intenta detallar las circunstancias que favorecieron tal trasvase de ideas entre Occidente y Japón y como acabaron llegando al ámbito de estos arquitectos. Al amparo de este marco teórico y tras redibujar las viviendas documentadas, se intentará describir los rasgos de la estructura material de las viviendas analizadas, así como cartografiar los patrones organizativos que las caracterizan. Para ello se empleará el rigor instrumental que aporta la teoría de grafos como método habitual para la representación, estudio y caracterización de sistemas. Los resultados de la investigación evidencian que hay una serie de estrategias — tanto materiales como organizativas— que enunciadas en sus primeros proyectos se van desarrollando en obras posteriores, conformado sistemas que están paulatinamente más organizados. Y que llegado un punto en la trayectoria de estos arquitectos, se observa que tales estrategias, se van superponiendo de distinta forma en diversos proyectos, por lo que es posible agruparlos y hablar de ellos atendiendo a características comunes. Finalmente, el estudio concluye que tanto a nivel material como reladonal, bien podría decirse que en el periodo estudiado, las estrategias empleadas por Sejima y Nishizawa para elaborar su arquitectura doméstica persiguen un objetivo común que se fundamenta en la elaboración de planteamientos sintéticos que les permiten explorar y responder creativamente ante las disyuntivas previamente establecidas, precisamente explotando el potencial de las paradojas que las originan. ABSTRACT As the title suggest itself, this thesis deals about the study of domestic architecture developed by Japanese architects Kazuyo Sejima and Ryue Nishizawa. More specifically, research focus its attention on a group of twenty five houses that both architects projected from 1987, when Sejima establishes her own practice, and 2010, as the moment in which their work obtains international acknowledgment, since this year they are awarded the Pritzker prize and cúrate the Venice Biennale. From the combined and systematic study of all these projects, and their different versions are expected to obtain a series of exegetical criteria to relate to each other, understand and explain better. These criteria are what we cali strategies. By the time when this research began, an editorial emptiness about the treaty issue was detected; there were barely texts that addressed this aspect of the work of Sejima and Nishizawa in depth, neither the ones written by the architects themselves ñor by other authors. Some critics have coined the ñame "wordless generation" to refer to both them as to the generation of architects that the couple leads, implying that it is an architecture devoid of explanation.3 However, this study argües that the fact that architects do not speak too much about his work and keep themselves focused on developing practical work attitude does not mean that dispense perform highly idealized and abstract compositional operations, fueled by a frame cultural and theoretical that can be described. After collect, sort and analyze a large enough number of verbal statements done by the architects about their work as to be meaningful, it was observed that of all the terms that the two partners that intégrate SANAA used to describe their projects, one of the most important and, perhaps one of the most general, is the word "system".4 The way in which both describe the principies of their architecture distinguishing between program components and the relationships established between them, and between them and the outside allow us the view that it is not accidental use of a term. Similarly, while it investigates the intellectual corpus of this theory it attempts to explain some of the circumstances that favored such transfer of ideas between the West and Japan and how eventually reaching the scope of these architects. Under this framework and after redraw the documented houses we attempt to describe the characteristics of the material structure of the projects tested, as well as mapping the organizational patterns that characterize them. For this, we use the instrumental rigor that brings graph theory, as a regular method of representation, study and characterization of systems used. The research results show that there are a number of strategies -both material and organizational level- that once they are set out in its first projects are developed in later works. Bringing up systems that are gradually more and more organized. And at one point in the career of these architects, such strategies are observed, they are superimposed differently on various projects, making it possible to group them and discuss them according to common characteristics. Finally, the study condueles that both materially and organizational it could be said that in the period studied, the strategies employed by Sejima and Nishizawa to develop its domestic architecture pursue a common goal, which is based on the development of synthetic approaches that allow them explore and respond creatively to the previously established dilemmas precisely exploiting the paradoxical potential that originates them

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

<p>Abstract</p> <p>Background</p> <p>A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., <inline-formula><m:math name="1467-4866-13-1-i1" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula>). To better understand the effect of ion activity ratios on CaCO₃precipitation kinetics and Sr²⁺co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio <inline-formula><m:math name="1467-4866-13-1-i2" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:mrow><m:mo class="MathClass-open">(</m:mo><m:mrow><m:mi>r</m:mi><m:mo class="MathClass-rel">=</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:mrow><m:mo class="MathClass-close">)</m:mo></m:mrow></m:math></inline-formula> was varied between 0.0032 and 4.15.</p> <p>Results</p> <p>Calcite was the only phase observed, by XRD, at the end of the experiments. Precipitation rates increased from 41.3 ± 3.4 μmol m^-2min^-1at <it>r = </it>0.0315 to a maximum rate of 74.5 ± 4.8 μmol m^-2min^-1at <it>r = </it>0.306 followed by a decrease to 46.3 ± 9.6 μmol m^-2min^-1at <it>r </it>= 1.822. The trend was simulated using a simple mass transfer model for solute uptake at the calcite surface. However, precipitation rates at fixed saturation states also evolved with time. Precipitation rates accelerated for low <it>r </it>values but slowed for high <it>r </it>values. These trends may be related to changes in effective reactive surface area. The <inline-formula><m:math xmlns:m="http://www.w3.org/1998/Math/MathML" name="1467-4866-13-1-i1"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula> ratios did not affect the distribution coefficient for Sr in calcite (D^P_Sr²⁺), apart from the indirect effect associated with the established positive correlation between D^P_Sr²⁺and calcite precipitation rate.</p> <p>Conclusion</p> <p>At a constant supersaturation state (Ω = 9.4), varying the ion activity ratio affects the calcite precipitation rate. This behavior is not predicted by affinity-based rate models. Furthermore, at the highest ion ratio tested, no precipitation was observed, while at the lowest ion ratio precipitation occurred immediately and valid rate measurements could not be made. The maximum measured precipitation rate was 2-fold greater than the minima, and occurred at a carbonate to calcium ion activity ratio of 0.306. These findings have implications for predicting the progress and cost of remediation operations involving enhanced calcite precipitation where mineral precipitation rates, and the spatial/temporal distribution of those rates, can have significant impacts on the mobility of contaminants.</p

Protection and consolidation of stone heritage by self-inoculation with indigenous carbonatogenic bacterial communities

Enhanced salt weathering resulting from global warming and increasing environmental pollution is endangering the survival of stone monuments and artworks. To mitigate the effects of these deleterious processes, numerous conservation treatments have been applied that, however, show limited efficacy. Here we present a novel, environmentally friendly, bacterial self-inoculation approach for the conservation of stone, based on the isolation of an indigenous community of carbonatogenic bacteria from salt damaged stone, followed by their culture and re-application back onto the same stone. This method results in an effective consolidation and protection due to the formation of an abundant and exceptionally strong hybrid cement consisting of nanostructured bacterial CaCO3 and bacterially derived organics, and the passivating effect of bacterial exopolymeric substances (EPS) covering the substrate. The fact that the isolated and identified bacterial community is common to many stone artworks may enable worldwide application of this novel conservation methodology.This work was supported by the Spanish Government (Grants MAT2012-37584, CGL2012-35992 and CGL2015-70642-R), the Junta de Andalucía through Proyecto de excelencia RNM-3493 and Project P11-RNM-7550, the Research Groups BIO 103 and RNM-179, and the University of Granada (Unidad Científica de Excelencia UCE-PP2016-05). Additional funds were provided by the Molecular Foundry (Lawrence Berkeley National Laboratory, LBNL, University of California, Berkeley, CA) for a research stay of M.S. (project #1451; User Agreement No. NPUSR009206)

The structure of spray-dried detergent powders

The complex multi-scale structure of spray-dried detergent granules has been characterized using a range of techniques including microscopy, wide-angle and small-angle X-ray scattering and X-ray microtomography. Four simple model formulations based on linear alkyl benzene sulphonate (NaLAS) and sodium sulphate were used to probe the influence of initial slurry water content and sodium silicate on the structure. The structure can be viewed as a porous matrix consisting of liquid crystalline NaLAS, sodium sulphate and binder in which large crystals of sodium sulphate are embedded. These large crystals were initially undissolved in the slurry and are consequently reduced in number in the product made from higher water content slurry. The both slurry water content and sodium silicate changed the polymorphs, and the d-spacing of the lamellae. The surface micro-structure and particle morphology can also be significantly affected with the high initial water content; particles having a distinct agglomerated and blistered structure

Mutagenesis-Mediated Virus Extinction: Virus-Dependent Effect of Viral Load on Sensitivity to Lethal Defection

Background: Lethal mutagenesis is a transition towards virus extinction mediated by enhanced mutation rates during viral genome replication, and it is currently under investigation as a potential new antiviral strategy. Viral load and virus fitness are known to influence virus extinction. Here we examine the effect or the multiplicity of infection (MOI) on progeny production of several RNA viruses under enhanced mutagenesis. Results: The effect of the mutagenic base analogue 5-fluorouracil (FU) on the replication of the arenavirus lymphocytic choriomeningitis virus (LCMV) can result either in inhibition of progeny production and virus extinction in infections carried out at low multiplicity of infection (MOI), or in a moderate titer decrease without extinction at high MOI. The effect of the MOI is similar for LCMV and vesicular stomatitis virus (VSV), but minimal or absent for the picornaviruses foot-and-mouth disease virus (FMDV) and encephalomyocarditis virus (EMCV). The increase in mutation frequency and Shannon entropy (mutant spectrum complexity) as a result of virus passage in the presence of FU was more accentuated at low MOI for LCMV and VSV, and at high MOI for FMDV and EMCV. We present an extension of the lethal defection model that agrees with the experimental results. Conclusions: (i) Low infecting load favoured the extinction of negative strand viruses, LCMV or VSV, with an increase of mutant spectrum complexity. (ii) This behaviour is not observed in RNA positive strand viruses, FMDV or EMCV. (iii) The accumulation of defector genomes may underlie the MOI-dependent behaviour. (iv) LCMV coinfections are allowed but superinfection is strongly restricted in BHK-21 cells. (v) The dissimilar effects of the MOI on the efficiency of mutagenic-based extinction of different RNA viruses can have implications for the design of antiviral protocols based on lethal mutagenesis, presently under development. © 2012 Moreno et al.Centro de Biología Molecular Severo Ochoa; Ministerio de Ciencia e Innovación (MICINN); Fundación Ramón ArecesPeer Reviewe

Database of spatial distribution of non indigenous species in Spanish marine waters

Research in marine Spanish waters are focused on several actions to achieve an effectively management on protected areas, with the active participation of the stakeholders and research as basic tools for decision-making. Among these actions, there is one about the knowledge and control on NIS. One of its objectives is the creation of NIS factsheets, which are going to be added to the National Marine Biodiversity Geographical System (GIS) providing complementary information about taxonomic classification, common names, taxonomic synonyms, species illustrations, identification morphological characters, habitat in the native and introduced regions, biological and ecological traits, GenBank DNA sequences, world distribution, first record and evolution in the introduced areas, likely pathways of introduction, effects in the habitats and interaction with native species, and potential management measures to apply. The database will also provide data for (1) the European online platforms, (2) the environmental assessment for the Descriptor 2 (D2-NIS) of the EU Marine Strategy Framework Directive (MSFD), as well as (3) supporting decisions made by stakeholders. It is the result of extensive collaboration among scientist, manager’s and citizen science in the Spanish North-Atlantic, South-Atlantic, Gibraltar Strait-Alboran, Levantine-Balearic and Canary Islands marine divisions, providing an updated overview of the spatial distribution of relevant extended and invasive NIS of recent and established NIS introduced by maritime transport and aquaculture pathways, as well as on cryptogenic or native species in expansion due to the climatic water warming trend

A Multi-Step Process of Viral Adaptation to a Mutagenic Nucleoside Analogue by Modulation of Transition Types Leads to Extinction-Escape

Resistance of viruses to mutagenic agents is an important problem for the development of lethal mutagenesis as an antiviral strategy. Previous studies with RNA viruses have documented that resistance to the mutagenic nucleoside analogue ribavirin (1-β-D-ribofuranosyl-1-H-1,2,4-triazole-3-carboxamide) is mediated by amino acid substitutions in the viral polymerase that either increase the general template copying fidelity of the enzyme or decrease the incorporation of ribavirin into RNA. Here we describe experiments that show that replication of the important picornavirus pathogen foot-and-mouth disease virus (FMDV) in the presence of increasing concentrations of ribavirin results in the sequential incorporation of three amino acid substitutions (M296I, P44S and P169S) in the viral polymerase (3D). The main biological effect of these substitutions is to attenuate the consequences of the mutagenic activity of ribavirin —by avoiding the biased repertoire of transition mutations produced by this purine analogue—and to maintain the replicative fitness of the virus which is able to escape extinction by ribavirin. This is achieved through alteration of the pairing behavior of ribavirin-triphosphate (RTP), as evidenced by in vitro polymerization assays with purified mutant 3Ds. Comparison of the three-dimensional structure of wild type and mutant polymerases suggests that the amino acid substitutions alter the position of the template RNA in the entry channel of the enzyme, thereby affecting nucleotide recognition. The results provide evidence of a new mechanism of resistance to a mutagenic nucleoside analogue which allows the virus to maintain a balance among mutation types introduced into progeny genomes during replication under strong mutagenic pressure

Genomic characterization of individuals presenting extreme phenotypes of high and low risk to develop tobacco-induced lung cancer

Single nucleotide polymorphisms (SNPs) may modulate individual susceptibility to carcinogens. We designed a genome-wide association study to characterize individuals presenting extreme phenotypes of high and low risk to develop tobacco-induced non-small cell lung cancer (NSCLC), and we validated our results. We hypothesized that this strategy would enrich the frequencies of the alleles that contribute to the observed traits. We genotyped 2.37 million SNPs in 95 extreme phenotype individuals, that is: heavy smokers that either developed NSCLC at an early age (extreme cases); or did not present NSCLC at an advanced age (extreme controls), selected from a discovery set (n=3631). We validated significant SNPs in 133 additional subjects with extreme phenotypes selected from databases including >39,000 individuals. Two SNPs were validated: rs12660420 (p(combined)=5.66x10(-5); ORcombined=2.80), mapping to a noncoding transcript exon of PDE10A; and rs6835978 (p(combined)=1.02x10(-4); ORcombined=2.57), an intronic variant in ATP10D. We assessed the relevance of both proteins in early-stage NSCLC. PDE10A and ATP10D mRNA expressions correlated with survival in 821 stage I-II NSCLC patients (p=0.01 and p<0.0001). PDE10A protein expression correlated with survival in 149 patients with stage I-II NSCLC (p=0.002). In conclusion, we validated two variants associated with extreme phenotypes of high and low risk of developing tobacco-induced NSCLC. Our findings may allow to identify individuals presenting high and low risk to develop tobacco-induced NSCLC and to characterize molecular mechanisms of carcinogenesis and resistance to develop NSCLC