L'increment de CO2 pot tenir efectes imprevisibles en el clima del planeta

L'ús de combustibles fòssils ha incrementat el CO2 a l'atmosfera i, en conseqüència, l'acidificació dels oceans al llarg dels últims cent anys. I això ha afectat els ecosistemes marins, especialment els organismes amb esquelet calcari com els coralls i certes microalgues. Un equip internacional d'investigadors, amb la participació de la UAB, ha examinat, per primer cop a escala global, com reaccionen en el seu hàbitat natural aquestes microalgues, i han observat que l'efecte és més sever de l'esperat: redueixen el gruix del seu esquel·let i empren més energia per construir-lo. Aquestes petites diferències fisiològiques les situen en desavantatge respecte a espècies competidores i poden arribar a ser substituides parcialment per d'altres. Donat que la captació del diòxid de carboni atmosfèric depèn en gran mesura de l'activitat d'aquests organismes, els efectes observats poden tenir conseqüències imprevisibles per al cicle global del carboni i, per tant, per al clima del planeta. La recerca ha estat publicada a Nature.El uso de combustibles fósiles ha incrementado el CO2 en la atmósfera y, en consecuencia, la acidificación de los océanos en los últimos cien años, lo que ha afectado a los ecosistemas marinos, especialmente a los organismos con esqueleto calcáreo como los corales y ciertas microalgas. Un equipo internacional de investigadores, con la participación de la UAB, ha examinado, por primera vez a escala global, cómo reaccionan en su hábitat natural estas microalgas, y han observado que el efecto es más severo de lo esperado: reducen el grueso de su esqueleto y emplean más energía para construirlo. Estas pequeñas diferencias fisiológicas las sitúan en desventaja respecto a especies competidoras, pudiendo llegar a ser sustituidas parcialmente por otras. Dado que la captación del dióxido de carbono atmosférico depende en gran medida de la actividad de estos organismos, los efectos observados pueden tener consecuencias imprevisibles para el ciclo global del carbono y, por tanto, para el clima del planeta. La investigación ha sido publicada en Nature

ABC likelihood-freee methods for model choice in Gibbs random fields

Gibbs random fields (GRF) are polymorphous statistical models that can be used to analyse different types of dependence, in particular for spatially correlated data. However, when those models are faced with the challenge of selecting a dependence structure from many, the use of standard model choice methods is hampered by the unavailability of the normalising constant in the Gibbs likelihood. In particular, from a Bayesian perspective, the computation of the posterior probabilities of the models under competition requires special likelihood-free simulation techniques like the Approximate Bayesian Computation (ABC) algorithm that is intensively used in population genetics. We show in this paper how to implement an ABC algorithm geared towards model choice in the general setting of Gibbs random fields, demonstrating in particular that there exists a sufficient statistic across models. The accuracy of the approximation to the posterior probabilities can be further improved by importance sampling on the distribution of the models. The practical aspects of the method are detailed through two applications, the test of an iid Bernoulli model versus a first-order Markov chain, and the choice of a folding structure for two proteins.Comment: 19 pages, 5 figures, to appear in Bayesian Analysi

Group 8 metal alkynyl complexes for nonlinear optics

International audienceStudies of the nonlinear optical (NLO) properties of Group 8 metal alkynyl complexes are summarized, with particular focus on results since 2003; structure-NLO property relationships are developed, optical nonlinearities of multipolar alkynyl complexes are described, and switching of the NLO response of molecules and molecular materials derived from Group 8 metal alkynyl complexes is discussed

Sediment budgets 1

Flood plains can act as important sinks of sediment and associated heavy metals, such as mercury. In this study, we present an estimate of the role of an Amazonian flood plain in sediment storage. The Curuai flood plain is located on the right bank of the Amazon River, 900 km upstream of the mouth. It is a complex system of more than 30 interconnected lakes, with a maximum inundated area of 2300 km2, representing 0.8% of the total flooded area of the Central Amazon basin. For the period 2000-2003, a mean average sediment deposition of 380 000 (±7.82%) t year-1 was determined using a box model calibrated using a network of gauging, meteorological and sediment monitoring stations operated over a 4 year period and analysis of multitemporal remote sensing images. This storage represents approximately 0.6% of the total annual sediment flux transported by the Amazon River. The associated mean specific sedimentation rate approaches 165 t km-2 year-1 if only the flooded area is considered

Synthesis, reactivity, and some photochemistry of ortho-N,N-dimethylaminomethyl substituted aryl and ferrocenyl pentamethylcyclopentadienyl dicarbonyl iron complexes

Supplementary materials: CCDC 928736, 928273, 928738, 928275, 928274 and 928737 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cifInternational audienceOrtho-lithiated N,N-dimethylaminomethyl ferrocene and benzyldimethylamine react with Cp*Fe(CO)2I to give the new complexes ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp) and Cp*Fe(CO)2-C6H4(o-CH2NMe2). Access to a wide variety of alkoxy-substituted complexes ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) can be easily achieved by tandem quaternization/alcoholysis of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp). Preliminary results show that chelated complexes can be obtained by displacement of one of the carbonyl ligands by photolysis. Crystal structures of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp), ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) (R = Ph, Bz, CHPh2 and d-menthyl) and [Cp*Fe(CO)2-C6H4(o-CH2NMe2)][I] are reported

Simulation-based model selection for dynamical systems in systems and population biology

Computer simulations have become an important tool across the biomedical sciences and beyond. For many important problems several different models or hypotheses exist and choosing which one best describes reality or observed data is not straightforward. We therefore require suitable statistical tools that allow us to choose rationally between different mechanistic models of e.g. signal transduction or gene regulation networks. This is particularly challenging in systems biology where only a small number of molecular species can be assayed at any given time and all measurements are subject to measurement uncertainty. Here we develop such a model selection framework based on approximate Bayesian computation and employing sequential Monte Carlo sampling. We show that our approach can be applied across a wide range of biological scenarios, and we illustrate its use on real data describing influenza dynamics and the JAK-STAT signalling pathway. Bayesian model selection strikes a balance between the complexity of the simulation models and their ability to describe observed data. The present approach enables us to employ the whole formal apparatus to any system that can be (efficiently) simulated, even when exact likelihoods are computationally intractable.Comment: This article is in press in Bioinformatics, 2009. Advance Access is available on Bioinformatics webpag

Enhanced two-photon absorption cross-sections of zinc(II) tetraphenylporphyrins peripherally substituted with d(6)-metal alkynyl complexes

International audienceThe syntheses of new Zn(II) tetraphenylporphyrin (ZnTPP) derivatives functionalized with electron-rich d6-transition metal alkynyl complexes at their periphery are reported. Z-scan measurements reveal remarkably large effective two-photon absorption (TPA) cross-sections in the visible range for these compounds

A Zinc(II) Tetraphenylporphyrin Peripherally Functionalized with Redox-Active "trans-[(η5-C5H5)Fe(η5-C5H4)C≡C](κ2- dppe)2Ru(C≡C)-" Substituents: Linear Electrochromism and Third-Order Nonlinear Optics

Dedicated to Dr. Claude Lapinte on the occasion of his retirement, in memory of the good times spent together in France and Australia.International audienceA nonametallic organometallic-coordination complex (4), assembled from redox-active ferrocenyl (Fc) and Ru(κ2-dppe)2 fragments (dppe = 1,2-bis(diphenylphosphino)ethane) as peripheral donor groups and a central Zn(II) tetraphenylporphyrin (ZnTPP) core, has been prepared and characterized. Complex 4 is obtained in one step from a pentametallic organometallic porphyrin precursor following substitution of the peripheral chloride ligands by ferrocenylalkynyl moieties (Ctriple bond; length of mdashCFc). The spectroelectrochemistry of 4, and that of previously reported porphyrins featuring related peripheral electron-rich d6-transition metal alkynyl units, has been investigated; the optical and redox properties of 4 are briefly discussed, and its potential, and that of a related pentanuclear tetraferrocenyl ZnTPP complex, to function as redox-switchable chromophores is examined. Preliminary studies of the cubic NLO properties of 4 have been undertaken by Z-scan studies at 560 nm and 630 nm, the results from which are also reported

Hidden Gibbs random fields model selection using Block Likelihood Information Criterion

Performing model selection between Gibbs random fields is a very challenging task. Indeed, due to the Markovian dependence structure, the normalizing constant of the fields cannot be computed using standard analytical or numerical methods. Furthermore, such unobserved fields cannot be integrated out and the likelihood evaluztion is a doubly intractable problem. This forms a central issue to pick the model that best fits an observed data. We introduce a new approximate version of the Bayesian Information Criterion. We partition the lattice into continuous rectangular blocks and we approximate the probability measure of the hidden Gibbs field by the product of some Gibbs distributions over the blocks. On that basis, we estimate the likelihood and derive the Block Likelihood Information Criterion (BLIC) that answers model choice questions such as the selection of the dependency structure or the number of latent states. We study the performances of BLIC for those questions. In addition, we present a comparison with ABC algorithms to point out that the novel criterion offers a better trade-off between time efficiency and reliable results

Bayesian Parameter Estimation for Latent Markov Random Fields and Social Networks

Undirected graphical models are widely used in statistics, physics and machine vision. However Bayesian parameter estimation for undirected models is extremely challenging, since evaluation of the posterior typically involves the calculation of an intractable normalising constant. This problem has received much attention, but very little of this has focussed on the important practical case where the data consists of noisy or incomplete observations of the underlying hidden structure. This paper specifically addresses this problem, comparing two alternative methodologies. In the first of these approaches particle Markov chain Monte Carlo (Andrieu et al., 2010) is used to efficiently explore the parameter space, combined with the exchange algorithm (Murray et al., 2006) for avoiding the calculation of the intractable normalising constant (a proof showing that this combination targets the correct distribution in found in a supplementary appendix online). This approach is compared with approximate Bayesian computation (Pritchard et al., 1999). Applications to estimating the parameters of Ising models and exponential random graphs from noisy data are presented. Each algorithm used in the paper targets an approximation to the true posterior due to the use of MCMC to simulate from the latent graphical model, in lieu of being able to do this exactly in general. The supplementary appendix also describes the nature of the resulting approximation.Comment: 26 pages, 2 figures, accepted in Journal of Computational and Graphical Statistics (http://www.amstat.org/publications/jcgs.cfm