Theoretical vibrational study of the FX⋅⋅⋅O(CH3)2 hydrogen‐bonded complex

This paper presents the first ab initio attempt to reconstruct the observed band profile of the stretching fundamental vFX (X=H,D) in the FX⋅⋅⋅O(CH3)2 hydrogen‐bonded system. The two‐dimensional potential energy surface V(rFH,RF⋅⋅⋅O) is evaluated by means of large basis set SCF calculations. The related force constants up to the fourth order are obtained via the analytical fit to a polynomial expansion. The vibrational problem is solved by means of a variational treatment which includes the effects of mechanical anharmonicity. The side bands of the stretching fundamental vFX are described in terms of the vFX ±nvFX⋅⋅⋅O combination bands in excellent agreement with experiment

Probabilistic and predictive performance-based approach for assessing reinforced concrete structures lifetime: The applet project

International audienceConcrete deterioration results in different damage extents, from cracking to concrete spalling, from losses of reinforcement cross-sections to bond losses. A relevant prediction of this performance is the basis for a successful management of the concrete structures. Conversely, the large amount of uncertainties related to parameters and models require a specific analysis in order to provide relevant results. The APPLET project intends to develop a probabilistic and predictive performance-based approach by quantifying the various sources of variability (material and structure), studying the interaction between environmental aggressive agents and the concrete material, ensuring a transfer of the physical-chemical models at the material scale towards models at the structure level, including and understanding in a better manner the corrosion process, integrating interface models between reinforcement and concrete, proposing relevant numerical models, integrating know-how from monitoring or inspection. To provide answers, a consortium of 19 partners has been established and has promoted a research project funded by the French Research Science Agency (ANR). Started in May 2007, the project has ended in November 2010. This paper will resume the most significant advances targeted by this research project

Size structure of phytoplankton biomass in the equatorial Atlantic Ocean

Abstract-The size structure of chlorophyll a (Chl a) and phaeopigments ((20, (10, (3, <2, and <1 ym) has been studied along three transects (4O, 23", and 35OW) covering the entire equatorial Atlantic Ocean, with special attention to the small sizes (<3 pm). Everywhere in the studied area, even in the equatorial upwelling, the bulk of Chl a is within organisms which pass through a 3 pm Nuclepore filter. The vertical distribution of the (1 pm Chl a is closely related to the depth of the nitracline. In the nitrate-depleted mixed layer, the (1 ym Chl a always dominates, and represents 71% of the total Chl a on the average. At the top of the nitracline, the < 1 ym Chl a concentration is maximum but represents only 50% of the total Chl a. In the nitrate-rich waters, whatever the depth, the percentage of (1 pm Chl a is everywhere (50% and decreases downwards. At the bottom of the photic zone, the < 1 prn Chl a values are nearly zero. When integrated over the whole euphotic layer, the < 1 ym Chl a represents about 25% of the total Chl a when nitrate is present at surface; this percentage reaches 60% when the top of the nitracline deepens to 100 m depth. Preliminary measurements of photosynthetic activity (light gradient and time course experiments) indicate that the < 1 ym fraction contains actively photosynthetic organisms but also organisms which are able to fix CO1 in the darkness in a significant proportion. The roles of sinking, nutrients, and light in the vertical distribution of picoplankton are discussed. Our results indicate that the size distribution of Chl a (and especially the relationship between abundance of picoplankton and nitrate distribution) is the same throughout the whole equatorial (MALONE, 1980). Recent studies have focused attention on a smaller size class of autotrophic organisms-the picoplankton ((2 pm, according to SIEBURTH et al., 1978). WATERBURY et al. (1979) and JOHNSON and SIEBURTH (1 979) show the existence of small unicellular cyanobacteria (procaryotes) with a widespread geographical distribution and the ability to achieve considerable densities. Recently, LI et al. (1983) in the eastern tropical Pacific, and PLATT et al. (1983) in the tropical North Atlantic (west of Azores) concluded that autotrophic picoplankton (< 1 prn) are capable of supplying 60% (range 20 to 80%) of the total primary production in the open ecosystem. These two last results are extremely important because they modify our concepts on the biological structure of the pelagic ecosystem, but they are limited in space and time. We .I

Random, blocky and alternating ordering in supramolecular polymers of chemically bidisperse monomers

As a first step to understanding the role of molecular or chemical polydispersity in self-assembly, we put forward a coarse-grained model that describes the spontaneous formation of quasi-linear polymers in solutions containing two self-assembling species. Our theoretical framework is based on a two-component self-assembled Ising model in which the bidispersity is parameterized in terms of the strengths of the binding free energies that depend on the monomer species involved in the pairing interaction. Depending upon the relative values of the binding free energies involved, different morphologies of assemblies that include both components are formed, exhibiting paramagnetic-, ferromagnetic- or anti ferromagnetic-like order,i.e., random, blocky or alternating ordering of the two components in the assemblies. Analyzing the model for the case of ferromagnetic ordering, which is of most practical interest, we find that the transition from conditions of minimal assembly to those characterized by strong polymerization can be described by a critical concentration that depends on the concentration ratio of the two species. Interestingly, the distribution of monomers in the assemblies is different from that in the original distribution, i.e., the ratio of the concentrations of the two components put into the system. The monomers with a smaller binding free energy are more abundant in short assemblies and monomers with a larger binding affinity are more abundant in longer assemblies. Under certain conditions the two components congregate into separate supramolecular polymeric species and in that sense phase separate. We find strong deviations from the expected growth law for supramolecular polymers even for modest amounts of a second component, provided it is chemically sufficiently distinct from the main one.Comment: Submitted to Macromolecules, 6 figures. arXiv admin note: substantial text overlap with arXiv:1111.176

Electronic structure of fluorides: general trends for ground and excited state properties

The electronic structure of fluorite crystals are studied by means of density functional theory within the local density approximation for the exchange correlation energy. The ground-state electronic properties, which have been calculated for the cubic structures $CaF_{2}$,$SrF_{2}$, $BaF_{2}$, $CdF_{2}$, $HgF_{2}$, $\beta$-$PbF_{2}$, using a plane waves expansion of the wave functions, show good comparison with existing experimental data and previous theoretical results. The electronic density of states at the gap region for all the compounds and their energy-band structure have been calculated and compared with the existing data in the literature. General trends for the ground-state parameters, the electronic energy-bands and transition energies for all the fluorides considered are given and discussed in details. Moreover, for the first time results for $HgF_{2}$ have been presented

Integrated Multiscale Modeling of the Nervous System: Predicting Changes in Hippocampal Network Activity by a Positive AMPA Receptor Modulator

One of the fundamental characteristics of the brain is its hierarchical organization. Scales in both space and time that must be considered when integrating across hierarchies of the nervous system are sufficiently great as to have impeded the development of routine multilevel modeling methodologies. Complex molecular interactions at the level of receptors and channels regulate activity at the level of neurons; interactions between multiple populations of neurons ultimately give rise to complex neural systems function and behavior. This spatial complexity takes place in the context of a composite temporal integration of multiple, different events unfolding at the millisecond, second, minute, hour, and longer time scales. In this study, we present a multiscale modeling methodology that integrates synaptic models into single neuron, and multineuron, network models. We have applied this approach to the specific problem of how changes at the level of kinetic parameters of a receptor-channel model are translated into changes in the temporal firing pattern of a single neuron, and ultimately, changes in the spatiotemporal activity of a network of neurons. These results demonstrate how this powerful methodology can be applied to understand the effects of a given local process within multiple hierarchical levels of the nervous system

The Zinc-Finger Protein SOP1 Is Required for a Subset of the Nuclear Exosome Functions in Arabidopsis

Correct gene expression requires tight RNA quality control both at transcriptional and post-transcriptional levels. Using a splicing-defective allele of PASTICCINO2 (PAS2), a gene essential for plant development, we isolated suppressor mutations modifying pas2-1 mRNA profiles and restoring wild-type growth. Three suppressor of pas2 (sop) mutations modified the degradation of mis-spliced pas2-1 mRNA species, allowing the synthesis of a functional protein. Cloning of the suppressor mutations identified the core subunit of the exosome SOP2/RRP4, the exosome nucleoplasmic cofactor SOP3/HEN2 and a novel zinc-finger protein SOP1 that colocalizes with HEN2 in nucleoplasmic foci. The three SOP proteins counteract post-transcriptional (trans)gene silencing (PTGS), which suggests that they all act in RNA quality control. In addition, sop1 mutants accumulate some, but not all of the misprocessed mRNAs and other types of RNAs that are observed in exosome mutants. Taken together, our data show that SOP1 is a new component of nuclear RNA surveillance that is required for the degradation of a specific subset of nuclear exosome targets. [Correction available at https://journals.plos.org/plosgenetics/article?id=10.1371/journal.pgen.1005958

CD160-Associated CD8 T-Cell Functional Impairment Is Independent of PD-1 Expression.

Expression of co-inhibitory molecules is generally associated with T-cell dysfunction in chronic viral infections such as HIV or HCV. However, their relative contribution in the T-cell impairment remains unclear. In the present study, we have evaluated the impact of the expression of co-inhibitory molecules such as 2B4, PD-1 and CD160 on the functions of CD8 T-cells specific to influenza, EBV and CMV. We show that CD8 T-cell populations expressing CD160, but not PD-1, had reduced proliferation capacity and perforin expression, thus indicating that the functional impairment in CD160+ CD8 T cells may be independent of PD-1 expression. The blockade of CD160/CD160-ligand interaction restored CD8 T-cell proliferation capacity, and the extent of restoration directly correlated with the ex vivo proportion of CD160+ CD8 T cells suggesting that CD160 negatively regulates TCR-mediated signaling. Furthermore, CD160 expression was not up-regulated upon T-cell activation or proliferation as compared to PD-1. Taken together, these results provide evidence that CD160-associated CD8 T-cell functional impairment is independent of PD-1 expression