Ice Formation on Kaolinite: Insights from Molecular Dynamics Simulations

The formation of ice affects many aspects of our everyday life as well as technologies such as cryotherapy and cryopreservation. Foreign substances almost always aid water freezing through heterogeneous ice nucleation, but the molecular details of this process remain largely unknown. In fact, insight into the microscopic mechanism of ice formation on different substrates is difficult to obtain even via state-of-the-art experimental techniques. At the same time, atomistic simulations of heterogeneous ice nucleation frequently face extraordinary challenges due to the complexity of the water-substrate interaction and the long timescales that characterize nucleation events. Here, we have investigated several aspects of molecular dynamics simulations of heterogeneous ice nucleation considering as a prototypical ice nucleating material the clay mineral kaolinite, which is of relevance in atmospheric science. We show via seeded molecular dynamics simulations that ice nucleation on the hydroxylated (001) face of kaolinite proceeds exclusively via the formation of the hexagonal ice polytype. The critical nucleus size is two times smaller than that obtained for homogeneous nucleation at the same supercooling. Previous findings suggested that the flexibility of the kaolinite surface can alter the time scale for ice nucleation within molecular dynamics simulations. However, we here demonstrate that equally flexible (or non flexible) kaolinite surfaces can lead to very different outcomes in terms of ice formation, according to whether or not the surface relaxation of the clay is taken into account. We show that very small structural changes upon relaxation dramatically alter the ability of kaolinite to provide a template for the formation of a hexagonal overlayer of water molecules at the water-kaolinite interface, and that this relaxation therefore determines the nucleation ability of this mineral

Transport collapse in dynamically evolving networks

Transport in complex networks can describe a variety of natural and human-engineered processes including biological, societal and technological ones. However, how the properties of the source and drain nodes can affect transport subject to random failures, attacks or maintenance optimization in the network remain unknown. In this paper, the effects of both the distance between the source and drain nodes and of the degree of the source node on the time of transport collapse are studied in scale-free and lattice-based transport networks. These effects are numerically evaluated for two strategies, which employ either transport-based or random link removal. Scale-free networks with small distances are found to result in larger times of collapse. In lattice-based networks, both the dimension and boundary conditions are shown to have a major effect on the time of collapse. We also show that adding a direct link between the source and the drain increases the robustness of scale-free networks when subject to random link removals. Interestingly, the distribution of the times of collapse is then similar to the one of lattice-based networks

Geometric Phantom Categories

In this paper we give a construction of phantom categories, i.e. admissible triangulated subcategories in bounded derived categories of coherent sheaves on smooth projective varieties that have trivial Hochschild homology and trivial Grothendieck group. We also prove that these phantom categories are phantoms in a stronger sense, namely, they have trivial K-motives and, hence, all their higher K-groups are trivial too.Comment: LaTeX, 18 page

Corporate voluntary greenhouse gas reporting: stakeholder pressure and the mediating role of the chief executive officer

The study sheds light on the extent to which various stakeholder pressures influence voluntary disclosure of greenhouse gas (GHG) emissions and how the impact is explained and moderated Chief executive office (CEO) characteristics of 215 FTSE350 listed United Kingdom (UK) companies for the year 2011. The study developed a classification of GHG emission disclosure based on the guidelines of GHG Protocol, DEFRA and Global Framework for Climate Risk Disclosure using content analysis. Evidence from the study suggests that some stakeholder pressure (regulatory, creditor, supplier, customer, board control) positively impacts on GHG disclosure information by firms. We found stakeholder pressure in the form of regulatory, mimetic and shareholders pressure positively influenced the disclosure of GHG information. We also found creditor pressure also had a significant negative relationship with GHG disclosure. While CEO age had a direct negative effect on GHG voluntary disclosure, its moderation effect on stakeholder pressure influence on GHG disclosure was only significant on regulatory pressure

Distinct levels in Pom1 gradients limit Cdr2 activity and localization to time and position division.

Where and when cells divide are fundamental questions. In rod-shaped fission yeast cells, the DYRK-family kinase Pom1 is organized in concentration gradients from cell poles and controls cell division timing and positioning. Pom1 gradients restrict to mid-cell the SAD-like kinase Cdr2, which recruits Mid1/Anillin for medial division. Pom1 also delays mitotic commitment through Cdr2, which inhibits Wee1. Here, we describe quantitatively the distributions of cortical Pom1 and Cdr2. These reveal low profile overlap contrasting with previous whole-cell measurements and Cdr2 levels increase with cell elongation, raising the possibility that Pom1 regulates mitotic commitment by controlling Cdr2 medial levels. However, we show that distinct thresholds of Pom1 activity define the timing and positioning of division. Three conditions-a separation-of-function Pom1 allele, partial downregulation of Pom1 activity, and haploinsufficiency in diploid cells-yield cells that divide early, similar to pom1 deletion, but medially, like wild-type cells. In these cells, Cdr2 is localized correctly at mid-cell. Further, Cdr2 overexpression promotes precocious mitosis only in absence of Pom1. Thus, Pom1 inhibits Cdr2 for mitotic commitment independently of regulating its localization or cortical levels. Indeed, we show Pom1 restricts Cdr2 activity through phosphorylation of a C-terminal self-inhibitory tail. In summary, our results demonstrate that distinct levels in Pom1 gradients delineate a medial Cdr2 domain, for cell division placement, and control its activity, for mitotic commitment

On the pp-supports of a holonomic D\mathcal{D}-module

For a smooth variety $Y$ over a perfect field of positive characteristic, the sheaf $D_Y$ of crystalline differential operators on $Y$ (also called the sheaf of $PD$-differential operators) is known to be an Azumaya algebra over $T^*_{Y'},$ the cotangent space of the Frobenius twist $Y'$ of $Y.$ Thus to a sheaf of modules $M$ over $D_Y$ one can assign a closed subvariety of $T^*_{Y'},$ called the $p$-support, namely the support of $M$ seen as a sheaf on $T^*_{Y'}.$ We study here the family of $p$-supports assigned to the reductions modulo primes $p$ of a holonomic $\mathcal{D}$-module. We prove that the Azumaya algebra of differential operators splits on the regular locus of the $p$-support and that the $p$-support is a Lagrangian subvariety of the cotangent space, for $p$ large enough. The latter was conjectured by Kontsevich. Our approach also provides a new proof of the involutivity of the singular support of a holonomic $\mathcal{D}$-module, by reduction modulo $p.$Comment: The article has been rewritten with much improved exposition as well as some additional results, e.g. Corollary 6.3.1. This is the final version, accepted for publication in Inventiones Mathematica

Dinitrogen fixation and dissolved organic nitrogen fueled primary production and particulate export during the VAHINE mesocosm experiment (New Caledonia lagoon)

International audienceIn the oligotrophic ocean characterized by nitrate (NO − 3) depletion in surface waters, dinitrogen (N 2) fixation and dissolved organic nitrogen (DON) can represent significant nitrogen (N) sources for the ecosystem. In this study, we deployed large in situ mesocosms in New Caledonia in order to investigate (1) the contribution of N 2 fixation and DON use to primary production (PP) and particle export and (2) the fate of the freshly produced particulate organic N (PON), i.e., whether it is preferentially accumulated and recycled in the water column or exported out of the system. The mesocosms were fertilized with phosphate (PO 3− 4) in order to prevent phosphorus (P) limitation and promote N 2 fixation. The diazotrophic community was dominated by diatom–diazotroph associations (DDAs) during the first part of the experiment for 10 days (P1) followed by the unicel-lular N 2-fixing cyanobacteria UCYN-C for the last 9 days (P2) of the experiment. N 2 fixation rates averaged 9.8 ± 4.0 and 27.7 ± 8.6 nmol L −1 d −1 during P1 and P2, respectively. NO − 3 concentrations ( 0.05) during P1 (9.0 ± 3.3 %) and P2 (12.6 ± 6.1 %). However, the e ratio that quantifies the efficiency of a system to export particulate organic carbon (POC export) compared to PP (e ratio = POC export / PP) was significantly higher (p 0.05) from the total amount of PON exported (0.10 ± 0.04 µmol L −1), suggesting a rapid and probably direct export of the recently fixed N 2 by the DDAs. During P2, both PON concentrations and PON export increased in the mesocosms by a factor 1.5–2. Unlike in P1, this PON production was not totally explained by the new N provided by N 2 fixation. The use of DON, whose concentrations decreased significantly (p < 0.05) from 5.3 ± 0.5 µmol L −1 to 4.4 ± 0.5 µmol L −1 , appeared to be the missing N source. The DON consumption (∼ 0.9 µmol L −1) during P2 is higher Published by Copernicus Publications on behalf of the European Geosciences Union. 4100 H. Berthelot et al.: Dinitrogen fixation and dissolved organic nitrogen fueled primary production than the total amount of new N brought by N 2 fixation (∼ 0.25 µmol L −1) during the same period. These results suggest that while DDAs mainly rely on N 2 fixation for their N requirements, both N 2 fixation and DON can be significant N sources for primary production and particulate export following UCYN-C blooms in the New Caledonia lagoon and by extension in the N-limited oceans where similar events are likely to occur

Adaptation of Proteins to the Cold in Antarctic Fish: A Role for Methionine?

The evolution of antifreeze glycoproteins has enabled notothenioid fish to flourish in the freezing waters of the Southern Ocean. Whereas successful at the biodiversity level to life in the cold, paradoxically at the cellular level these stenothermal animals have problems producing, folding, and degrading proteins at their ambient temperatures of -1.86 °C. In this first multi-species transcriptome comparison of the amino acid composition of notothenioid proteins with temperate teleost proteins, we show that, unlike psychrophilic bacteria, Antarctic fish provide little evidence for the mass alteration of protein amino acid composition to enhance protein folding and reduce protein denaturation in the cold. The exception was the significant overrepresentation of positions where leucine in temperate fish proteins was replaced by methionine in the notothenioid orthologues. We hypothesize that these extra methionines have been preferentially assimilated into the genome to act as redox sensors in the highly oxygenated waters of the Southern Ocean. This redox hypothesis is supported by analyses of notothenioids showing enrichment of genes associated with responses to environmental stress, particularly reactive oxygen species. So overall, although notothenioid fish show cold-associated problems with protein homeostasis, they may have modified only a selected number of biochemical pathways to work efficiently below 0 °C. Even a slight warming of the Southern Ocean might disrupt the critical functions of this handful of key pathways with considerable impacts for the functioning of this ecosystem in the future