Early maturation processes in coal. Part 1: Pyrolysis mass balances and structural evolution of coalified wood from the Morwell Brown Coal seam

In this work, we develop a theoretical approach to evaluate maturation process of kerogen-like material, involving molecular dynamic reactive modeling with a reactive force field to simulate the thermal stress. The Morwell coal has been selected to study the thermal evolution of terrestrial organic matter. To achieve this, a structural model is first constructed based on models from the literature and analytical characterization of our samples by modern 1-and 2-D NMR, FTIR, and elemental analysis. Then, artificial maturation of the Morwell coal is performed at low conversions in order to obtain, quantitative and qualitative, detailed evidences of structural evolution of the kerogen upon maturation. The observed chemical changes are a defunctionalization of the carboxyl, carbonyl and methoxy functional groups coupling with an increase of cross linking in the residual mature kerogen. Gaseous and liquids hydrocarbons, essentially CH4, C4H8 and C14+ liquid hydrocarbons, are generated in low amount, merely by cleavage of the lignin side chain

Effect of NASA Light-emitting Diode Irradiation on Wound Healing

Objective: The purpose of this study was to assess the effects of hyperbaric oxygen (HBO) and near-infrared light therapy on wound healing. Background Data: Light-emitting diodes (LED), originally developed for NASA plant growth experiments in space show promise for delivering light deep into tissues of the body to promote wound healing and human tissue growth. In this paper, we review and present our new data of LED treatment on cells grown in culture, on ischemic and diabetic wounds in rat models, and on acute and chronic wounds in humans. Materials and Methods: In vitro and in vivo (animal and human) studies utilized a variety of LED wavelength, power intensity, and energy density parameters to begin to identify conditions for each biological tissue that are optimal for biostimulation. Results: LED produced in vitro increases of cell growth of 140–200% in mouse-derived fibroblasts, rat-derived osteoblasts, and rat-derived skeletal muscle cells, and increases in growth of 155–171% of normal human epithelial cells. Wound size decreased up to 36% in conjunction with HBO in ischemic rat models. LED produced improvement of greater than 40% in musculoskeletal training injuries in Navy SEAL team members, and decreased wound healing time in crew members aboard a U.S. Naval submarine. LED produced a 47% reduction in pain of children suffering from oral mucositis. Conclusion: We believe that the use of NASA LED for light therapy alone, and in conjunction with hyperbaric oxygen, will greatly enhance the natural wound healing process, and more quickly return the patient to a preinjury/ illness level of activity. This work is supported and managed through the NASA Marshall Space Flight Center–SBIR Program

High-Temperature Quantum Tunneling and Hydrogen Bonding Rearrangements Characterize the Solid-Solid Phase Transitions in a Phosphonium-Based Protic Ionic Liquid

We report the complex phase behavior of the glass forming protic ionic liquid (PIL) d3-octylphosphonium bis(trifluoromethylsulfonyl)imide [C8H17PD3][NTf2] by means of solid-state NMR spectroscopy. Combined line shape and spin relaxation studies of the deuterons in the PD3 group of the octylphosphonium cation allow to map and correlate the phase behavior for a broad temperature range from 71 K to 343 K. In the solid PIL at 71 K, we observed a static state, characterized by the first deuteron quadrupole coupling constant reported for PD3 deuterons. A transition enthalpy of about 12 kJmol 1 from the static to the mobile state with increasing temperature suggests the breaking of a weak, charge-enhanced hydrogen bond between cation and anion. The highly mobile phase above 100 K exhibits an almost disappearing activation barrier, strongly indicating quantum tunneling. Thus, we provide first evidence of tunneling driven mobility of the hydrogen bonded P D moieties in the glassy state of PILs, already at surprisingly high temperatures up to 200 K. Above 250 K, the mobile phase turns from anisotropic to isotropic motion, and indicates strong internal rotation of the PD3 group. The analyzed line shapes and spin relaxation times allow us to link the structural and dynamical behavior at molecular level with the phase behavior beyond the DSC traces

Data-driven campaigning and democratic disruption : evidence from six advanced democracies

Data-driven campaigning has become one of the key foci for academic and non-academic audiences interested in political communication. Widely seen to have transformed political practice, it is often argued that data-driven campaigning is a force of significant democratic disruption because it contributes to a fragmentation of political discourse, undermines prevailing systems of electoral accountability and subverts ‘free’ and ‘fair’ elections. In this article, we present one of the very first cross-national analyses of data-driven campaigning by political parties. Drawing on empirical research conducted by experts in six advanced democracies, we show that the data-driven campaign practices seen to threaten democracy are often not manifest in party campaigns. Instead, we see a set of practices that build on pre-existing techniques and which are far less sophisticated than is often assumed. Indeed, we present evidence that most political parties lack the capacity to execute the hyper-intensive practices often associated with data-driven campaigning. Hence, while there is reason to remain alert to the challenges data-driven campaigning produces for democratic norms, we argue that this practice is not inherently disruptive, but rather exemplifies the evolving nature of political campaigning in the 21st century

Pathogenic variants of sphingomyelin synthase SMS2 disrupt lipid landscapes in the secretory pathway

Sphingomyelin is a dominant sphingolipid in mammalian cells. Its production in the trans-Golgi traps cholesterol synthesized in the ER to promote formation of a sphingomyelin/sterol gradient along the secretory pathway. This gradient marks a fundamental transition in physical membrane properties that help specify organelle identify and function. We previously identified mutations in sphingomyelin synthase SMS2 that cause osteoporosis and skeletal dysplasia. Here, we show that SMS2 variants linked to the most severe bone phenotypes retain full enzymatic activity but fail to leave the ER owing to a defective autonomous ER export signal. Cells harboring pathogenic SMS2 variants accumulate sphingomyelin in the ER and display a disrupted transbilayer sphingomyelin asymmetry. These aberrant sphingomyelin distributions also occur in patient-derived fibroblasts and are accompanied by imbalances in cholesterol organization, glycerophospholipid profiles, and lipid order in the secretory pathway. We postulate that pathogenic SMS2 variants undermine the capacity of osteogenic cells to uphold nonrandom lipid distributions that are critical for their bone forming activity.Peer reviewe

Stochastic population growth in spatially heterogeneous environments

Classical ecological theory predicts that environmental stochasticity increases extinction risk by reducing the average per-capita growth rate of populations. To understand the interactive effects of environmental stochasticity, spatial heterogeneity, and dispersal on population growth, we study the following model for population abundances in $n$ patches: the conditional law of $X_{t+dt}$ given $X_t=x$ is such that when $dt$ is small the conditional mean of $X_{t+dt}^i-X_t^i$ is approximately $[x^i\mu_i+\sum_j(x^j D_{ji}-x^i D_{ij})]dt$, where $X_t^i$ and $\mu_i$ are the abundance and per capita growth rate in the $i$-th patch respectivly, and $D_{ij}$ is the dispersal rate from the $i$-th to the $j$-th patch, and the conditional covariance of $X_{t+dt}^i-X_t^i$ and $X_{t+dt}^j-X_t^j$ is approximately $x^i x^j \sigma_{ij}dt$. We show for such a spatially extended population that if $S_t=(X_t^1+...+X_t^n)$ is the total population abundance, then $Y_t=X_t/S_t$, the vector of patch proportions, converges in law to a random vector $Y_\infty$ as $t\to\infty$, and the stochastic growth rate $\lim_{t\to\infty}t^{-1}\log S_t$ equals the space-time average per-capita growth rate \sum_i\mu_i\E[Y_\infty^i] experienced by the population minus half of the space-time average temporal variation \E[\sum_{i,j}\sigma_{ij}Y_\infty^i Y_\infty^j] experienced by the population. We derive analytic results for the law of $Y_\infty$, find which choice of the dispersal mechanism $D$ produces an optimal stochastic growth rate for a freely dispersing population, and investigate the effect on the stochastic growth rate of constraints on dispersal rates. Our results provide fundamental insights into "ideal free" movement in the face of uncertainty, the persistence of coupled sink populations, the evolution of dispersal rates, and the single large or several small (SLOSS) debate in conservation biology.Comment: 47 pages, 4 figure

Grey and white matter correlates of recent and remote autobiographical memory retrieval:Insights from the dementias

The capacity to remember self-referential past events relies on the integrity of a distributed neural network. Controversy exists, however, regarding the involvement of specific brain structures for the retrieval of recently experienced versus more distant events. Here, we explored how characteristic patterns of atrophy in neurodegenerative disorders differentially disrupt remote versus recent autobiographical memory. Eleven behavioural-variant frontotemporal dementia, 10 semantic dementia, 15 Alzheimer's disease patients and 14 healthy older Controls completed the Autobiographical Interview. All patient groups displayed significant remote memory impairments relative to Controls. Similarly, recent period retrieval was significantly compromised in behavioural-variant frontotemporal dementia and Alzheimer's disease, yet semantic dementia patients scored in line with Controls. Voxel-based morphometry and diffusion tensor imaging analyses, for all participants combined, were conducted to investigate grey and white matter correlates of remote and recent autobiographical memory retrieval. Neural correlates common to both recent and remote time periods were identified, including the hippocampus, medial prefrontal, and frontopolar cortices, and the forceps minor and left hippocampal portion of the cingulum bundle. Regions exclusively implicated in each time period were also identified. The integrity of the anterior temporal cortices was related to the retrieval of remote memories, whereas the posterior cingulate cortex emerged as a structure significantly associated with recent autobiographical memory retrieval. This study represents the first investigation of the grey and white matter correlates of remote and recent autobiographical memory retrieval in neurodegenerative disorders. Our findings demonstrate the importance of core brain structures, including the medial prefrontal cortex and hippocampus, irrespective of time period, and point towards the contribution of discrete regions in mediating successful retrieval of distant versus recently experienced events

Contrasting prefrontal cortex contributions to episodic memory dysfunction in behavioural variant frontotemporal dementia and alzheimer's disease

Recent evidence has questioned the integrity of episodic memory in behavioural variant frontotemporal dementia (bvFTD), where recall performance is impaired to the same extent as in Alzheimer's disease (AD). While these deficits appear to be mediated by divergent patterns of brain atrophy, there is evidence to suggest that certain prefrontal regions are implicated across both patient groups. In this study we sought to further elucidate the dorsolateral (DLPFC) and ventromedial (VMPFC) prefrontal contributions to episodic memory impairment in bvFTD and AD. Performance on episodic memory tasks and neuropsychological measures typically tapping into either DLPFC or VMPFC functions was assessed in 22 bvFTD, 32 AD patients and 35 age- and education-matched controls. Behaviourally, patient groups did not differ on measures of episodic memory recall or DLPFC-mediated executive functions. BvFTD patients were significantly more impaired on measures of VMPFC-mediated executive functions. Composite measures of the recall, DLPFC and VMPFC task scores were covaried against the T1 MRI scans of all participants to identify regions of atrophy correlating with performance on these tasks. Imaging analysis showed that impaired recall performance is associated with divergent patterns of PFC atrophy in bvFTD and AD. Whereas in bvFTD, PFC atrophy covariates for recall encompassed both DLPFC and VMPFC regions, only the DLPFC was implicated in AD. Our results suggest that episodic memory deficits in bvFTD and AD are underpinned by divergent prefrontal mechanisms. Moreover, we argue that these differences are not adequately captured by existing neuropsychological measures