Short-Lived Interfaces in Energy Materials

The kinetics of most chemical energy storage/conversion systems depend on the mass transport through matter, which is rate-limited by various kinetic barriers. The distinction of the barriers by static and dynamic interfaces helps in reducing their impact and therefore enhancing the overall kinetics. The concept is introduced along examples of static and dynamic interfaces in hydrogen storage, thermal energy storage in absorptive media, and electrochemical water splitting and CO2 reduction. In addition to the description of analysis methods to probe static and dynamic interfaces, the general strategy as well as concrete examples to overcome them are discussed.

A Mechanistic DNA Repair and Survival Model (Medras): Applications to Intrinsic Radiosensitivity, Relative Biological Effectiveness and Dose-Rate

Variations in the intrinsic radiosensitivity of different cells to ionizing radiation is now widely believed to be a significant driver in differences in response to radiotherapy. While the mechanisms of radiosensitivity have been extensively studied in the laboratory, there are a lack of models which integrate this knowledge into a predictive framework. This paper presents an overview of the Medras model, which has been developed to provide a mechanistic framework in which different radiation responses can be modelled and individual responses predicted. This model simulates the repair of radiation-induced DNA damage, incorporating the overall kinetics of repair and its fidelity, to predict a range of biological endpoints including residual DNA damage, mutation, chromosome aberration, and cell death. Validation of this model against a range of exposure types is presented, including considerations of varying radiation qualities and dose-rates. This approach has the potential to inform new tools to deliver mechanistic predictions of radiation sensitivity, and support future developments in treatment personalization.

Role of TLR4 in Persistent Leptospira interrogans Infection: A Comparative In Vivo Study in Mice

Toll-Like Receptor (TLR) 4, the LPS receptor, plays a central role in the control of leptospirosis and absence of TLR4 results in lethal infection in mice. Because human TLR4 does not sense the atypical leptospiral-LPS, we hypothesized that TLR4/MD-2 humanized transgenic mice (huTLR4) may be more susceptible to leptospirosis than wild-type mice, and thus may constitute a model of acute human leptospirosis. We infected huTLR4 mice, which express human TLR4 but not murine TLR4, with a high dose of L. interrogans serovar Copenhageni FioCruz (Leptospira) in comparison to C57BL/6J wild-type (WT) and, as a control, a congenic strain in which the tlr4 coding sequences are deleted (muTLR4Lps-del). We show that the huTLR4 gene is fully functional in the murine background. We found that dissemination of Leptospira in blood, shedding in urine, colonization of the kidney and overall kinetics of leptospirosis progression is equivalent between WT and huTLR4 C57BL/6J mice. Furthermore, inflammation of the kidney appeared to be subdued in huTLR4 compared to WT mice in that we observed less infiltrates of mononuclear lymphocytes, less innate immune markers and no relevant differences in fibrosis markers. Thus, huTLR4 mice showed less inflammation and kidney pathology, and are not more susceptible to leptospirosis than WT mice. This study is significant as it indicates that one intact TLR4 gene, be it mouse or human, is necessary to control acute leptospirosis.

Thermal Decomposition of Spherically Granulated Malachite: Physico-Geometrical Constraints and Overall Kinetics

The thermal decomposition of spherically granulated malachite particles was investigated to unveil the specific kinetic features of the reaction in sample in granular form toward the improvement of the thermal...

CO2 Conversion to Methanol over Novel Carbon Nanofiber-Based Cu/ZrO2 Catalysts—A Kinetics Study

Ongoing industrialization has deteriorated the global environment. Global warming is a human-induced issue affecting the environment. The alarming increase in CO2 emissions is among the major contributors to global warming. The conversion of CO2 to methanol is an economically viable and environmentally friendly solution to mitigate its concentration. Here, hydrogenation of CO2 was studied over carbon nanofiber-based Cu/ZrO2 catalysts. Kinetics investigations were carried out for the reaction. Overall, kinetics data indicated that CO2 conversion follows a pseudo-first-order reaction. The kinetics studies were further modeled by using an artificial neural network, which supported the experimental kinetics study.

Mechanistic Determinants of Slow Axonal Transport and Presynaptic Targeting of Clathrin Packets

SUMMARYClathrin has established roles in endocytosis, with clathrin-cages enclosing membrane infoldings, followed by rapid disassembly and reuse of monomers. However, in neurons, clathrin synthesized in cell-bodies is conveyed into axons and synapses via slow axonal transport; as shown by classic pulse-chase radiolabeling. What is the cargo-structure, and mechanisms underlying transport and presynaptic-targeting of clathrin? What is the precise organization at synapses? Combining live-imaging, mass-spectrometry (MS), Apex-labeled EM-tomography and super-resolution, we found that unlike dendrites where clathrin transiently assembles/disassembles as expected, axons contain stable ‘transport-packets’ that move intermittently with an anterograde bias; with actin/myosin-VI as putative tethers. Transport-packets are unrelated to endocytosis, and the overall kinetics generate a slow biased flow of axonal clathrin. Synapses have integer-numbers of clathrin-packets circumferentially abutting the synaptic-vesicle cluster, advocating a model where delivery of clathrin-packets by slow axonal transport generates a radial organization of clathrin at synapses. Our experiments reveal novel trafficking mechanisms, and an unexpected nanoscale organization of synaptic clathrin.

Kinetic control on the distribution of secondary precipitates during CO2-basalt interactions

A combined experimental and numerical study was undertaken to better understand the spatial distribution of secondary mineral growth along a basalt column. The work demonstrated that few and large crystals formed at random locations. This can only be explained in terms of an overall control by mineral nucleation. The main implication is that a new probabilistic approach must be developed in order to get the overall kinetics and the distribution of crystal growth in the numerical models right.

Influence of Initiation Site and Lamellar Divergency on the Overall Kinetics of Cellular Growth and Coarsening in Aged U-Nb Alloys

Overall kinetics of lamellar overaging reactions in U-5.5Nb and U-7.5Nb were analyzed by Avrami-Arrhenius analyses of volume fractions measured from an extensive temperature-time (T-t) matrix of specimens. The cellular initiation site (grain boundaries, inclusions) and regimes of lamellar divergency-cum-slowing growth rate were explicitly accounted for. Avrami exponents n from T-t regimes of constant-growth rate were consistent with theory (1<n<3); those from divergent T-t regimes were smaller, n~0.7, which is not surprising given their different growth rate behavior. The apparent activation energies Q were similar for grain-boundary and inclusion-nucleated discontinuous precipitation, indicating that their nucleation site does not alter their overall kinetics. Avrami Analysis of Isothermal Aging Kinetics

Kinetics of methyl methacrylate combustion over a Pt/alumina catalyst

The combustion of methyl methacrylate (MMA) over a commercial Pt/?-alumina catalyst was investigated, in the lean air mixtures specific for the depollution applications. The experiments were performed at temperatures between 150 and 360?C, with MMA concentrations of 460 to 800 ppmv and the gas flow rates between 200 and 300 mL min-1. The results evidenced a negative influence of MMA concentration on the combustion kinetics. A kinetic model of the combustion process was developed, based on the Langmuir?Hinshelwood mechanism, assuming the surface reaction between adsorbed oxygen atoms and adsorbed MMA molecules as the controlling step. The rate expression included the inhibition effects of MMA and water adsorption on the process kinetics. The MMA combustion process simulations evidenced the significant influences of the bulk gas to catalyst particle mass transfer, on the overall kinetics.