Temperature-dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, alpha-pinene and delta-3-carene

Pulsed laser methods for OH generation and detection were used to study atmospheric degradation reactions for three important biogenic gases: OHCisoprene (Reaction R1), OH+α-pinene (Reaction R2) and OH+Δ- 3-carene (Reaction R3). Gas-phase rate coefficients were characterized by non-Arrhenius kinetics for all three reactions. For (R1), k1 (241-356 K)= (1:93±0:08)× 10-11 exp{(466±12)/T} cm3 molecule-1 s-1 was determined, with a room temperature value of k1 (297 K)= (9:3± 0:4)×10-11 cm3 molecule-1 s-1, independent of bath-gas pressure (5-200 Torr) and composition (MDN2 or air). Accuracy and precision were enhanced by online optical monitoring of isoprene, with absolute concentrations obtained via an absorption cross section, αisoprene = (1:28±0:06)× 10-17 cm2 molecule-1 at λ = 184:95 nm, determined in this work. These results indicate that significant discrepancies between previous absolute and relative-rate determinations of k1 result in part from σ values used to derive the isoprene concentration in high-precision absolute determinations. Similar methods were used to determine rate coefficients (in 10-11 cm3 molecule-1 s-1/ for (R2)-(R3): k2 (238-357 K)= (1:83±0:04) ×exp{(330±6)/T } and k3 (235-357 K)= (2:48±0:14) ×exp{(357±17)/T }. This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime conditions. Room temperature values of k2 (296 K)= (5:4±0:2) ×10-11 cm3 molecule-1 s-1 and k3 (297 K)= (8:1±0:3)×10-11 cm3 molecule-1 s-1 were independent of bathgas pressure (7-200 Torr, N2 or air) and in good agreement with previously reported values. In the course of this work, 184.95 nm absorption cross sections were determined: σ = (1:54±0:08) ×10-17 cm2 molecule-1 for α-pinene and (2:40±0:12)×10-17 cm2 molecule-1 for 1-3-carene

Subsumption architecture for enabling strategic coordination of robot swarms in a gaming scenario

The field of swarm robotics breaks away from traditional research by maximizing the performance of a group - swarm - of limited robots instead of optimizing the intelligence of a single robot. Similar to current-generation strategy video games, the player controls groups of units - squads - instead of the individual participants. These individuals are rather unintelligent robots, capable of little more than navigating and using their weapons. However, clever control of the squads of autonomous robots by the game players can make for intense, strategic matches. The gaming framework presented in this article provides players with strategic coordination of robot squads. The developed swarm intelligence techniques break up complex squad commands into several commands for each robot using robot formations and path finding while avoiding obstacles. These algorithms are validated through a 'Capture the Flag' gaming scenario where a complex squad command is split up into several robot commands in a matter of milliseconds

Self-consistent Coulomb picture of an electron-electron bilayer system

In this work we implement the self-consistent Thomas-Fermi approach and a local conductivity model to an electron-electron bilayer system. The presence of an incompressible strip, originating from screening calculations at the top (or bottom) layer is considered as a source of an external potential fluctuation to the bottom (or top) layer. This essentially yields modifications to both screening properties and the magneto-transport quantities. The effect of the temperature, inter-layer distance and density mismatch on the density and the potential fluctuations are investigated. It is observed that the existence of the incompressible strips plays an important role simply due to their poor screening properties on both screening and the magneto-resistance (MR) properties. Here we also report and interpret the observed MR Hysteresis within our model.Comment: 12 pages, 12 figures, submitted to PR

The Inflammasome Drives GSDMD-Independent Secondary Pyroptosis and IL-1 Release in the Absence of Caspase-1 Protease Activity.

Inflammasomes activate the protease caspase-1, which cleaves interleukin-1β and interleukin-18 to generate the mature cytokines and controls their secretion and a form of inflammatory cell death called pyroptosis. By generating mice expressing enzymatically inactive caspase-1 <sup>C284A</sup> , we provide genetic evidence that caspase-1 protease activity is required for canonical IL-1 secretion, pyroptosis, and inflammasome-mediated immunity. In caspase-1-deficient cells, caspase-8 can be activated at the inflammasome. Using mice either lacking the pyroptosis effector gasdermin D (GSDMD) or expressing caspase-1 <sup>C284A</sup> , we found that GSDMD-dependent pyroptosis prevented caspase-8 activation at the inflammasome. In the absence of GSDMD-dependent pyroptosis, the inflammasome engaged a delayed, alternative form of lytic cell death that was accompanied by the release of large amounts of mature IL-1 and contributed to host protection. Features of this cell death modality distinguished it from apoptosis, suggesting it may represent a distinct form of pro-inflammatory regulated necrosis

Excitation and relaxation in atom-cluster collisions

Electronic and vibrational degrees of freedom in atom-cluster collisions are treated simultaneously and self-consistently by combining time-dependent density functional theory with classical molecular dynamics. The gradual change of the excitation mechanisms (electronic and vibrational) as well as the related relaxation phenomena (phase transitions and fragmentation) are studied in a common framework as a function of the impact energy (eV...MeV). Cluster "transparency" characterized by practically undisturbed atom-cluster penetration is predicted to be an important reaction mechanism within a particular window of impact energies.Comment: RevTeX (4 pages, 4 figures included with epsf

Breakup Density in Spectator Fragmentation

Proton-proton correlations and correlations of protons, deuterons and tritons with alpha particles from spectator decays following 197Au + 197Au collisions at 1000 MeV per nucleon have been measured with two highly efficient detector hodoscopes. The constructed correlation functions, interpreted within the approximation of a simultaneous volume decay, indicate a moderate expansion and low breakup densities, similar to assumptions made in statistical multifragmentation models. PACS numbers: 25.70.Pq, 21.65.+f, 25.70.Mn, 25.75.GzComment: 11 pages, LaTeX with 3 included figures; Also available from http://www-kp3.gsi.de/www/kp3/aladin_publications.htm

Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction

The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH+O2 (Reaction R5a), CH3C(O)OH+O3 (Reaction R5b), CH3+CO2+OH+O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293±2)K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37±0.10, α(R5b) =0.12±0.04 and α(R5c) =0.51±0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) =(2.4±0.4)×10-11 cm3 molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5% in OH concentrations in tropical rainforest areas and increases of up to 10% at altitudes of 6-8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx

Carrier-envelope phase effects on the strong-field photoemission of electrons from metallic nanostructures

Sharp metallic nanotapers irradiated with few-cycle laser pulses are emerging as a source of highly confined coherent electron wavepackets with attosecond duration and strong directivity. The possibility to steer, control or switch such electron wavepackets by light is expected to pave the way towards direct visualization of nanoplasmonic field dynamics and real-time probing of electron motion in solid state nanostructures. Such pulses can be generated by strong-field induced tunneling and acceleration of electrons in the near-field of sharp gold tapers within one half-cycle of the driving laser field. Here, we show the effect of the carrier-envelope phase of the laser field on the generation and motion of strong-field emitted electrons from such tips. This is a step forward towards controlling the coherent electron motion in and around metallic nanostructures on ultrashort length and time scales