Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O-2. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.08 +/- 0.04) + (1.57 +/- 0.32 kJ mol(-1))/RT ln10 The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H2SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O + SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T -> S process in H2SiOO. This process has a small spin orbit coupling matrix element, consistent with an estimate of its rate constant of 1 x 10(9) s(-1) obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O-2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2 + O-2 and SiCl2 + O-2

The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed

Are watershed management plans selected and preferred by stakeholders considering current climate conditions robust against climate change scenarios? A sensitivity study of stakeholders spatially-explicit preferences

In the light of the changing climate, the importance of designing effective watershed management plans that are likely to be implemented is becoming ever more important. This research introduces a new concept, consensus, for incorporation into stakeholder-guided interactive optimization of watershed management plans. User preferences were mathematically simulated based upon scenarios of possible stakeholder attitudes in sub-basins of an agricultural watershed in Indiana, USA, and incorporated into an existing interactive genetic algorithm (GA) framework. These simulated users along with the watershed hydrologic model were used to evaluate overall preference for and performance of hundreds of different possible distributions of wetlands throughout the Eagle Creek Watershed, weighing cost and environmental concerns on and off of their property. Solutions generated using the interactive GA with the consensus measure performed at least as well as the non-interactively generated baseline solutions, and many out-performed the baseline solutions, with higher peak flow reductions for similar total wetland areas. This result is opposite of what was expected. Previous research has characterized adding stakeholders to the optimization process as a “tradeoff” process, where users sacrifice performance for certain intangible factors. In addition to adding a consensus measure to the interactive GA as an additional objective function, this research also developed a method to select short climate model realizations that best represent extreme flow events arising from climate extremes in the projected future. When the interactively and non-interactively generated solutions were subjected to these extreme climate years, their performance was reduced, even when adjusted for the different magnitudes of expected maximum peak flows. Data issues arising from an interruption to the interactive optimization at generation 30 likely led to some irregularities in the results of this research. Nevertheless, it appears that designing watershed management plans that perform well in the present does not necessarily lead to strong performance in the projected future. Any attempts to address climate change in management plans must do so explicitly.Keywords: flooding, interactive genetic algorithms, climate model ensemble, watershed management plans, human computation, stakeholders, wetlands, WRESTOR

Search for GeV Gamma-ray Counterparts of Gravitational Wave Events by CALET

We present results on searches for gamma-ray counterparts of the LIGO/Virgo gravitational-wave events using CALorimetric Electron Telescope ({\sl CALET}) observations. The main instrument of {\sl CALET}, CALorimeter (CAL), observes gamma-rays from $\sim1$ GeV up to 10 TeV with a field of view of nearly 2 sr. In addition, the {\sl CALET} gamma-ray burst monitor (CGBM) views $\sim$3 sr and $\sim2\pi$ sr of the sky in the 7 keV -- 1 MeV and the 40 keV -- 20 MeV bands, respectively, by using two different crystal scintillators. The {\sl CALET} observations on the International Space Station started in October 2015, and here we report analyses of events associated with the following gravitational wave events: GW151226, GW170104, GW170608, GW170814 and GW170817. Although only upper limits on gamma-ray emission are obtained, they correspond to a luminosity of $10^{49}\sim10^{53}$ erg s$^{-1}$ in the GeV energy band depending on the distance and the assumed time duration of each event, which is approximately the order of luminosity of typical short gamma-ray bursts. This implies there will be a favorable opportunity to detect high-energy gamma-ray emission in further observations if additional gravitational wave events with favorable geometry will occur within our field-of-view. We also show the sensitivity of {\sl CALET} for gamma-ray transient events which is the order of $10^{-7}$~erg\,cm$^{-2}$\,s$^{-1}$ for an observation of 100~s duration.Comment: 12 pages, 8 figures, 1 table. Accepted for publication in Astrophysical Journa

On-orbit Operations and Offline Data Processing of CALET onboard the ISS

The CALorimetric Electron Telescope (CALET), launched for installation on the International Space Station (ISS) in August, 2015, has been accumulating scientific data since October, 2015. CALET is intended to perform long-duration observations of high-energy cosmic rays onboard the ISS. CALET directly measures the cosmic-ray electron spectrum in the energy range of 1 GeV to 20 TeV with a 2% energy resolution above 30 GeV. In addition, the instrument can measure the spectrum of gamma rays well into the TeV range, and the spectra of protons and nuclei up to a PeV. In order to operate the CALET onboard ISS, JAXA Ground Support Equipment (JAXA-GSE) and the Waseda CALET Operations Center (WCOC) have been established. Scientific operations using CALET are planned at WCOC, taking into account orbital variations of geomagnetic rigidity cutoff. Scheduled command sequences are used to control the CALET observation modes on orbit. Calibration data acquisition by, for example, recording pedestal and penetrating particle events, a low-energy electron trigger mode operating at high geomagnetic latitude, a low-energy gamma-ray trigger mode operating at low geomagnetic latitude, and an ultra heavy trigger mode, are scheduled around the ISS orbit while maintaining maximum exposure to high-energy electrons and other high-energy shower events by always having the high-energy trigger mode active. The WCOC also prepares and distributes CALET flight data to collaborators in Italy and the United States. As of August 31, 2017, the total observation time is 689 days with a live time fraction of the total time of approximately 84%. Nearly 450 million events are collected with a high-energy (E>10 GeV) trigger. By combining all operation modes with the excellent-quality on-orbit data collected thus far, it is expected that a five-year observation period will provide a wealth of new and interesting results.Comment: 11 pages, 7 figures, published online 27 February 201

Interactive Watershed Optimization in the Presence of Spatially-varying and Uncertain Stakeholder Preferences

Watershed planning over a geographic area is a difficult task primarily due to the presence of large number of stakeholders and decision makers whose intrinsic conflicting and/or subjective preferences often lead to uncertainty in perceived fitness of planning decisions. Deciding which watershed strategy should be implemented at what location requires a participatory approach to design and decision making, if adoption of landscape decisions is critical to success. Analytical participatory design (APD) approaches aim to enable farmers, environmentalists, government agencies, and other stakeholders to visualize the landscape, explore and design competitive scenarios of implementing certain management practices on the landscape. Since these approaches improve decision makers' awareness of opportunities and constraints in the co-existing physical and human systems, it is hypothesized that they can be used to generate acceptable decisions that are robust to uncertainties in stakeholder preferences. An APD method based on Interactive optimization is described in this paper and tested for design of wetlands in a study watershed site (Eagle Creek Watershed) in the state of Indiana. The method is then used to test research hypothesis by involving multiple virtual stakeholders as surrogates to diverse human users and their preferences. The results indicate that, while, as expected, the interactive optimization approach results in lower values of the financial and environmental objective criteria (which are being traded off against users' diverse subjective personal criteria), it also results in a relatively high degree of user consensus, indicating high likelihood of adoption of the generated solutions by the stakeholders

Transient increase in alcohol self-administration following a period of chronic exposure to corticosterone

Stressful life events and chronic stressors have been associated with escalations in alcohol drinking. Stress exposure leads to the secretion of glucocorticoids (cortisol in the human; corticosterone (CORT) in the rodent). To model a period of heightened elevations in CORT, the present work assessed the effects of chronic exposure to the stress hormone CORT on alcohol self-administration. Male Long Evans rats were trained to self-administer a sweetened alcohol solution (2% sucrose/15% alcohol) resulting in moderate levels of daily alcohol intake (0.5–0.7 g/kg). Following stable baseline operant self-administration, rats received CORT in the drinking water for 7 days. A transient increase in alcohol self-administration was observed on the first self-administration session following CORT exposure, and behavior returned to control levels by the second session. Control experiments determined that this increase in alcohol self-administration was specific to alcohol, unrelated to general motor activation, and functionally dissociated from decreased CORT levels at the time of testing. These results indicate that repeated exposure to heightened levels of stress hormone (e.g., as may be experienced during stressful episodes) has the potential to lead to exacerbated alcohol intake in low to moderate drinkers. Given that maladaptive drinking patterns, such as escalated alcohol drinking following stressful episodes, have the potential to put an individual at risk for future drinking disorders, utilization of this model will be important for examination of neuroadaptations that occur as a consequence of CORT exposure in order to better understand escalated drinking following stressful episodes in nondependent individuals

Oral Rehabilitation of Patients Sustaining Orofacial Injuries: The UPenn Initiative

Tissue injuries in the oral and maxillofacial structures secondary to trauma, warfare, ablative cancer, and benign tumor surgery result in significant losses of speech, masticatory and swallowing functions, aesthetic deformities, and overall psychological stressors and compromise. Optimal oral rehabilitation remains a formidable challenge and an unmet clinical need due to the influence of multiple factors related to the physiologic limitations of tissue repair, the lack of site and function-specific donor tissues and constructs, and an integrated team of multidisciplinary professionals. The advancements in stem cell biology, biomaterial science, and tissue engineering technologies, particularly the 3-dimensional bioprinting technology, together with digital imaging and computer-aided design and manufacturing technologies, have paved the path for personalized/precision regenerative medicine. At the University of Pennsylvania, we have launched the initiative to integrate multidisciplinary health professionals and translational/clinical scientists in medicine, dentistry, stem cell biology, tissue engineering, and regenerative medicine to develop a comprehensive, patient-centered approach for precision and personalized reconstruction, as well as oral rehabilitation of patients sustaining orofacial tissue injuries and defects, especially oral cancer patients

Stress Hormone Exposure Reduces mGluR5 Expression in the Nucleus Accumbens: Functional Implications for Interoceptive Sensitivity to Alcohol

Escalations in alcohol drinking associated with experiencing stressful life events and chronic life stressors may be related to altered sensitivity to the interoceptive/subjective effects of alcohol. Indeed, through the use of drug discrimination methods, rats show decreased sensitivity to the discriminative stimulus (interoceptive) effects of alcohol following exposure to the stress hormone corticosterone (CORT). This exposure produces heightened elevations in plasma CORT levels (eg, as may be experienced by an individual during stressful episodes). We hypothesized that decreased sensitivity to alcohol may be related, in part, to changes in metabotropic glutamate receptors-subtype 5 (mGluR5) in the nucleus accumbens, as these receptors in this brain region are known to regulate the discriminative stimulus effects of alcohol. In the accumbens, we found reduced mGluR5 expression (immunohistochemistry and Western blot) and decreased neural activation (as measured by c-Fos immunohistochemistry) in response to a moderate alcohol dose (1 g/kg) following CORT exposure (7 days). The functional role of these CORT-induced adaptations in relation to the discriminative stimulus effects of alcohol was confirmed, as both the systemic administration of 3-Cyano-N-(1,3-diphenyl-1H-pyrazol-5-yl)benzamide (CDPPB) an mGluR5 positive allosteric modulator and the intra-accumbens administration of (R,S)-2-Amino-2-(2-chloro-5-hydroxyphenyl)acetic acid sodium salt (CHPG) an mGluR5 agonist restored sensitivity to alcohol in discrimination-trained rats. These results suggest that activation of mGluR5 may alleviate the functional impact of the CORT-induced downregulation of mGluR5 in relation to sensitivity to alcohol. Understanding the contribution of such neuroadaptations to the interoceptive effects of alcohol may enrich our understanding of potential changes in subjective sensitivity to alcohol during stressful episodes

Enhanced AMPA receptor activity increases operant alcohol self-administration and cue-induced reinstatement: AMPA receptors and alcohol

Long-term alcohol exposure produces neuroadaptations that contribute to the progression of alcohol abuse disorders. Chronic alcohol consumption results in strengthened excitatory neurotransmission and increased AMPA receptor signaling in animal models. However, the mechanistic role of enhanced AMPA receptor activity in alcohol reinforcement and alcohol-seeking behavior remains unclear. This study examined the role of enhanced AMPA receptor function using the selective positive allosteric modulator, aniracetam, in modulating operant alcohol self-administration and cue-induced reinstatement. Male alcohol-preferring (P-) rats, trained to self-administer alcohol (15%, v/v) versus water were pretreated with aniracetam to assess effects on maintenance of alcohol self-administration. To determine reinforcer specificity, P-rats were trained to self-administer sucrose (0.8%, w/v) versus water, and effects of aniracetam were tested. The role of aniracetam in modulating relapse of alcohol-seeking was assessed using a response-contingent cue-induced reinstatement procedure in P-rats trained to self-administer 15% alcohol. Aniracetam pretreatment significantly increased alcohol-reinforced responses relative to vehicle treatment. This increase was not attributed to aniracetam-induced hyperactivity as aniracetam pretreatment did not alter locomotor activity. AMPA receptor involvement was confirmed because DNQX (AMPA receptor antagonist) blocked the aniracetam-induced increase in alcohol self-administration. Aniracetam did not alter sucrose-reinforced responses in sucrose-trained P-rats, suggesting that enhanced AMPA receptor activity is selective in modulating the reinforcing function of alcohol. Finally, aniracetam pretreatment potentiated cue-induced reinstatement of alcohol-seeking behavior versus vehicle treated-P-rats. These data suggest that enhanced glutamate activity at AMPA receptors may be key in facilitating alcohol consumption and seeking behavior which could ultimately contribute to the development of alcohol abuse disorders