Intra- and Intermolecular C−H Activation by Bis(phenolate)pyridineiridium(III) Complexes

A bis(phenolate)pyridine pincer ligand (henceforth abbreviated as ONO) has been employed to support a variety of iridium complexes in oxidation states I, III, and IV. Complexes (ONO)IrL_2Me (L = PPh_3, PEt_3) react with I_2 to cleave the Ir–C bond and liberate MeI, apparently via a mechanism beginning with electron transfer to generate an intermediate Ir(IV) complex, which can be isolated and characterized for the case L = PEt_3. The PPh_3 complex is transformed in benzene at 65 °C to the corresponding phenyl complex, with loss of methane, and subsequently to a species resulting from metalation of a PPh_3 ligand. Labeling and kinetics studies indicate that PPh_3 is the initial site of C–H activation, even though the first observed product is that resulting from intermolecular benzene activation. C–H activation of acetonitrile has also been observed

Ruin Probabilities and Overshoots for General Levy Insurance Risk Processes

We formulate the insurance risk process in a general Levy process setting, and give general theorems for the ruin probability and the asymptotic distribution of the overshoot of the process above a high level, when the process drifts to -\infty a.s. and the positive tail of the Levy measure, or of the ladder height measure, is subexponential or, more generally, convolution equivalent. Results of Asmussen and Kluppelberg [Stochastic Process. Appl. 64 (1996) 103-125] and Bertoin and Doney [Adv. in Appl. Probab. 28 (1996) 207-226] for ruin probabilities and the overshoot in random walk and compound Poisson models are shown to have analogues in the general setup. The identities we derive open the way to further investigation of general renewal-type properties of Levy processes.Comment: Published at http://dx.doi.org/10.1214/105051604000000927 in the Annals of Applied Probability (http://www.imstat.org/aap/) by the Institute of Mathematical Statistics (http://www.imstat.org

Instability of fixed, low-thrust drag compensation

FORCED drag compensation using continuous low-thrustpropulsion has been considered for satellites in low Earth orbit. This simple, but nonoptimal, scheme merely requires that the thrust vector is directed opposite to the drag vector and that the magnitude of the two are equal. In principle, the drag force acting on the spacecraft could be determined onboard using accurate accelerometers. However, for small, low-cost spacecraft such sensors may beunavailable. An alternative strategy would be to Ž x the thrust magnitude equal to the expected air drag that would be experienced by the spacecraft. The thrust levelwould be periodically updated based on ground-based orbit determination. In this Engineering Note, it is shown that such a forced circular orbit with a Ž fixed thrust levelis exponentially unstable for all physically reasonable atmosphere models

The cognitive demands of second order manual control: Applications of the event related brain potential

Three experiments are described in which tracking difficulty is varied in the presence of a covert tone discrimination task. Event related brain potentials (ERPs) elicited by the tones are employed as an index of the resource demands of tracking. The ERP measure reflected the control order variation, and this variable was thereby assumed to compete for perceptual/central processing resources. A fine-grained analysis of the results suggested that the primary demands of second order tracking involve the central processing operations of maintaining a more complex internal model of the dynamic system, rather than the perceptual demands of higher derivative perception. Experiment 3 varied tracking bandwidth in random input tracking, and the ERP was unaffected. Bandwidth was then inferred to compete for response-related processing resources that are independent of the ERP

Cross-cultural generalizability of suicide first aid actions: an analysis of agreement across expert consensus studies from a range of countries and cultures

Background A number of Delphi expert consensus studies have been carried out with different countries and cultural groups to develop guidelines on how a member of the public should provide assistance to a person who is suicidal. The present study aimed to determine whether cross-culturally generalizable suicide first aid actions are possible by comparing agreement across these Delphi studies. Methods Data on endorsement rates for items were compared across six Delphi studies. These studies involved panels of professionals and consumer advocates from English-speaking countries, professionals from Sri Lanka, professionals from Japan, professionals from India, professionals from the Philippines, and professionals and consumer advocates in refugee and immigrant mental health. Correlations were calculated between item endorsement rates across panels. Results There were 18 items that were highly endorsed across all eight of the Delphi panels and an additional 15 items highly endorsed across the panels from the three lower middle-income countries (India, Philippines and Sri Lanka). Correlations across panels in item endorsement rates were all 0.60 or above, but were higher between panels from countries that are socioeconomically similar. Conclusions There is broad agreement across the diverse expert panels about what are appropriate suicide first aid actions for members of the public, indicating that cross-cultural generalizability is possible. However, there is also some cultural specificity, indicating the need for local tailoring

Laboratory Measurements Of White Dwarf Photospheric Spectral Lines: H Beta

We spectroscopically measure multiple hydrogen Balmer line profiles from laboratory plasmas to investigate the theoretical line profiles used in white dwarf (WD) atmosphere models. X-ray radiation produced at the Z Pulsed Power Facility at Sandia National Laboratories initiates plasma formation in a hydrogen-filled gas cell, replicating WD photospheric conditions. Here we present time-resolved measurements of H beta and fit this line using different theoretical line profiles to diagnose electron density, n(e), and n = 2 level population, n2. Aided by synthetic tests, we characterize the validity of our diagnostic method for this experimental platform. During a single experiment, we infer a continuous range of electron densities increasing from n(e) similar to 4 to similar to 30 x 10(16) cm(-3) throughout a 120-ns evolution of our plasma. Also, we observe n(2) to be initially elevated with respect to local thermodynamic equilibrium (LTE); it then equilibrates within similar to 55 ns to become consistent with LTE. This supports our electrontemperature determination of T-e similar to 1.3 eV (similar to 15,000 K) after this time. At n(e) greater than or similar to 10(17) cm(-3), we find that computer-simulation-based line-profile calculations provide better fits (lower reduced chi(2)) than the line profiles currently used in the WD astronomy community. The inferred conditions, however, are in good quantitative agreement. This work establishes an experimental foundation for the future investigation of relative shapes and strengths between different hydrogen Balmer lines.Laboratory Directed Research and Development programUnited States Department of Energy DE-AC04-94AL85000, DE-SC0010623National Science Foundation DGE-1110007Astronom

Leaving College: Why Students Withdrew from a University

The purpose of this study was to determine the reasons why students withdrew during a semester from a mid-sized, comprehensive university located in the Midwest. Six hundred forty-five students were asked to complete the ACT Withdrawing/Non-returning Student Survey during the 1992-93 academic year and summer semester. Three hundred sixty-five completed surveys were returned for a 57% response rate. Respondents indicated many different reasons for leaving which varied by year in school and whether or not the respondent was a graduate or undergraduate student. There was no typical withdrawing student and there were many reasons students withdrew over which the university has little or no control. The report concludes with a discussion of Vincent Tinto\u27s (1993) ideas concerning institutional departure. The retention and persistence of students in higher education has been the focus of serious intellectual inquiry for many years. Various concepts of institutional departure, persistence and models for programmatic interventions to reduce departure have been developed. (For example, see Pascarella & Terenzini, 1991; Stage & Rushin, 1993; Steele, Kennedy, & Gordon, 1993; Tinto, 1993; Wolfe, 1993.) The purpose of this study was to focus on one aspect of student attrition, and. to investigate the reasons and general trends as . to why students withdrew during a semester from a midsized comprehensive university located in the Midwest. This information could then be used to guide institutional action