Femtosecond probing of bimolecular reactions: The collision complex

Progress has been made in probing the femtosecond dynamics of transition states of chemical reactions.(1) The "half-collision" case of unimolecular reactions has been experimentally investigated for a number of systems and much theoretical work has already been developed.(2) For bimolecular reactions, the case of full collision, the zero of time is a problem which makes the femtosecond temporal resolution of the dynamics a difficult task

Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2

In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions

Political and Media Discourses about Integrating Refugees in the UK

The file attached to this record is the author's final peer reviewed version. The Publisher's final version can be found by following the DOI link.This article addresses political and media discourses about integrating refugees in the UK in the context of the “refugee crisis”. A discursive psychological approach is presented as the best way to understand what talk about the concept is used to accomplish in these debates. A large corpus of political discussions (13 hours of debate featuring 146 politicians) and 960 newspaper articles from the UK were discourse analysed. The analysis identified five dilemmas about integration: Integration is positive and necessary, but challenging; Host communities are presented as welcoming, but there are limits to their capacity; Refugees are responsible for integration, but host communities need to provide support; Good refugees integrate, bad ones don't; Refugees are vulnerable and are skilled. All are used to warrant the inclusion or exclusion of refugees. The responsibility of western nations to support refugees is therefore contingent on the refugees behaving in specific ways

Testing Theoretical Evolutionary Models with AB Dor C and the Initial Mass Function

We assess the constraints on the evolutionary models of young low-mass objects that are provided by the measurements of the companion AB Dor C by Close and coworkers and by a new comparison of model-derived IMFs of star-forming regions to the well-calibrated IMF of the solar neighborhood. After performing an independent analysis of Close's imaging and spectroscopic data for AB Dor C, we find that AB Dor C is not detected at a significant level (SN 1.2) in the SDI images when one narrow-band image is subtracted from another, but that it does appear in the individual SDI frames as well as the images at JHK. Using the age of 75-150 Myr for AB Dor from Luhman, Stauffer, & Mamajek, the luminosity predicted by the models of Chabrier & Baraffe is consistent with the value that we estimate. We measure a spectral type of M6+/-1 from the K-band spectrum of AB Dor C, which is earlier than the value of M8+/-1 from Close and is consistent with the model predictions when a dwarf temperature scale is adopted. In a test of these models at much younger ages, we show that the low-mass IMFs that they produce for star-forming regions are similar to the IMF of the solar neighborhood. If the masses of the low-mass stars and brown dwarfs in these IMFs of star-forming regions were underestimated by a factor of two as suggested by Close, then the IMF characterizing the current generation of Galactic star formation would have to be radically different from the IMF of the solar neighborhood.Comment: 15 pages, accepted to the Astrophysical Journa

A study of weather-dependent data links for deep space applications

Weather-dependent data links for deep space applications, and five potential system

The Peak Brightness and Spatial Distribution of AGB Stars Near the Nucleus of M32

The bright stellar content near the center of the Local Group elliptical galaxy M32 is investigated with 0.12 arcsec FWHM H and K images obtained with the Gemini Mauna Kea telescope. Stars with K = 15.5, which are likely evolving near the tip of the asymptotic giant branch (AGB), are resolved to within 2 arcsec of the nucleus, and it is concluded that the peak stellar brightness near the center of M32 is similar to that in the outer regions of the galaxy. Moreover, the projected density of bright AGB stars follows the visible light profile to within 2 arcsec of the nucleus, indicating that the brightest stars are well mixed throughout the galaxy. Thus, there is no evidence for an age gradient, and the radial variations in spectroscopic indices and ultraviolet colors that have been detected previously must be due to metallicity and/or some other parameter. We suggest that either the bright AGB stars formed as part of a highly uniform and coherent galaxy-wide episode of star formation, or they originated in a separate system that merged with M32.Comment: 9 pages of text, 3 figures. ApJ (Letters) in pres

Carcinogenic effects of ptaquiloside in bracken fern and related compounds

Consumption of the bracken fern Pteridium aquilinum by cattle has been shown to induce bladder and intestinal carcinomas in cattle and to cause a number of diseases in other farm animals. An unstable glucoside named ptaquiloside, containing a reactive cyclopropane ring, has been isolated from the fern and its potent carcinogenicity proven. Nineteen of 31 ferns tested by chemotaxonomic methods in Japan have been found to contain potentially carcinogenic ptaquilosides as have Cheilanthes sieberi and Pteridium esculentum. Hydrolysis of ptaquilosides leads to pterosins; under milder conditions a dienone which is believed to be the primary carcinogen is obtained. Hypacrone, a sesquiterpine containing a reactive cyclopropane ring, has been isolated from Hypolepis punctata and its structure proved by synthesis. Illudins, structurally similar to ptaquiloside, have been isolated from the basidiomycete Omphalotus illudens. These give anti-tumour activity and similar reactivity with nucleophiles to ptaquiloside. Compound CC-1065, a highly toxic antibiotic also containing a cyclopropane ring, has been isolated from Streptomyces zelensis. The mechanism of its reactivity with DNA has been compared to that of ptaquiloside and the small structural differences between carcinogenic and anti-tumour activity discussed. Both CC-1065 and adozelesin, a synthetic analogue with anti-tumour activity, have been shown to alkylate the N-3 atom of adenine in a certain sequence of DNA. The reactivity of cysteine with ptaquilosides and illudins is discussed, as is the role of cysteine alkylating agents in apoptosis. © 2000 Cancer Research Campaig

Changes in catch rates and length and age at maturity, but not growth, of an estuarine plotosid (Cnidoglanis macrocephalus) after heavy fishing

The hypothesis that heavy fishing pressure has led to changes in the biological characteristics of the estuary cobbler (Cnidoglanis macrocephalus) was tested in a large seasonally open estuary in southwestern Australia, where this species completes its life cycle and is the most valuable commercial fish species. Comparisons were made between seasonal data collected for this plotosid (eeltail catfish) in Wilson Inlet during 2005–08 and those recorded with the same fishery-independent sampling regime during 1987–89. These comparisons show that the proportions of larger and older individuals and the catch rates in the more recent period were far lower, i.e., they constituted reductions of 40% for fish ≥430 mm total length, 62% for fish ≥4 years of age, and 80% for catch rate. In addition, total mortality and fishing-induced mortality estimates increased by factors of ~2 and 2.5, respectively. The indications that the abundance and proportion of older C. macrocephalus declined between the two periods are consistent with the perception of long-term commercial fishermen and their shift toward using a smaller maximum gill net mesh to target this species. The sustained heavy fishing pressure on C. macrocephalus between 1987–89 and 2005–08 was accompanied by a marked reduction in length and age at maturity of this species. The shift in probabilistic maturation reaction norms toward smaller fish in 2005–08 and the lack of a conspicuous change in growth between the two periods indicate that the maturity changes were related to fishery-induced evolution rather than to compensatory responses to reduced fish densities

Depletion of carriers and negative differential conductivity in an intrinsic graphene under a dc electric field

The heating of carriers in an intrinsic graphene under an abrupt switching off a dc electric field is examined taking into account both the energy relaxation via acoustic and optic phonons and the interband generation-recombination processes. The later are caused by the interband transitions due to optical phonon modes and thermal radiation. Description of the temporal and steady-state responses, including the nonequilibrium concentration and energy as well as the current-voltage characteristics, is performed. At room temperature, a nearly-linear current-voltage characteristic and a slowly-varied concentration take place for fields up to -- 20 kV/cm. Since a predominant recombination of high-energy carriers due to optical phonon emission at low temperatures, a depletion of concentration takes place below -- 250 K. For lower temperatures the current tends to be saturated and a negative differential conductivity appears below -- 170 K in the region of fields -- 10 V/cm.Comment: 8 pages, 10 figures, extended versio