Isomeric effects in the gas-phase reactions of dichloroethene, C2H2Cl2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH$_4^+$, H$_3$O$^+$, SF$_3^+$, CF$_3^+$, CF$^+$, SF5$^+$, SF$_2^+$, SF$^+$, CF$_2^+$, SF$_4^+$, O$_2^+$, Xe$^+$, N$_2$O$^+$, CO$_2^+$, Kr$^+$, CO$^+$, N$^+$, N$_2^+$, Ar$^+$, F$^+$ and Ne$^+$) with the three structural isomers of dichloroethene, i.e. 1,1-C$_2$H$_2$Cl$_2$, cis-1,2-C$_2$H$_2$Cl$_2$ and trans-1,2-C$_2$H$_2$Cl$_2$ is reported. The recombination energy of these ions spans the range 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube. Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C$_2$H$_2$Cl$_2$ with photon energies in the range 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H$_3$O$^+$, CF$_3^+$, and CF$^+$. For 1,1-C$_2$H$_2$Cl$_2$ the reaction with H$_3$O$^+$ proceeds at the collisional rate with the only ionic product being 1,1-C$_2$H$_2$Cl$_2$H$^+$. However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C$_2$H$_2$Cl$_2$, but only proceeds with 14 % and 18 % efficiency, respectively. The CF$_3^+$ reaction proceeds with 56-80 % efficiency, the only ionic product for 1,1-C$_2$H$_2$Cl$_2$ being C$_2$H$_2$Cl$^+$ formed via Cl- abstraction, whereas the only ionic product for both 1,2-isomers is CHCl$_2^+$ corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C$_2$H$_2$Cl$_2$ isomers, have been found in the reactions of SF$^+$, CO$_2^+$, CO$^+$, N$_2^+$, and Ar$^+$. Although these five ions have recombination energies above the ionization energy of any of the C$_2$H$_2$Cl$_2$ isomers and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C$_2$H$_2$Cl$_2$ is responsible for the observed effects

Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube reactions of CHF3: comparison of product branching ratios

The threshold photoelectron and threshold photoelectron photoion coincidence spectra of CHF$_3$ in the range 13.5 – 24.5 eV have been recorded. Ion yields and branching ratios have been determined for the three fragments CF$_3^+$, CHF2$^+$ and CF$^+$. The mean kinetic energy releases into fragment ions involving either C-H or C-F bond cleavage have been measured, and compared with statistical and impulsive models. CHF$_3^+$ behaves in a non-statistical manner characteristic of the small-molecule limit, with the ground electronic state and low-lying excited states of CHF$_3^+$ being largely repulsive along the C-H and C-F coordinates, respectively. The rate coefficients and product ion branching ratios have been measured at 298 K in a selected ion flow tube for the reactions of CHF$_3$ with a large number of gas-phase cations whose recombination energies span the range 6.3 through 21.6 eV. A comparison between the branching ratios from the two experiments, together with an analysis of the threshold photoelectron spectrum of CHF$_3$, shows that long-range charge transfer probably occurs for the Ar$^+$ and F$^+$ atomic ions whose recombination energies lie above ca. 15 eV. Below this energy, the mechanism involves a combination of short-range charge transfer and chemical reactions involving a transition state intermediate

The photoionization dynamics of the three structural isomers of dichloroethene

Using tunable vacuum-UV radiation from a synchrotron, the threshold photoelectron spectrum, threshold photoelectron photoion coincidence spectrum and ion breakdown diagram of the 1,1, cis-1,2 and trans-1,2 isomers of C$_2$H$_2$Cl$_2$ have been recorded in the range 9-23 eV. The energies of the peaks in the threshold photoelectron spectrum are in good agreement with outer-valence Greens function caculations. The major difference between the isomers, both predicted and observed experimentally is that the F and G states of C$_2$H$_2$Cl$_2^+$ are approximately degenerate for 1,1 and trans-1,2, but well separated for the cis-1,2 isomer. The ground and low-lying valence states of C$_2$H$_2$Cl$_2^+$ are bound, with higher-lying states dissociating to C$_2$H$_2$Cl$^+$ or C$_2$H$_2^+$. The translational kinetic energy release into C$_2$H$_2$Cl$^+$ + Cl is determined as a function of energy. Isolated-state behaviour for the low-lying electronic states of C$_2$H$_2$Cl$_2^+$ becomes more statistical as the energy increases

Transitioning behaviourally infected HIV-positive young people into adult care: Experiences from the young person’s point of view

Background. There is limited literature on the transition of young people living with HIV/AIDS (YPLHIV) from adolescent/young adult HIV care to adult HIV care in sub-Saharan Africa.Objective. We aimed to share the experiences of HIV-seropositive young adults transitioning into adult care, to inform best practice for such transitioning.Methods. We conducted a retrospective evaluation of the transition of 30 young adults aged ≥25 years from our adolescent/young adult HIV clinic at the Infectious Diseases Institute, Makerere University, Kampala, Uganda, to adult HIV healthcare services between January 2010 and January 2012.Results. Six major themes emerged from the evaluation: (i) adjustment to adult healthcare providers, (ii) the adult clinic logistics, (iii) positive attributes of the adult clinic, (iv) transfer to other health centres, (v) perceived sense of stigma, and (vi) patient-proposed recommendations. A model for transitioning YPLHIV to adult care was proposed.Conclusion. There is a paucity of evidence to inform best practice for transitioning YPLHIV to adult care in resource-limited settings. Ensuring continuity in HIV care and treatment beyond young adult HIV programmes is essential, with provision of enhanced support beyond the transition clinic and youth-friendly approaches by adult-oriented care providers.S Afr J HIV Med 2013;14(1):20-23. DOI:10.7196/SAJHIVMED.88

Extinction by Miscalculation:

Species at Risk Act, Sakinaw sockeye, Cultus sockeye, fisheries management, extinction.

A selected ion flow tube study of the ion-molecule reactions of monochloroethene, trichloroethene and tetrachloroethene

Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 eV (H$_3$O$^+$) through to 21.56 eV (Ne$^+$). Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene (J. Phys. Chem. A., 2006, 110, 5760), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionisation energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionisation energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yield is a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important

Exact Results on the Space of Vacua of Four Dimensional SUSY Gauge Theories

We consider four dimensional quantum field theories which have a continuous manifold of inequivalent exact ground states -- a moduli space of vacua. Classically, the singular points on the moduli space are associated with extra massless particles. Quantum mechanically these singularities can be smoothed out. Alternatively, new massless states appear there. These may be the elementary massless particles or new massless bound states.Comment: 19 pages, RU-94-1

C-erbB2 mRNA expression in human breast tumours: comparison with c-erbB2 DNA amplification and correlation with prognosis.

In this study, we have investigated the expression of the proto-oncogene c-erbB2 in a total of 70 human primary breast tumours. In agreement with other workers, we observed c-erbB2 gene amplification in 17.5% of the tumours studied. In addition, we carried out a comprehensive analysis of c-erbB2 mRNA expression in the tumours using RNase mapping and in situ hybridisation techniques. Our results indicated a more frequent (30%) overexpression of c-erbB2 mRNA, which was associated only with breast carcinomas of a ductal origin. Furthermore, analysis of the c-erbB2 mRNA gene locus in the same tumours demonstrated that enhanced c-erbB2 expression could occur in the presence or absence of gene amplification, suggesting that additional molecular mechanisms may result in overexpression of c-erbB2 mRNA in human mammary tumours. In situ hybridisation showed that elevated levels of c-erbB2 mRNA were specific to malignant cells within the breast tumour. Analysis of the association between c-erbB2 mRNA overexpression and clinicopathological factors revealed a significant correlation with poor tumour grade, but not with steroid receptor status or patient menopausal status. No significant correlation was observed between overexpression of c-erbB2 mRNA and early disease recurrence in our group of patients, although there was a definite trend towards poorer prognosis

Minimizing energy below the glass thresholds

Focusing on the optimization version of the random K-satisfiability problem, the MAX-K-SAT problem, we study the performance of the finite energy version of the Survey Propagation (SP) algorithm. We show that a simple (linear time) backtrack decimation strategy is sufficient to reach configurations well below the lower bound for the dynamic threshold energy and very close to the analytic prediction for the optimal ground states. A comparative numerical study on one of the most efficient local search procedures is also given.Comment: 12 pages, submitted to Phys. Rev. E, accepted for publicatio

Detection of a Fully-resolved Compton Shoulder of the Iron K-alpha Line in the Chandra X-ray Spectrum of GX 301-2

We report the detection of a fully-resolved, Compton-scattered emission line in the X-ray spectrum of the massive binary GX 301-2 obtained with the High Energy Transmission Grating Spectrometer onboard the Chandra X-ray Observatory. The iron K-alpha fluorescence line complex observed in this system consists of an intense narrow component centered at an energy of E = 6.40 keV and a redward shoulder that extends down to ~6.24 keV, which corresponds to an energy shift of a Compton back-scattered iron K-alpha photon. From detailed Monte Carlo simulations and comparisons with the observed spectra, we are able to directly constrain the physical properties of the scattering medium, including the electron temperature and column density, as well as an estimate for the metal abundance.Comment: 13 pages, 4 figures, 1 table, accepted for publication in ApJ Lette