Stereoselective cis -Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions

A highly stereoselective gold(I)-catalyzed cis-vinylcyclopropanation of alkenes has been developed. Allylic gold carbenes, generated via a retro-Buchner reaction of 7-alkenyl-1,3,5-cycloheptatrienes, react with alkenes to form vinylcyclopropanes. The gold(I)-catalyzed retro-Buchner reaction of these substrates proceeds by simple heating at a temperature much lower than that required for the reaction of 7-aryl-1,3,5-cycloheptatrienes (75 °C vs 120 °C). A newly developed Julia−Kocienski reagent enables the synthesis of the required cycloheptatriene derivatives in one step from readily available aldehydes or ketones. On the basis of mechanistic investigations, a stereochemical model for the cis selectivity was proposed. An unprecedented gold-catalyzed isomerization of cis– to trans-cyclopropanes has also been discovered and studied by DFT calculations

Holstein polarons in a strong electric field: delocalized and stretched states

The coherent dynamics of a Holstein polaron in strong electric fields is considered under different regimes. Using analytical and numerical analysis, we show that even for small hopping constant and weak electron-phonon interaction, the original discrete Wannier-Stark (WS) ladder electronic states are each replaced by a semi-continuous band if a resonance condition is satisfied between the phonon frequency and the ladder spacing. In this regime, the original localized WS states can become {\em delocalized}, yielding both `tunneling' and `stretched' polarons. The transport properties of such a system would exhibit a modulation of the phonon replicas in typical tunneling experiments. The modulation will reflect the complex spectra with nearly-fractal structure of the semi-continuous band. In the off-resonance regime, the WS ladder is strongly deformed, although the states are still localized to a degree which depends on the detuning: Both the spacing between the levels in the deformed ladder and the localization length of the resulting eigenfunctions can be adjusted by the applied electric field. We also discuss the regime beyond small hopping constant and weak coupling, and find an interesting mapping to that limit via the Lang-Firsov transformation, which allows one to extend the region of validity of the analysis.Comment: 10 pages, 13 figures, submitted to PR

Nonadiabatic approach to dimerization gap and optical absorption coefficient of the Su-Schrieffer-Heeger model

An analytical nonadiabatic approach has been developed to study the dimerization gap and the optical absorption coefficient of the Su-Schrieffer-Heeger model where the electrons interact with dispersive quantum phonons. By investigating quantitatively the effects of quantum phonon fluctuations on the gap order and the optical responses in this system, we show that the dimerization gap is much more reduced by the quantum lattice fluctuations than the optical absorption coefficient is. The calculated optical absorption coefficient and the density of states do not have the inverse-square-root singularity, but have a peak above the gap edge and there exist a significant tail below the peak. The peak of optical absorption spectrum is not directly corresponding to the dimerized gap. Our results of the optical absorption coefficient agree well with those of the experiments in both the shape and the peak position of the optical absorption spectrum.Comment: 14 pages, 7 figures. to be published in PR

The Theory of Brown Dwarfs and Extrasolar Giant Planets

Straddling the traditional realms of the planets and the stars, objects below the edge of the main sequence have such unique properties, and are being discovered in such quantities, that one can rightly claim that a new field at the interface of planetary science and and astronomy is being born. In this review, we explore the essential elements of the theory of brown dwarfs and giant planets, as well as of the new spectroscopic classes L and T. To this end, we describe their evolution, spectra, atmospheric compositions, chemistry, physics, and nuclear phases and explain the basic systematics of substellar-mass objects across three orders of magnitude in both mass and age and a factor of 30 in effective temperature. Moreover, we discuss the distinctive features of those extrasolar giant planets that are irradiated by a central primary, in particular their reflection spectra, albedos, and transits. Aspects of the latest theory of Jupiter and Saturn are also presented. Throughout, we highlight the effects of condensates, clouds, molecular abundances, and molecular/atomic opacities in brown dwarf and giant planet atmospheres and summarize the resulting spectral diagnostics. Where possible, the theory is put in its current observational context.Comment: 67 pages (including 36 figures), RMP RevTeX LaTeX, accepted for publication in the Reviews of Modern Physics. 30 figures are color. Most of the figures are in GIF format to reduce the overall size. The full version with figures can also be found at: http://jupiter.as.arizona.edu/~burrows/papers/rm

State of the world’s plants and fungi 2020

Kew’s State of the World’s Plants and Fungi project provides assessments of our current knowledge of the diversity of plants and fungi on Earth, the global threats that they face, and the policies to safeguard them. Produced in conjunction with an international scientific symposium, Kew’s State of the World’s Plants and Fungi sets an important international standard from which we can annually track trends in the global status of plant and fungal diversity

Breaking the ceremonial order: patients' and doctors' accounts of removal from a general practitioner's list

The removal of patients from general practitioners' (GPs) lists in the UK offers important sociological insights into what happens when the doctor-patient relationship 'goes wrong'. An interactionist analysis shows how removers (doctors) and removed (patients) strategically invoke 'rules of conduct' to account for difficulties in the doctor-patient relationship and for GPs' decisions to end their relationships with patients. In this paper we extend this analysis through recourse to Bourdieu's theory of practice, by juxtaposing 'paired' accounts of the same removal event by both remover and removed. Our analysis demonstrates the unthinking or non-reflective nature of people's understanding of the rules governing social interactions, but also demonstrates how apparent rule violations make the rules explicit and expose patterns of power distribution. We argue that removal of patients amounts to a strategic exercise of symbolic power by GPs, and that this is experienced as an overtly violent symbolic act by patients. A theoretical reconciliation of interactionist theories of the doctor-patient relationship with Bourdieu's theory of practice is both possible and profitable, providing a micro-macro link in which issues of capital and power within the health (care) field are brought to the fore