Enantioselective isothiourea catalysed Michael-Michael-lactonisation cascade; synthesis of δ-lactones and 1,2,3,4-substituted cyclopentanes

The authors thank the EPSRC (ERTR – grant code EP/J500549/1; ABF - grant code EP/J018139/1), the Spanish government for a FPU Fellowship and the University of Seville (V Plan Propio de Investigación) for financial support (PER). This work was supported by the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013) ERC grant agreement no. 279850. ADS thanks the Royal Society for a Wolfson Research Merit Award.This manuscript describes the application of α,β-unsaturated acyl ammonium intermediates in a Michael-Michael-lactonisation cascade process to furnish δ-lactones. Generation of α,β-unsaturated acyl ammonium intermediates was achieved upon addition of isothiourea catalyst HyperBTM into α,β-unsaturated acid chlorides. Subsequent reaction with enonemalonates gave access to δ-lactones in 20-64% yield, 72.5:27.5 to 95:5 er and 81:19 to >95:5 dr. Additionally, application of a ring-opening protocol yielded1,2,3,4-substituted cyclopentanes in 28-77% yield, 76:24 to 98:2 er and 86:14 to >95:5 dr. Interestingly, highest er was observed at high reaction temperatures, with 70˚C proving optimal. This effect was investigated by conducting an Eyring analysis, which indicated that differential activation entropy rather than differential activation enthalpy is responsible for enantiodiscrimination in this process.PostprintPeer reviewe

Ballistic Composite Fermions in Semiconductor Nanostructures

We report the results of two fundamental transport measurements at a Landau level filling factor $\nu$ of 1/2. The well known ballistic electron transport phenomena of quenching of the Hall effect in a mesoscopic cross-junction and negative magnetoresistance of a constriction are observed close to B~=~0 and $\nu~=~ 1/2$. The experimental results demonstrate semi-classical charge transport by composite fermions, which consist of electrons bound to an even number of flux quanta.Comment: 9 pages TeX 3.1415 C version 6.1, 3 PostScript figure

Calorons in Weyl Gauge

We demonstrate by explicit construction that while the untwisted Harrington-Shepard caloron $A_\mu$ is manifestly periodic in Euclidean time, with period $\beta=\frac{1}{T}$, when transformed to the Weyl ($A_0=0$) gauge, the caloron gauge field $A_i$ is periodic only up to a large gauge transformation, with winding number equal to the caloron's topological charge. This helps clarify the tunneling interpretation of these solutions, and their relation to Chern-Simons numbers and winding numbers.Comment: 10 pages, 10 figures, a sign typo in equation 27 is correcte

From Instantons to Sphalerons: Time-Dependent Periodic Solutions of SU(2)-Higgs Theory

We solve numerically for periodic, spherically symmetric, classical solutions of SU(2)-Higgs theory in four-dimensional Euclidean space. In the limit of short periods the solutions approach tiny instanton-anti-instanton superpositions while, for longer periods, the solutions merge with the static sphaleron. A previously predicted bifurcation point, where two branches of periodic solutions meet, appears for Higgs boson masses larger than $3.091 M_W$.Comment: 14 pages, RevTeX with eps figure

Analysis of the temperature-dependent quantum point contact conductance in view of the metal-insulator transition in two dimensions

The temperature dependence of the conductance of a quantum point contact has been measured. The conductance as a function of the Fermi energy shows temperature-independent fixed points, located at roughly multiple integers of $e^{2}/h$. Around the first fixed point at e$^{2}$/h, the experimental data for different temperatures can been scaled onto a single curve. For pure thermal smearing of the conductance steps, a scaling parameter of one is expected. The measured scaling parameter, however, is significantly larger than 1. The deviations are interpreted as a signature of the potential landscape of the quantum point contact, and of the source-drain bias voltage. We relate our results phenomenologically to the metal-insulator transition in two dimensions.Comment: 5 pages, 3 figure

Surveying Battery Cell Sections to Determine the Composition and Spatial Distribution of Discharge Products using an Automated Microprobe

Determining the spatial distribution and composition of hydrohetaerolite in polished sections of discharged Leclanché cells requires the measurement of oxygen concentrations on microcrystalline material. This can be done if the composition of the mounting medium is included in the matrix correction of raw intensities. The method of Pouchou and Pichoir (PAP) is used initially to correct raw intensities obtained from surveys of microcrystalline standard material. Mean analyses agree well with the known compositions provided a correction is made for the oxygen content of the mounting medium. The same correction is then applied to the raw data collected when surveying cell sections, yielding spatially correlated analyses of hydro-hetaerolite formed as a discharge product. The surveying technique could be applied to lead-acid, Leclanché and alkaline cells

Brane-world black holes and the scale of gravity

A particle in four dimensions should behave like a classical black hole if the horizon radius is larger than the Compton wavelength or, equivalently, if its degeneracy (measured by entropy in units of the Planck scale) is large. For spherically symmetric black holes in 4 + d dimensions, both arguments again lead to a mass threshold MC and degeneracy scale Mdeg of the order of the fundamental scale of gravity MG. In the brane-world, deviations from the Schwarzschild metric induced by bulk effects alter the horizon radius and effective four-dimensional Euclidean action in such a way that MC \simeq Mdeg might be either larger or smaller than MG. This opens up the possibility that black holes exist with a mass smaller than MG and might be produced at the LHC even if M>10 TeV, whereas effects due to bulk graviton exchanges remain undetectable because suppressed by inverse powers of MG. Conversely, even if black holes are not found at the LHC, it is still possible that MC>MG and MG \simeq 1TeV.Comment: 4 pages, no figur

Bad bosses and self-verification: the moderating role of core self-evaluations with trust in workplace management

Who responds most strongly to supervisor social undermining? Building on self-verification theory (Swann, 1983, 1987), we theorize that employees with positive views of the self (i.e., higher core self-evaluations [CSEs]) who also maintain higher trust in workplace management are more likely to experience heightened stress and turnover intentions when undermined. We argue that this subset of employees (high CSE, high trust) are more likely to feel misunderstood when undermined by their supervisor and that this lack of self-verification partially explains their stronger responses to supervisor undermining. We find initial support for the first part of our model in a study of 259 healthcare workers in the United States and replicate and extend our findings in the second study of 330 employees in the United Kingdom. Our results suggest that the employees Human Resources often wishes to attract and retain—employees with high CSE and high trust in workplace management—react most strongly to supervisor social undermining

A study of the quantum classical crossover in the spin dynamics of the 2D S=5/2 antiferromagnet Rb2MnF4: neutron scattering, computer simulations, and analytic theories

We report comprehensive inelastic neutron scattering measurements of the magnetic excitations in the 2D spin-5/2 Heisenberg antiferromagnet Rb2MnF4 as a function of temperature from deep in the Neel ordered phase up to paramagnetic, 0.13 < kBT/4JS < 1.4. Well defined spin-waves are found for wave-vectors larger than the inverse correlation length $\eta^{-1}$ for temperatures up to near the Curie-Weiss temperature, $\Theta_{CW}$. For wave-vectors smaller than $\eta^{-1}$, relaxational dynamics occurs. The observed renormalization of spin-wave energies, and evolution of excitation line-shapes, with increasing temperature are quantitatively compared with finite-temperature spin-wave theory, and computer simulations for classical spins. Random phase approximation calculations provide a good description of the low-temperature renormalisation of spin-waves. In contrast, lifetime broadening calculated using the first Born approximation shows, at best, modest agreement around the zone boundary at low temperatures. Classical dynamics simulations using an appropriate quantum-classical correspondence were found to provide a good description of the intermediate- and high-temperature regimes over all wave-vector and energy scales, and the crossover from quantum to classical dynamics observed around $\Theta_{CW}/S$, where the spin S=5/2. A characterisation of the data over the whole wave-vector/energy/temperature parameter space is given. In this, $T^2$ behaviour is found to dominate the wave-vector and temperature dependence of the line widths over a large parameter range, and no evidence of hydrodynamic behaviour or dynamical scaling behaviour found within the accuracy of the data sets.Comment: 28 pages 20 figures, Published in J. Stat. Mech. (2008) P05017 without change

Tourism policy and destination marketing in developing countries: the chain of influence

Tourism marketers including destination marketing organisations (DMOs) and international tour operators play a pivotal role in destination marketing, especially in creating destination images. These images, apparent in tourist brochures, are designed to influence tourist decision-making and behaviour. This paper proposes the concept of a “chain of influence” in destination marketing and image-making, suggesting that the content of marketing materials is influenced by the priorities of those who design these materials, e.g. tour operators and DMOs. A content analysis of 2,000 pictures from DMO and tour operator brochures revealed synergies and divergence between these marketers. The brochure content was then compared to the South African tourism policy, concluding that the dominant factor in the chain of influence in the South African context is in fact its organic image