On an alleged truth/falsity asymmetry in context shifting experiments

Keith DeRose has argued that context shifting experiments should be designed in a specific way in order to accommodate what he calls a ‘truth/falsity asymmetry’. I explain and critique DeRose's reasons for proposing this modification to contextualist methodology, drawing on recent experimental studies of DeRose's bank cases as well as experimental findings about the verification of affirmative and negative statements. While DeRose's arguments for his particular modification to contextualist methodology fail, the lesson of his proposal is that there is good reason to pay close attention to several subtle aspects of the design of context shifting experiments.

Self-assembly studies of a chiral bisurea-based superhydrogelator

A chiral bisurea-based superhydrogelator that is capable of forming supramolecular hydrogels at concentrations as low as 0.2 mm is reported. This soft material has been characterized by thermal studies, rheology, X-ray diffraction analysis, transmission electron microscopy (TEM), and by various spectroscopic techniques (electronic and vibrational circular dichroism and by FTIR and Raman spectroscopy). The expression of chirality on the molecular and supramolecular levels has been studied and a clear amplification of its chirality into the achiral analogue has been observed. Furthermore, thermal analysis showed that the hydroACHTUNGTRENUNGgel- ACHTUNGTRENUNGation of compound 1 has a high response to temperature, which corresponds to an enthalpy-driven self-assembly process. These particular thermal characteristics make these materials easy to handle for soft-application technologies

Oppositely charged polyelectrolytes: complex formation and effects of chain asymmetry

The formation of complexes in solutions of oppositely charged polyions has been studied by Monte Carlo simulations. The amount as well as the length, and thus, the absolute charge of one of the polyions have been varied. There is an increasing tendency to form large clusters as the excess of one kind of polyion decreases. When all polyions have the same length, this tendency reaches a maximum near, but off, equivalent amounts of the two types of polyions. When one kind of polyion is made shorter, the propensity to form large clusters decreases and the fluctuations in cluster charge increases. Simple free-energy expressions have been formulated on the basis of a set of simple rules that help rationalize the observations. By calculating cluster distributions in both grand canonical and canonical ensembles, it has been possible to show the extent of finite-size effects in the simulations.

Variation, asymmetry and working memory in the process of second language acquisition

Calls for understanding the interface between L2 linguistic knowledge and development (Gregg 1996; Carroll 2001; Towell 2003) provide a context for analysing the role of memory (Paradis 2004), specifically working memory (Baddeley 1986, 2003) in L2 development. Miyake and Friedman (1998) have claimed that Working Memory (WM) may be the key to L2 acquisition, especially in explaining individual variation in L2 acquisition. Recent findings found a robust connection between greater working memory (WM) capacity and rapid, successful acquisition of L2 vocabulary, reading and oral fluency (Service 1992; Harrington and Sawyer 1992; Fortkamp 1999). This study adds to the growing body of research by investigating correlations between WM and variation in grammatical development, focusing on asymmetries in processing L2 English wh-constructions in an immersion setting.

Pairwise assembly of organopalladium(II) units with cyanurato(3-) and trithiocyanurato(3-) ligands: formation of chiral Pd12, Pd10 and Pd9 cage-molecules

The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which twelve organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally-arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structures derived from the corresponding Pd12 cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl]2 with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3-) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.

An optically transparent thin-layer electrochemical cell for the study of vibrational circular dichroism of chiral redox-active molecules

An optically transparent thin-layer electrochemical (OTTLE) cell with a locally extended optical path has been developed in order to perform vibrational circular dichroism (VCD) spectroscopy on chiral molecules prepared in specific oxidation states by means of electrochemical reduction or oxidation. The new design of the electrochemical cell successfully addresses the technical challenges involved in achieving sufficient infrared absorption. The VCD-OTTLE cell proves to be a valuable tool for the investigation of chiral redox-active molecules.

Arrays of chiral nanotubes and a layered coordination polymer containing gallium-sulfide supertetrahedral clusters

We report here a unique chiral hybrid gallium sulfide, [NC2H8]2[Ga10S16(N2C12H12)(NC2H7)2] 1, consisting of helical chains of organically-functionalised supertetrahedral clusters which form quadruple-stranded helical nanotubes of ca. 3 nm diameter. This material therefore consists of discrete metal-organic nanotubes which, to the best of our knowledge, are extremely rare. Whilst solvothermal reactions involving 1,2-di(4-pyridyl)ethylene (DPE) resulted in the formation of such single-walled chiral nanotubes, the use of longer 4,4’-trimethylenedipyridine (TMP) ligands resulted in the synthesis of a two-dimensional hybrid gallium sulfide, [C5H6N]3[Ga10S16(OH)(N2C13H14)] 2 in which, for the first time, inorganic and organic linkages between supertetrahedral clusters coexist.

Spectral asymmetry of the massless Dirac operator on a 3-torus

Consider the massless Dirac operator on a 3-torus equipped with Euclidean metric and standard spin structure. It is known that the eigenvalues can be calculated explicitly: the spectrum is symmetric about zero and zero itself is a double eigenvalue. The aim of the paper is to develop a perturbation theory for the eigenvalue with smallest modulus with respect to perturbations of the metric. Here the application of perturbation techniques is hindered by the fact that eigenvalues of the massless Dirac operator have even multiplicity, which is a consequence of this operator commuting with the antilinear operator of charge conjugation (a peculiar feature of dimension 3). We derive an asymptotic formula for the eigenvalue with smallest modulus for arbitrary perturbations of the metric and present two particular families of Riemannian metrics for which the eigenvalue with smallest modulus can be evaluated explicitly. We also establish a relation between our asymptotic formula and the eta invariant.

Structure and stress of Re(11%21); chiral terraces at a racemic surface

The surface structure and morphology of the clean Re(11%21) surface has been investigated through combined low energy electron diffraction intensity analysis of data taken at multiple angles of incidence, scanning tunneling microscopy, and first-principles density functional calculations. The results show how this globally racemic surface terminates in two chirally distinct terraces, which show largescale out-of-plane atomic relaxations and in-plane lateral movement of the uppermost atoms. We further identify and discuss the initial stages of step bunching upon adsorption of oxygen that leads ultimately to the large-scale faceting of the surface. Finally, we present calculations of surface stress and the response to applied surface strain, which suggest routes to the exertion of control over the expression of chirality at the surface.

Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

The annual-cycle modulation of meridional asymmetry in ENSO’s atmospheric response and its dependence on ENSO zonal structure

Previous studies documented that a distinct southward shift of central-Pacific low-level wind anomalies occurring during the ENSO decaying phase, is caused by an interaction between the Western Pacific annual cycle and El Niño-Southern Oscillation (ENSO) variability. The present study finds that the meridional movement of the central-Pacific wind anomalies appears only during traditional Eastern-Pacific (or EP) El Niño events rather than in Central-Pacific (CP) El Niño events in which sea surface temperature (SST) anomalies are confined to the central Pacific. The zonal structure of ENSO-related SST anomalies therefore has an important effect on meridional asymmetry in the associated atmospheric response and its modulation by the annual cycle. In contrast to EP El Niño events, the SST anomalies of CP El Niño events extend further west towards to the warm pool region with its climatological warm SSTs. In the warm pool region, relatively small SST anomalies thus are able to excite convection anomalies on both sides of the equator, even with a meridionally asymmetric SST background state. Therefore, almost meridionally symmetric precipitation and wind anomalies are observed over the central Pacific during the decaying phase of CP El Niño events. The SST anomaly pattern of La Niña events is similar to CP El Niño events with a reversed sign. Accordingly, no distinct southward displacement of the atmospheric response occurs over the central Pacific during the La Niña decaying phase. These results have important implications for ENSO climate impacts over East Asia, since the anomalous low-level anticyclone over the western North Pacific is an integral part of the annual cycle-modulated ENSO response.

Revisiting asymmetry for the decaying phases of El Niño and La Niña

This study investigated the relationship between the asymmetry in the duration of El Ni?o and La Ni?a and the length of their decaying phases. The results suggested that the duration asymmetry comes from the long decaying ENSO cases rather than the short decaying ones. The evolutions of short decaying El Ni?o and La Ni?a are approximately a mirror image with a rapid decline in the following summer for the warm and cold events. However, a robust asymmetry was found in long decaying cases, with a prolonged and re-intensified La Ni?a in the following winter. The asymmetry for long decaying cases starts from the westward extension of the zonal wind anomalies in a mature winter, and is further contributed to by the air-sea interaction over the tropical Pacific in the following seasons.

Dawn-dusk asymmetry in particles of solar wind origin within the magnetosphere

Solar wind/magnetosheath plasma in the magnetosphere can be identified using a component that has a higher charge state, lower density and, at least soon after their entry into the magnetosphere, lower energy than plasma from a terrestrial source. We survey here observations taken over 3 years of He2+ ions made by the Magnetospheric Ion Composition Sensor (MICS) of the Charge and Mass Mgnetospheric Ion Composition Experiment (CAMMICE) instrument aboard POLAR. The occurrence probability of these solar wind ions is then plotted as a function of Magnetic Local Time (MLT) and invariant latitude (3) for various energy ranges. For all energies observed by MICS (1.8–21.4 keV) and all solar wind conditions, the occurrence probabilities peaked around the cusp region and along the dawn flank. The solar wind conditions were filtered to see if this dawnward asymmetry is controlled by the Svalgaard-Mansurov effect (and so depends on the BY component of the interplanetary magnetic field, IMF) or by Fermi acceleration of He2+ at the bow shock (and so depends on the IMF ratio BX/BY ). It is shown that the asymmetry remained persistently on the dawn flank, suggesting it was not due to effects associated with direct entry into the magnetosphere. This asymmetry, with enhanced fluxes on the dawn flank, persisted for lower energy ions (below a “cross-over” energy of about 23 keV) but reversed sense to give higher fluxes on the dusk flank at higher energies. This can be explained by the competing effects of gradient/curvature drifts and the convection electric field on ions that are convecting sunward on re-closed field lines. The lower-energy He2+ ions E × B drift dawnwards as they move earthward, whereas the higher energy ions curvature/gradient drift towards dusk. The convection electric field in the tail is weaker for northward IMF. Ions then need less energy to drift to the dusk flank, so that the cross-over energy, at which the asymmetry changes sense, is reduced.

Switchable amplification of vibrational circular dichroism as a probe of local chiral structure

A new method to detect the vibrational circular dichroism (VCD) of a localized part of a chiral molecular system is reported. A local VCD amplifier was implemented, and the distance dependence of the amplification was investigated in a series of peptides. The results indicate a characteristic distance of 2.0±0.3 bonds, which suggests that the amplification is a localized phenomenon. The amplifier can be covalently coupled to a specific part of a molecule, and can be switched ON and OFF electrochemically. By subtracting the VCD spectra obtained when the amplifier is in the ON and OFF states, the VCD of the local environment of the amplifier can be separated from the total VCD spectrum. Switchable local VCD amplification thus makes it possible to “zoom in” on a specific part of a chiral molecule.

Emulation of chiral hydrogenation catalysts by adsorbtion of small molecules onto Ni surfaces

Adsorption of small molecules on the Ni{111} and NiO{111} surfaces is investigated under UHV and elevated pressures (~10-1 mbar) of hydrogen and water. The molecules considered are chosen for their relevance to understanding the mechanism of enantioselective hydrogenation on Raney Nickel modified by chiral molecules. Adsorption of water onto, and its subsequent reaction with, oxygen-covered Ni{111} is dependent on the initial atomic oxygen coverage. An OH species (O1s binding energy 531.5eV), oriented perpendicular to the surface, forms at atomic oxygen coverages <0.25ML. The reaction does not consume all the adsorbed oxygen for coverages ≥0.12ML. The p(2×2) atomic oxygen uperstructure is unreactive, while an OH species is formed on the p(√3×√3) superstructure at binding energy 530.9eV. L-alanine is adsorbed on Ni{111} as a model chiral modifier molecule. At low coverages, alanine forms a presumed tridentate alaninate species for coverages ≥0.11ML at 250K. A minority, bidentate zwitterionic species forms at coverages >0.11ML, but was not observed at 300K. Saturation occurs at 0.25ML. At high alanine coverages (≥0.19ML) and H2 pressure (≥1×10-2 mbar), the tridentate L-alaninate converts to bidentate zwitterionic L-alanine at 300K. Thermal evolution of L-alanine on Ni{111} under varying hydrogen pressures is examined. Adsorption of L-alanine onto hydroxylated NiO{111} at 300K in UHV, mimicking a catalyst surface under aqueous conditions, yields the tridentate alaninate which is immune to the effects of elevated hydrogen pressure. Exposing the L-alanine/Ni{111} adsorption system to water (≤10-1 mbar) oxidises the surface and recreates the L-alanine/hydroxylated NiO{111} system. Pyruvic acid on Ni{111} is examined as a model for hydrogenation substrate adsorption. Behaviour is coverage dependent and several conformations are possible at low coverages (≤0.1ML). Annealing at coverages <0.2ML causes a condensation reaction, releasing water onto the surface. High coverages do not condense and a saturation coverage of ~0.35ML is found.