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.

High-latitude influence of the quasi-biennial oscillation

The interannual variability of the stratospheric winter polar vortex is correlated with the phase of the quasi-biennial oscillation (QBO) of tropical stratospheric winds. This dynamical coupling between high and low latitudes, often referred to as the Holton–Tan effect, has been the subject of numerous observational and modelling studies, yet important questions regarding its mechanism remain unanswered. In particular it remains unclear which vertical levels of the QBO exert the strongest influence on the winter polar vortex, and how QBO–vortex coupling interacts with the effects of other sources of atmospheric interannual variability such as the 11-year solar cycle or the El Nino Southern Oscillation. As stratosphere-resolving general circulation models begin to resolve the QBO and represent its teleconnections with other parts of the climate system, it seems timely to summarize what is currently known about the QBO’s high-latitude influence. In this review article, we offer a synthesis of the modelling and observational analyses of QBO–vortex coupling that have appeared in the literature, and update the observational record.

Comparative effect of dairy fatty acids on cell adhesion molecules, nitric oxide and relative gene expression in healthy and diabetic human aortic endothelial cells

Dairy intake, despite its high saturated fatty acid (SFA) content, is associated with a lower risk of cardiovascular disease and diabetes. This in vitro study determined the effect of individual fatty acids (FA) found in dairy, and FA mixtures representative of a high SFA and a low SFA dairy lipid on markers of endothelial function in healthy and type II diabetic aortic endothelial cells.

Dimer formation by symbiotic donor–acceptor interaction between two molecules of a specially designed dioxomolybdenum(VI) complex containing both donor and acceptor centers – A structural, spectroscopic and DFT study

This work presents a model study for the formation of a dimeric dioxomolybdenum(VI) complex [MoO2L]2, generated by simultaneous satisfaction of acceptor and donor character existing in the corresponding monomeric Mo(VI) complex MoO2L. This mononuclear complex is specially designed to contain a coordinatively unsaturated Mo(VI) acceptor centre and a free donor group, (e.g. –NH2 group) strategically placed in the ligand skeleton [H2L = 2-hydroxyacetophenonehydrazone of 2-aminobenzoylhydrazine]. Apart from the dimer [MoO2L]2, complexes of the type MoO2L·B (where B = CH3OH, γ-picoline and imidazole) are also reported. All the complexes are characterized by elemental analysis, spectroscopic (UV–Vis, IR, 1H NMR) techniques and cyclic voltammetry. Single crystal X-ray structures of [MoO2L]2 (1), MoO2L·CH3OH (2), and MoO2L.(γ-pic) (3) have been determined and discussed. DFT calculation on these complexes corroborates experimental data and provides clue for the facile formation of this type of dimer not reported previously. The process of dimer formation may also be viewed as an interaction between two molecules of a specially designed complex acting as a monodentate ligand. This work is expected to open up a new field of design and synthesis of dimeric complexes through the process of symbiotic donor–acceptor (acid–base) interaction between two molecules of a specially designed monomer.

Tripodal molecules for the promotion of phosphoester hydrolysis

A series of low molecular weight tripodal amide/histidine-containing compounds (1–2) have been synthesised and shown to increase the rate of bis-(p-nitrophenyl) phosphate (BNPP) and soman (GD) breakdown in buffered aqueous solution.

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.

A numerical model of the ionospheric signatures of time-varying magnetic reconnection: III. Quasi-instantaneous convection responses in the Cowley-Lockwood paradigm

Using a numerical implementation of the Cowley and Lockwood (1992) model of flow excitation in the magnetosphere–ionosphere (MI) system, we show that both an expanding (on a _12-min timescale) and a quasiinstantaneous response in ionospheric convection to the onset of magnetopause reconnection can be accommodated by the Cowley–Lockwood conceptual framework. This model has a key feature of time dependence, necessarily considering the history of the coupled MI system. We show that a residual flow, driven by prior magnetopause reconnection, can produce a quasi-instantaneous global ionospheric convection response; perturbations from an equilibrium state may also be present from tail reconnection, which will superpose constructively to give a similar effect. On the other hand, when the MI system is relatively free of pre-existing flow, we can most clearly see the expanding nature of the response. As the open-closed field line boundary will frequently be in motion from such prior reconnection (both at the dayside magnetopause and in the cross-tail current sheet), it is expected that there will usually be some level of combined response to dayside reconnection.

On the quasi-periodic nature of magnetopause flux transfer events

The recurrence rate of flux transfer events (FTEs) observed near the dayside magnetopause is discussed. A survey of magnetopause observations by the ISEE satellites shows that the distribution of the intervals between FTE signatures has a mode value of 3 min, but is highly skewed, having upper and lower decile values of 1.5 min and 18.5 min, respectively. The mean value is found to be 8 min, consistent with previous surveys of magnetopause data. The recurrence of quasi-periodic events in the dayside auroral ionosphere is frequently used as evidence for an association with magnetopause FTEs, and the distribution of their repetition intervals should be matched to that presented here if such an association is to be confirmed. A survey of 1 year's 15-s data on the interplanetary magnetic field (IMF) suggests that the derived distribution could arise from fluctuations in the IMF Bz component, rather than from a natural oscillation frequency of the magnetosphere-ionosphere system.

Energy consistent discontinuous Galerkin methods for a quasi-incompressible diffuse two phase flow model

We design consistent discontinuous Galerkin finite element schemes for the approximation of a quasi-incompressible two phase flow model of Allen–Cahn/Cahn–Hilliard/Navier–Stokes–Korteweg type which allows for phase transitions. We show that the scheme is mass conservative and monotonically energy dissipative. In this case the dissipation is isolated to discrete equivalents of those effects already causing dissipation on the continuous level, that is, there is no artificial numerical dissipation added into the scheme. In this sense the methods are consistent with the energy dissipation of the continuous PDE system.

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.

GPVI potentiation of platelet activation by thrombin and adhesion molecules independent of Src kinases and Syk.

We show that Syk is critical for lamellipodia formation on a range of immobilized proteins but that this can be overcome by addition of thrombin. Further, we reveal a novel role for GPVI in supporting thrombin-induced activation, independent of Syk and Src kinases.

Elucidating the structure of chiral molecules by using amplified vibrational circular dichroism: from theory to experimental realization

Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.

Quasi-sure existence of Gaussian rough paths and large deviation principles for capacities

We construct a quasi-sure version (in the sense of Malliavin) of geometric rough paths associated with a Gaussian process with long-time memory. As an application we establish a large deviation principle (LDP) for capacities for such Gaussian rough paths. Together with Lyons' universal limit theorem, our results yield immediately the corresponding results for pathwise solutions to stochastic differential equations driven by such Gaussian process in the sense of rough paths. Moreover, our LDP result implies the result of Yoshida on the LDP for capacities over the abstract Wiener space associated with such Gaussian process.

Generalized convective quasi-equilibrium principle

A generalization of Arakawa and Schubert's convective quasi-equilibrium principle is presented for a closure formulation of mass-flux convection parameterization. The original principle is based on the budget of the cloud work function. This principle is generalized by considering the budget for a vertical integral of an arbitrary convection-related quantity. The closure formulation includes Arakawa and Schubert's quasi-equilibrium, as well as both CAPE and moisture closures as special cases. The formulation also includes new possibilities for considering vertical integrals that are dependent on convective-scale variables, such as the moisture within convection. The generalized convective quasi-equilibrium is defined by a balance between large-scale forcing and convective response for a given vertically-integrated quantity. The latter takes the form of a convolution of a kernel matrix and a mass-flux spectrum, as in the original convective quasi-equilibrium. The kernel reduces to a scalar when either a bulk formulation is adopted, or only large-scale variables are considered within the vertical integral. Various physical implications of the generalized closure are discussed. These include the possibility that precipitation might be considered as a potentially-significant contribution to the large-scale forcing. Two dicta are proposed as guiding physical principles for the specifying a suitable vertically-integrated quantity.