Development of novel brush-type chiral stationary phases based on terpenoid selectors: HPLC evaluation and theoretical investigation of enantioselective binding interactions

The terpenoid chiral selectors dehydroabietic acid, 12,14-dinitrodehydroabietic acid and friedelin have been covalently linked to silica gel yielding three chiral stationary phases CSP 1, CSP 2 and CSP 3, respectively. The enantiodiscriminating capability of each one of these phases was evaluated by HPLC with four families of chiral aromatic compounds composed of alcohols, amines, phenylalanine and tryptophan amino acid derivatives and beta-lactams. The CSP 3 phase, containing a selector with a large friedelane backbone is particularly suitable for resolving free alcohols and their derivatives bearing fluorine substituents, while CSP 2 with a dehydroabietic architecture is the only phase that efficiently discriminates 1, 1'-binaphthol atropisomers. CSP 3 also gives efficient resolution of the free amines. All three phases resolve well the racemates of N-trifluoracetyl and N-3,5-dinitrobenzoyl phenylalanine amino acid ester derivatives. Good enantioseparation of beta-lactams and N-benzoyl tryptophan amino acid derivatives was achieved on CSP 1. In order to understand the structural factors that govern the chiral molecular recognition ability of these phases, molecular dynamics simulations were carried out in the gas phase with binary diastereomeric complexes formed by the selectors of CSP 1 and CSP 2 and several amino acid derivatives. Decomposition of molecular mechanics energies shows that van der Waals interactions dominate the formation of the diastereomeric transient complexes while the electrostatic binding interactions are primarily responsible for the enantioselective binding of the (R)- and (S)-analytes. Analysis of the hydrogen bonds shows that electrostatic interactions are mainly associated with the formation of N-(HO)-O-...=C enantio selective hydrogen bonds between the amide binding sites from the selectors and the carbonyl groups of the analytes. The role of mobile phase polarity, a mixture of n-hexane and propan-2-ol in different ratios, was also evaluated through molecular dynamics simulations in explicit solvent. (c) 2006 Elsevier Ltd. All rights reserved.

Identification of components of the Sigma B Regulon in Listeria monocytogenes that contribute to acid and salt tolerance

Sigma B (σB) is an alternative sigma factor that controls the transcriptional response to stress in Listeria monocytogenes and is also known to play a role in the virulence of this human pathogen. In the present study we investigated the impact of a sigB deletion on the proteome of L. monocytogenes grown in a chemically defined medium both in the presence and in the absence of osmotic stress (0.5 M NaCl). Two new phenotypes associated with the sigB deletion were identified using this medium. (i) Unexpectedly, the strain with the ΔsigB deletion was found to grow faster than the parent strain in the growth medium, but only when 0.5 M NaCl was present. This phenomenon was independent of the carbon source provided in the medium. (ii) The ΔsigB mutant was found to have unusual Gram staining properties compared to the parent, suggesting that σB contributes to the maintenance of an intact cell wall. A proteomic analysis was performed by two-dimensional gel electrophoresis, using cells growing in the exponential and stationary phases. Overall, 11 proteins were found to be differentially expressed in the wild type and the ΔsigB mutant; 10 of these proteins were expressed at lower levels in the mutant, and 1 was overexpressed in the mutant. All 11 proteins were identified by tandem mass spectrometry, and putative functions were assigned based on homology to proteins from other bacteria. Five proteins had putative functions related to carbon utilization (Lmo0539, Lmo0783, Lmo0913, Lmo1830, and Lmo2696), while three proteins were similar to proteins whose functions are unknown but that are known to be stress inducible (Lmo0796, Lmo2391, and Lmo2748). To gain further insight into the role of σB in L. monocytogenes, we deleted the genes encoding four of the proteins, lmo0796, lmo0913, lmo2391, and lmo2748. Phenotypic characterization of the mutants revealed that Lmo2748 plays a role in osmotolerance, while Lmo0796, Lmo0913, and Lmo2391 were all implicated in acid stress tolerance to various degrees. Invasion assays performed with Caco-2 cells indicated that none of the four genes was required for mammalian cell invasion. Microscopic analysis suggested that loss of Lmo2748 might contribute to the cell wall defect observed in the ΔsigB mutant. Overall, this study highlighted two new phenotypes associated with the loss of σB. It also demonstrated clear roles for σB in both osmotic and low-pH stress tolerance and identified specific components of the σB regulon that contribute to the responses observed.

Wave activity for large-amplitude disturbances described by the primitive equations on the sphere

Pseudomomentum and pseudoenergy are both measures of wave activity for disturbances in a fluid, relative to a notional background state. Together they give information on the propagation, growth, and decay of disturbances. Wave activity conservation laws are most readily derived for the primitive equations on the sphere by using isentropic coordinates. However, the intersection of isentropic surfaces with the ground (and associated potential temperature anomalies) is a crucial aspect of baroclinic wave evolution. A new expression is derived for pseudoenergy that is valid for large-amplitude disturbances spanning isentropic layers that may intersect the ground. The pseudoenergy of small-amplitude disturbances is also obtained by linearizing about a zonally symmetric background state. The new expression generalizes previous pseudoenergy results for quasigeostrophic disturbances on the β plane and complements existing large-amplitude results for pseudomomentum. The pseudomomentum and pseudoenergy diagnostics are applied to an extended winter from the European Centre for Medium-Range Weather Forecasts Interim Re-Analysis data. The time series identify distinct phenomena such as a baroclinic wave life cycle where the wave activity in boundary potential temperature saturates nonlinearly almost two days before the peak in wave activity near the tropopause. The coherent zonal propagation speed of disturbances at tropopause level, including distinct eastward, westward, and stationary phases, is shown to be dictated by the ratio of total hemispheric pseudoenergy to pseudomomentum. Variations in the lower-boundary contribution to pseudoenergy dominate changes in propagation speed; phases of westward progression are associated with stronger boundary potential temperature perturbations.

Transpolar voltage and polar cap flux during the substorm cycle and steady convection events

Transpolar voltages observed during traversals of the polar cap by the Defense Meteorological Satellite Program (DMSP) F-13 spacecraft during 2001 are analyzed using the expanding-contracting polar cap model of ionospheric convection. Each of the 10,216 passes is classified by its substorm phase or as a steady convection event (SCE) by inspection of the AE indices. For all phases, we detect a contribution to the transpolar voltage by reconnection in both the dayside magnetopause and in the crosstail current sheet. Detection of the IMF influence is 97% certain during quiet intervals and >99% certain during substorm/SCE growth phases but falls to 75% in substorm expansion phases: It is only 27% during SCEs. Detection of the influence of the nightside voltage is only 19% certain during growth phases, rising during expansion phases to a peak of 96% in recovery phases: During SCEs, it is >99%. The voltage during SCEs is dominated by the nightside, not the dayside, reconnection. On average, substorm expansion phases halt the growth phase rise in polar cap flux rather than reversing it. The main destruction of the excess open flux takes place during the 6- to 10-hour interval after the recovery phase (as seen in AE) and at a rate which is relatively independent of polar cap flux because the NENL has by then retreated to the far tail. The best estimate of the voltage associated with viscous-like transfer of closed field lines into the tail is around 10 kV.

Observed and simulated precursors of stratospheric polar vortex anomalies in the Northern Hemisphere

The Northern Hemisphere stratospheric polar vortex is linked to surface weather. After Stratospheric Sudden Warmings in winter, the tropospheric circulation is often nudged towards the negative phase of the Northern Annular Mode (NAM) and the North Atlantic Oscillation (NAO). A strong stratospheric vortex is often associated with subsequent positive NAM/NAO conditions. For stratosphere–troposphere associations to be useful for forecasting purposes it is crucial that changes to the stratospheric vortex can be understood and predicted. Recent studies have proposed that there exist tropospheric precursors to anomalous vortex events in the stratosphere and that these precursors may be understood by considering the relationship between stationary wave patterns and regional variability. Another important factor is the extent to which the inherent variability of the stratosphere in an atmospheric model influences its ability to simulate stratosphere–troposphere links. Here we examine the lower stratosphere variability in 300-year pre-industrial control integrations from 13 coupled climate models. We show that robust precursors to stratospheric polar vortex anomalies are evident across the multi-model ensemble. The most significant tropospheric component of these precursors consists of a height anomaly dipole across northern Eurasia and large anomalies in upward stationary wave fluxes in the lower stratosphere over the continent. The strength of the stratospheric variability in the models was found to depend on the variability of the upward stationary wave fluxes and the amplitude of the stationary waves.

Multiple stationary solutions of an irradiated slab

A mathematical model describing the heat budget of an irradiated medium is introduced. The one-dimensional form of the equations and boundary conditions are presented and analysed. Heat transport at one face of the slab occurs by absorption (and reflection) of an incoming beam of short-wave radiation with a fraction of this radiation penetrating into the body of the slab, a diffusive heat flux in the slab and a prescribed incoming heat flux term. The other face of the slab is immersed in its own melt and is considered to be a free surface. Here, temperature continuity is prescribed and evolution of the surface is determined by a Stefan condition. These boundary conditions are flexible enough to describe a range of situations such as a laser shining on an opaque medium, or the natural environment of polar sea ice or lake ice. A two-stream radiation model is used which replaces the simple Beer’s law of radiation attenuation frequently used for semi-infinite domains. The stationary solutions of the governing equations are sought and it is found that there exists two possible stationary solutions for a given set of boundary conditions and a range of parameter choices. It is found that the existence of two stationary solutions is a direct result of the model of radiation absorption, due to its effect on the albedo of the medium. A linear stability analysis and numerical calculations indicate that where two stationary solutions exist, the solution corresponding to a larger thickness is always stable and the solution corresponding to a smaller thickness is unstable. Numerical simulations reveal that when there are two solutions, if the slab is thinner than the smaller stationary thickness it will melt completely, whereas if the slab is thicker than the smaller stationary thickness it will evolve toward the larger stationary thickness. These results indicate that other mechanisms (e.g. wave-induced agglomeration of crystals) are necessary to grow a slab from zero initial thickness in the parameter regime that yields two stationary solutions.

Motion of the dayside polar cap boundary during substorm cycles: I. Observations of pulses in the magnetopause reconnection rate

Using data from the EISCAT (European Incoherent Scatter) VHF radar and DMSP (Defense Meteorological Satellite Program) spacecraft passes, we study the motion of the dayside open-closed field line boundary during two substorm cycles. The satellite data show that the motions of ion and electron temperature boundaries in EISCAT data, as reported by Moen et al. (2004), are not localised around the radar; rather, they reflect motions of the open-closed field line boundary at all MLT throughout the dayside auroral ionosphere. The boundary is shown to erode equatorward when the IMF points southward, consistent with the effect of magnetopause reconnection. During the substorm expansion and recovery phases, the dayside boundary returns poleward, whether the IMF points northward or southward. However, the poleward retreat was much faster during the substorm for which the IMF had returned to northward than for the substorm for which the IMF remained southward – even though the former substorm is much the weaker of the two. These poleward retreats are consistent with the destruction of open flux at the tail current sheet. Application of a new analysis of the peak ion energies at the equatorward edge of the cleft/cusp/mantle dispersion seen by the DMSP satellites identifies the dayside reconnection merging gap to extend in MLT from about 9.5 to 15.5 h for most of the interval. Analysis of the boundary motion, and of the convection velocities seen near the boundary by EISCAT, allows calculation of the reconnection rate (mapped down to the ionosphere) from the flow component normal to the boundary in its own rest frame. This reconnection rate is not, in general, significantly different from zero before 06:45 UT (MLT<9.5 h) – indicating that the X line footprint expands over the EISCAT field-of-view to earlier MLT only occasionally and briefly. Between 06:45 UT and 12:45UT (9.5

A Tropospheric Assessment of the ERA-40, NCEP, and JRA-25 Global Reanalyses in the Polar Regions

The reliability of the global reanalyses in the polar regions is investigated. The overview stems from an April 2006 Scientific Committee on Antarctic Research (SCAR) workshop on the performance of global reanalyses in high latitudes held at the British Antarctic Survey. Overall, the skill is much higher in the Arctic than the Antarctic, where the reanalyses are only reliable in the summer months prior to the modern satellite era. In the Antarctic, large circulation differences between the reanalyses are found primarily before 1979, when vast quantities of satellite sounding data started to be assimilated. Specifically for ERA-40, this data discontinuity creates a marked jump in Antarctic snow accumulation, especially at high elevations. In the Arctic, the largest differences are related to the reanalyses depiction of clouds and their associated radiation impacts; ERA-40 captures the cloud variability much better than NCEP1 and JRA-25, but the ERA-40 and JRA-25 clouds are too optically thin for shortwave radiation. To further contrast the reanalyses skill, cyclone tracking results are presented. In the Southern Hemisphere, cyclonic activity is markedly different between the reanalyses, where there are few matched cyclones prior to 1979. In comparison, only some of the weaker cyclones are not matched in the Northern Hemisphere from 1958-2001, again indicating the superior skill in this hemisphere. Although this manuscript focuses on deficiencies in the reanalyses, it is important to note that they are a powerful tool for climate studies in both polar regions when used with a recognition of their limitations.

An objective climatology of the dynamical forcing of polar lows in the Nordic seas

A new objective climatology of polar lows in the Nordic (Norwegian and Barents) seas has been derived from a database of diagnostics of objectively identified cyclones spanning the period January 2000 to April 2004. There are two distinct parts to this study: the development of the objective climatology and a characterization of the dynamical forcing of the polar lows identified. Polar lows are an intense subset of polar mesocyclones. Polar mesocyclones are distinguished from other cyclones in the database as those that occur in cold air outbreaks over the open ocean. The difference between the wet-bulb potential temperature at 700 hPa and the sea surface temperature (SST) is found to be an effective discriminator between the atmospheric conditions associated with polar lows and other cyclones in the Nordic seas. A verification study shows that the objective identification method is reliable in the Nordic seas region. After demonstrating success at identifying polar lows using the above method, the dynamical forcing of the polar lows in the Nordic seas is characterized. Diagnostics of the ratio of mid-level vertical motion attributable to quasi-geostrophic forcing from upper and lower levels (U/L ratio) are used to determine the prevalence of a recently proposed category of extratropical cyclogenesis, type C, for which latent heat release is crucial to development. Thirty-one percent of the objectively identified polar low events (36 from 115) exceeded the U/L ratio of 4.0, previously identified as a threshold for type C cyclones. There is a contrast between polar lows to the north and south of the Nordic seas. In the southern Norwegian Sea, the population of polar low events is dominated by type C cyclones. These possess strong convection and weak low-level baroclinicity. Over the Barents and northern Norwegian seas, the well-known cyclogenesis types A and B dominate. These possess stronger low-level baroclinicity and weaker convection.

A new look at stratospheric sudden warmings. Part III. Polar vortex evolution and vertical structure

The evolution of the Arctic polar vortex during observed major mid-winter stratospheric sudden warmings (SSWs) is investigated for the period 1957-2002, using European Centre for Medium-Range Weather Forecasts (ECMWF) ERA-40 Ertel’s potential vorticity (PV) and temperature fields. Time-lag composites of vertically weighted PV, calculated relative to the SSW onset time, are derived for both vortex displacement SSWs and vortex splitting SSWs, by averaging over the 15 recorded displacement and 13 splitting events. The evolving vertical structure of the polar vortex during a typical SSW of each type is clearly illustrated by plotting an isosurface of the composite PV field, and is shown to be very close to that observed during representative individual events. Results are verified by comparison with an elliptical diagnostic vortex moment technique. For both types of SSW, little variation is found between individual events in the orientation of the developing vortex relative to the underlying topography, i.e. the location of the vortex during SSWs of each type is largely fixed in relation to the Earth’s surface. During each type of SSW, the vortex is found to have a distinctive vertical structure. Vortex splitting events are typically barotropic, with the vortex split occurring near-simultaneously over a large altitude range (20-40 km). In the majority of cases, of the two daughter vortices formed, it is the ‘Siberian’ vortex that dominates over its ‘Canadian’ counterpart. In contrast, displacement events are characterized by a very clear baroclinic structure; the vortex tilts significantly westward with height, so that the top and bottom of the vortex are separated by nearly 180◦ longitude before the upper vortex is sheared away and destroyed.

The Splitting of the Stratospheric Polar Vortex in the Southern Hemisphere, September 2002: Dynamical Evolution

The polar vortex of the Southern Hemisphere (SH) split dramatically during September 2002. The large-scale dynamical effects were manifest throughout the stratosphere and upper troposphere, corresponding to two distinct cyclonic centers in the upper troposphere–stratosphere system. High-resolution (T511) ECMWF analyses, supplemented by analyses from the Met Office, are used to present a detailed dynamical analysis of the event. First, the anomalous evolution of the SH polar vortex is placed in the context of the evolution that is usually witnessed during spring. Then high-resolution fields of potential vorticity (PV) from ECMWF are used to reveal several dynamical features of the split. Vortex fragments are rapidly sheared out into sheets of high (modulus) PV, which subsequently roll up into distinct synoptic-scale vortices. It is proposed that the stratospheric circulation becomes hydrodynamically unstable through a significant depth of the troposphere–stratosphere system as the polar vortex elongates.