Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130◦C, 138◦C, 140◦C and 150◦C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two C H bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid–gas–solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol−1 to 368 kJ mol−1 for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

In vitro fermentation of a red wine extract by human gut microbiota: changes in microbial groups and formation of phenolic metabolites

An in vitro batch culture fermentation experiment was conducted with fecal inocula from three healthy volunteers in the presence and absence of a red wine extract. Changes in main bacterial groups were determined by FISH during a 48 h fermentation period. The catabolism of main flavonoids (i.e., flavan-3-ols and anthocyanins) and the formation of a wide a range of phenolic microbial metabolites were determined by a targeted UPLC-PAD-ESI-TQ MS method. Statistical analysis revealed that catechol/pyrocatechol, as well as 4-hydroxy-5-(phenyl)-valeric, 3- and 4-hydroxyphenylacetic, phenylacetic, phenylpropionic, and benzoic acids, showed the greatest increases in concentration during fermentation, whereas 5-(3′-hydroxyphenyl)-γ-valerolactone, its open form 4-hydroxy-5-(3′-hydroxyphenyl)-valeric acid, and 3,4-dihydroxyphenylacetic acid represented the largest interindividual variations in the catabolism of red wine polyphenols. Despite these changes, microbial catabolism did not produce significant changes in the main bacterial groups detected, although a slight inhibition of the Clostridium histolyticum group was observed.

Communities of practice in UK large contracting firms: contrasting application and non-utilized merits

The idea of a community of practice (CoP) has been offered as the engine to unlock the potential of organizational resources, mainly knowledge and people, to achieve the strategic goal of sustained competitiveness. The relevance and application of CoPs in large UK contracting companies was investigated using two case studies. Contrasting variations in the understanding of the concept between the two contracting companies were observed. While a CoP was applied in one company with strategic intent, the concept was not fully understood in the other. In one company, only a third of CoP members surveyed agreed that CoPs were a vehicle for driving best practice and innovation throughout the business; this compared with more than 60% in agreement in the other contracting firm. The higher agreement and satisfaction of CoP members in the latter case study was the result of the management's understanding and commitment. CoPs require time and organizational support to mature. The strategic inception and management support of CoP application is vital for their maturation and progress. Although the construction industry change discourses portray CoPs as fostering an environment of trust, and hence serving as innovation and competiveness enablers, their potential contribution to contracting firms does not provide a compelling case and hence merits further research studies.

The evolution of innovation capability in multinational enterprise subsidiaries: dual network embeddedness and the divergence of subsidiary specialisation in Taiwan

This paper examines how innovation-related capabilities for production, design and marketing develop at the subsidiary level within multinational enterprises (MNEs). We focus on how subsidiary autonomy and changing opportunities to access internal (MNE) and external (host country) sources of capability contribute in a combined way to the accumulation of specialist capabilities in five Taiwan-based MNE subsidiaries in the semiconductor industry. Longitudinal analysis shows how the accumulation process is subject to discontinuities, as functional divisions are (re)opened and closed during the lifetime of the subsidiary. A composite set of innovation output measures also shows significant variations in within-function levels of capability across our sample. We conclude that subsidiary specialisation and unique subsidiary-specific advantages have evolved in a way that is strongly influenced by the above factors.

Vertical propagation of information in a middle atmosphere data assimilation system by gravity-wave drag feedbacks

The mesospheric response to the 2002 Antarctic Stratospheric Sudden Warming (SSW) is analysed using the Canadian Middle Atmosphere Model Data Assimilation System (CMAM-DAS), where it represents a vertical propagation of information from the observations into the data-free mesosphere. The CMAM-DAS simulates a cooling in the lowest part of the mesosphere which is accomplished by resolved motions, but which is extended to the mid- to upper mesosphere by the response of the model's non-orographic gravity-wave drag parameterization to the change in zonal winds. The basic mechanism is that elucidated by Holton consisting of a net eastward wave-drag anomaly in the mesosphere during the SSW, although in this case there is a net upwelling in the polar mesosphere. Since the zonal-mean mesospheric response is shown to be predictable, this demonstrates that variations in the mesospheric state can be slaved to the lower atmosphere through gravity-wave drag.

EEG activation differences in the pre-motor cortex and supplementary motor area between normal individuals with high and low traits of autism

The human mirror neuron system (hMNS) is believed to provide a basic mechanism for social cognition. Event-related desynchronization (ERD) in alpha (8–12 Hz) and low beta band (12–20 Hz) over sensori-motor cortex has been suggested to index mirror neurons' activity. We tested whether autistic traits revealed by high and low scores on the Autistic Quotient (AQ) in the normal population are linked to variations in the electroencephalogram (EEG) over motor, pre-motor cortex and supplementary motor area (SMA) during action observation. Results revealed that in the low AQ group, the pre-motor cortex and SMA were more active during hand action than static hand observation whereas in the high AQ group the same areas were active both during static and hand action observation. In fact participants with high traits of autism showed greater low beta ERD while observing the static hand than those with low traits and this low beta ERD was not significantly different when they watched hand actions. Over primary motor cortex, the classical alpha and low beta ERD during hand actions relative to static hand observation was found across all participants. These findings suggest that the observation–execution matching system works differently according to the degree of autism traits in the normal population and that this is differentiated in terms of the EEG according to scalp site and bandwidth.

Assessing the impact of occupant behaviour on the electricity consumption for lighting and small power in office buildings

Lighting and small power will typically account for more than half of the total electricity consumption in an office building. Significant variations in electricity used by different tenants suggest that occupants can have a significant impact on the electricity demand for these end-uses. Yet current modelling techniques fail to represent the interaction between occupant and the building environment in a realistic manner. Understanding the impact of such behaviours is crucial to improve the methodology behind current energy modelling techniques, aiming to minimise the significant gap between predicted and in-use performance of buildings. A better understanding of the impact of occupant behaviour on electricity consumption can also inform appropriate energy saving strategies focused on behavioural change. This paper reports on a study aiming to assess the intent of occupants to switch off lighting and appliances when not in use in office buildings. Based on the Theory of Planned Behaviour, the assessment takes the form of a questionnaire and investigates three predictors to behaviour individually: 1) behavioural attitude; 2) subjective norms; 3) perceived behavioural control. The paper details the development of the assessment procedure and discusses preliminary findings from the study. The questionnaire results are compared against electricity consumption data for individual zones within a multi-tenanted office building. Initial results demonstrate a statistically significant correlation between perceived behavioural control and energy consumption for lighting and small power

A comparative study of the main mechanisms controlling indoor air pollution in residential flats

The relative contribution of the main mechanisms that control indoor air quality in residential flats was examined. Indoor and outdoor concentration measurements of different type pollutants (black carbon, SO2, O3, NO, NO2,) were monitored in three naturally ventilated residential flats in Athens, Greece. At each apartment, experiments were conducted during the cold as well as during the warm period of the year. The controlling parameters of transport and deposition mechanisms were calculated from the experimental data. Deposition rates of the same pollutant differ according to the site (different construction characteristics) and to the measuring period for the same site (variations in relative humidity and differences in furnishing). Differences in the black carbon deposition rates were attributed to different black carbon size distributions. The highest deposition rates were observed for O3 in the residential flats with the older construction and the highest humidity levels. The calculated parameters as well as the measured outdoor concentrations were used as input data of a one-compartment indoor air quality model, and the indoor concentrations, the production, and loss rates of the different pollutants were calculated. The model calculated concentrations are in good agreement with the measured values. Model simulations revealed that the mechanism that mainly affected the change rate of indoor black carbon concentrations was the transport from the outdoor environment, while the removal due to deposition was insignificant. During model simulations, it was also established that that the change rate of SO2 concentrations was governed by the interaction between the transport and the deposition mechanisms while NOX concentrations were mainly controlled through photochemical reactions and the transport from outdoors.

Water quality trends in the Windrush catchment: Nitrogen speciation and sediment interactions

For the predominantly agricultural River Windrush catchment, spatial variations in concentrations of nitrogen species and suspended sediment were strongly related to geology and land use. Temporal patterns of NO3- and NO2- concentrations during the three year study were highly correlated with seasonal variations in baseflow. Suspended sediment concentrations were mainly controlled by storm discharge. Variations in total ammonium concentrations reflected both flow controls. Suspended sediment effects total ammonium and organic nitrogen transport to the aquatic system, and in-stream cycling processes. Organic nitrogen did not display consistent seasonal variations, but concentrations occasionally exceeding those of NO3-. Overall, NO3- and organic nitrogen were the most important at 60% and -40%, of total nitrogen load, respectively. Future assessments of agriculture impact on river water quality should consider the total nitrogen load, and not solely that of NO3-.

Stream water quality and nutrient export in the Slapton Catchments

A weekly programme of water quality monitoring has been conducted by Slapton Ley Field Centre since 1970. Samples have been collected for the four main streams draining into Slapton Ley, from the Ley itself and from other sites within the catchment. On occasions, more frequent sampling has been undertaken during short-term research projects, usually in relation to nutrient export from the catchment. These water quality data, unparalleled in length for a series of small drainage basins in the British Isles, provide a unique resource for analysis of spatial and temporal variations in stream water quality within an agricultural area. Not surprisingly, given the eutrophic status of the Ley, most attention has focused on the nutrients nitrate and phosphate. A number of approaches to modelling nutrient loss have been attempted, including time series analysis and the application of nutrient export and physically-based models.

Middle and Late Cenomanian anoxia in shallow and deeper shelf environments of western Morocco

The response of shallow-water sequences to oceanic anoxic event 2 and mid-Cenomanian events 1a and 1b was investigated along the west African margin of Morocco north of Agadir (Azazoul) and correlated with the deep-water sequence of the Tarfaya Basin (Mohammed Beach) based on biostratigraphy, mineralogy, phosphorus and stable isotopes. In the deeper Mohammed Beach section results show double peaks in δ13Corg for mid-Cenomanian events 1a and 1b (Rotalipora reicheli biozone, lower CC10a biozone), the characteristic oceanic anoxic event 2 δ13C excursion (Rotalipora cushmani extinction, top of CC10a biozone) and laminated (anoxic) black shale. In the shallow environment north of Agadir, a fluctuating sea-level associated with dysoxic, brackish and mesotrophic conditions prevailed during the middle to late Cenomanian, as indicated by oyster biostromes, nannofossils, planktonic and benthonic foraminiferal assemblages. Anoxic conditions characteristic of oceanic anoxic event 2 (for example, laminated black shales) did not reach into shallow-water environments until the maximum transgression of the early Turonian. Climate conditions decoupled along the western margin of Morocco between mid-Cenomanian event 1b and the Cenomanian–Turonian boundary, as also observed in eastern Tethys. North of Agadir alternating humid and dry seasonal conditions prevailed, whereas in the Tarfaya Basin the climate was dry and seasonal. This climatic decoupling can be attributed to variations in the Intertropical Convergence Zone and in the intensity of the north-east trade winds in tropical areas.

A mechanism for Atlantic multidecadal variability in the Kiel Climate Model

Atlantic Multidecadal Variability (AMV) is investigated in a millennial control simulation with the Kiel Climate Model (KCM), a coupled atmosphere–ocean–sea ice model. An oscillatory mode with approximately 60 years period and characteristics similar to observations is identified with the aid of three-dimensional temperature and salinity joint empirical orthogonal function analysis. The mode explains 30 % of variability on centennial and shorter timescales in the upper 2,000 m of the North Atlantic. It is associated with changes in the Atlantic Meridional Overturning Circulation (AMOC) of ±1–2 Sv and Atlantic Sea Surface Temperature (SST) of ±0.2 °C. AMV in KCM results from an out-of-phase interaction between horizontal and vertical ocean circulation, coupled through Irminger Sea convection. Wintertime convection in this region is mainly controlled by salinity anomalies transported by the Subpolar Gyre (SPG). Increased (decreased) dense water formation in this region leads to a stronger (weaker) AMOC after 15 years, and this in turn leads to a weaker (stronger) SPG after another 15 years. The key role of salinity variations in the subpolar North Atlantic for AMV is confirmed in a 1,000 year long simulation with salinity restored to model climatology: No low frequency variations in convection are simulated, and the 60 year mode of variability is absent.

On the seasonal onset of polar mesospheric clouds and the breakdown of the stratospheric polar vortex in the Southern Hemisphere

Southern Hemisphere (SH) polar mesospheric clouds (PMCs), also known as noctilucent clouds, have been observed to be more variable and, in general, dimmer than their Northern Hemisphere (NH) counterparts. The precise cause of these hemispheric differences is not well understood. This paper focuses on one aspect of the hemispheric differences: the timing of the PMC season onset. Observations from the Aeronomy of Ice in the Mesosphere satellite indicate that in recent years the date on which the PMC season begins varies much more in the SH than in the NH. Using the Canadian Middle Atmosphere Model, we show that the generation of sufficiently low temperatures necessary for cloud formation in the SH summer polar mesosphere is perturbed by year‐to‐year variations in the timing of the late‐spring breakdown of the SH stratospheric polar vortex. These stratospheric variations, which persist until the end of December, influence the propagation of gravity waves up to the mesosphere. This adds a stratospheric control to the temperatures in the polar mesopause region during early summer, which causes the onset of PMCs to vary from one year to another. This effect is much stronger in the SH than in the NH because the breakdown of the polar vortex occurs much later in the SH, closer in time to the PMC season.

Influence of the quasi-biennial oscillation on the extratropical winter stratosphere in an atmospheric general circulation model and in reanalysis data

The interannual variability of the stratospheric polar vortex during winter in both hemispheres is observed to correlate strongly with the phase of the quasi-biennial oscillation (QBO) in tropical stratospheric winds. It follows that the lack of a spontaneously generated QBO in most atmospheric general circulation models (AGCMs) adversely affects the nature of polar variability in such models. This study examines QBO–vortex coupling in an AGCM in which a QBO is spontaneously induced by resolved and parameterized waves. The QBO–vortex coupling in the AGCM compares favorably to that seen in reanalysis data [from the 40-yr ECMWF Re-Analysis (ERA-40)], provided that careful attention is given to the definition of QBO phase. A phase angle representation of the QBO is employed that is based on the two leading empirical orthogonal functions of equatorial zonal wind vertical profiles. This yields a QBO phase that serves as a proxy for the vertical structure of equatorial winds over the whole depth of the stratosphere and thus provides a means of subsampling the data to select QBO phases with similar vertical profiles of equatorial zonal wind. Using this subsampling, it is found that the QBO phase that induces the strongest polar vortex response in early winter differs from that which induces the strongest late-winter vortex response. This is true in both hemispheres and for both the AGCM and ERA-40. It follows that the strength and timing of QBO influence on the vortex may be affected by the partial seasonal synchronization of QBO phase transitions that occurs both in observations and in the model. This provides a mechanism by which changes in the strength of QBO–vortex correlations may exhibit variability on decadal time scales. In the model, such behavior occurs in the absence of external forcings or interannual variations in sea surface temperatures.

Hurricane-type vortices in a general circulation model

A very high resolution atmospheric general circulation model, T106-L19, has been used for the simulation of hurricanes in a multi-year numerical experiment. Individual storms as well as their geographical and seasonal distribution agree remarkably well with observations. In spite of the fact that only the thermal and dynamical structure of the storms have been used as criteria of their identification, practically all of them occur in areas where the sea surface temperature is higher or equal to 26 °C. There are considerable variations from year to year in the number of storms in spite of the fact that there are no interannual variations in the SST pattern. It is found that the number of storms in particular areas appear to depend on the intensity of the Hadley-Walker cell. The result is clearly resolution-dependant. At lower horizonal resolution, T42, for example, the intensity of the storms is significantly reduced and their overall structure is less realistic, including their vertical form and extent.