Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semisolid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KMSUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Synthesis and evaluation of a solid supported molecular tweezer type receptor for cholesterol

A new macroporous stationary phase bearing 'tweezer' receptors that exhibit specificity for cholesterol has been constructed from rigid multifunctional vinylic monomers derived from 3,5-dibromobenzoic acid, propargyl alcohol and cholesterol. The synthesis of the novel tweezer monomer that contains two cholesterol receptor arms using palladium mediated Sonogashira methodologies and carbonate couplings is reported. The subsequent co-polymerisation of this tweezer monomer with a range of cross-linking agents via a 'pseudo' molecular imprinting approach afforded a diverse set of macroporous materials. The selectivity and efficacy of these materials for cholesterol binding was assessed using a chromatographic screening process. The optimum macroporous stationary phase material composition was subsequently used to construct monolithic solid phase extraction columns for use in the selective extraction of cholesterol from multi-component mixtures of structurally related steroids.

Big and little Meccano

The emergence of the mechanical bond during the past 25 years is giving chemistry a fillip in more ways than one. While its arrival on the scene is already impacting materials science and molecular nanotechnology, it is providing a new lease of life to chemical synthesis where mechanical bond formation Occurs as a consequence of the all-important templation Orchestrated by molecular recognition and self-assembly. The way in which covalent bond formation activates noncovalent bonding interactions, switching on molecular recognition that leads to self-assembly, and the template-directed synthesis of mechanically interlocked molecules-of which the so-called catenanes and rotaxanes may be regarded as the prototypes-has introduced a level of integration into chemical synthesis that has not previously been attained jointly at the supramolecular and molecular levels. The challenge now is to carry this I vel of integration during molecular synthesis beyond relatively small molecules into the realms of precisely functionalized extended molecular Structures and superstructures that perform functions in a collective manner as the key sources of instruction, activation, and performance in multi-component integrated Circuits and devices. These forays into organic chemistry by a scientific nomad are traced through thick and thin from the Athens of the North to the Windy City by Lake Michigan with interludes on the edge of the Canadian Shield beside Lake Ontario, in the Socialist Republic of South Yorkshire, on the Plains of Cheshire beside the Wirral, in the Midlands in the Heartland of Albion, and in the City of Angels beside the Peaceful Sea. (C) 2008 Elsevier Ltd. All rights reserved.

Similarity solutions for multicomponent flows

A one-dimensional shock-reflection test problem in the case of slab, cylindrical or spherical symmetry is discussed for multi-component flows. The differential equations for a similarity solution are derived and then solved numerically in conjunction with the Rankine-Hugoniot shock relations.

Zinc mediated azide-alkyne ligation to 1,5- and 1,4,5-substituted 1,2,3-triazoles

A mild method for regioselective formation of 1,5-substituted 1,2,3-triazoles is described. The zinc-mediated reaction works at room temperature and is successful across a wide range of azido/alkynyl substrates. Additionally, the triazole 4-position can be further functionalized through the intermediate aryl-zinc to accommodate a diverse three-component coupling strategy.

The variable link between PNA and NAO in observations and in multi-century CGCM simulations

The link between the Pacific/North American pattern (PNA) and the North Atlantic Oscillation (NAO) is investigated in reanalysis data (NCEP, ERA40) and multi-century CGCM runs for present day climate using three versions of the ECHAM model. PNA and NAO patterns and indices are determined via rotated principal component analysis on monthly mean 500 hPa geopotential height fields using the varimax criteria. On average, the multi-century CGCM simulations show a significant anti-correlation between PNA and NAO. Further, multi-decadal periods with significantly enhanced (high anti-correlation, active phase) or weakened (low correlations, inactive phase) coupling are found in all CGCMs. In the simulated active phases, the storm track activity near Newfoundland has a stronger link with the PNA variability than during the inactive phases. On average, the reanalysis datasets show no significant anti-correlation between PNA and NAO indices, but during the sub-period 1973–1994 a significant anti-correlation is detected, suggesting that the present climate could correspond to an inactive period as detected in the CGCMs. An analysis of possible physical mechanisms suggests that the link between the patterns is established by the baroclinic waves forming the North Atlantic storm track. The geopotential height anomalies associated with negative PNA phases induce an increased advection of warm and moist air from the Gulf of Mexico and cold air from Canada. Both types of advection contribute to increase baroclinicity over eastern North America and also to increase the low level latent heat content of the warm air masses. Thus, growth conditions for eddies at the entrance of the North Atlantic storm track are enhanced. Considering the average temporal development during winter for the CGCM, results show an enhanced Newfoundland storm track maximum in the early winter for negative PNA, followed by a downstream enhancement of the Atlantic storm track in the subsequent months. In active (passive) phases, this seasonal development is enhanced (suppressed). As the storm track over the central and eastern Atlantic is closely related to the NAO variability, this development can be explained by the shift of the NAO index to more positive values.

Development and illustrative outputs of the Community Integrated Assessment System (CIAS), a multi-institutional modular integrated assessment approach for modelling climate change.

This paper describes the development and first results of the “Community Integrated Assessment System” (CIAS), a unique multi-institutional modular and flexible integrated assessment system for modelling climate change. Key to this development is the supporting software infrastructure, SoftIAM. Through it, CIAS is distributed between the community of institutions which has each contributed modules to the CIAS system. At the heart of SoftIAM is the Bespoke Framework Generator (BFG) which enables flexibility in the assembly and composition of individual modules from a pool to form coupled models within CIAS, and flexibility in their deployment onto the available software and hardware resources. Such flexibility greatly enhances modellers’ ability to re-configure the CIAS coupled models to answer different questions, thus tracking evolving policy needs. It also allows rigorous testing of the robustness of IA modelling results to the use of different component modules representing the same processes (for example, the economy). Such processes are often modelled in very different ways, using different paradigms, at the participating institutions. An illustrative application to the study of the relationship between the economy and the earth’s climate system is provided.

El Nino-mean state-seasonal cycle interactions in a multi-model ensemble

The modelled El Nino-mean state-seasonal cycle interactions in 23 coupled ocean-atmosphere GCMs, including the recent IPCC AR4 models, are assessed and compared to observations and theory. The models show a clear improvement over previous generations in simulating the tropical Pacific climatology. Systematic biases still include too strong mean and seasonal cycle of trade winds. El Nino amplitude is shown to be an inverse function of the mean trade winds in agreement with the observed shift of 1976 and with theoretical studies. El Nino amplitude is further shown to be an inverse function of the relative strength of the seasonal cycle. When most of the energy is within the seasonal cycle, little is left for inter-annual signals and vice versa. An interannual coupling strength (ICS) is defined and its relation with the modelled El Nino frequency is compared to that predicted by theoretical models. An assessment of the modelled El Nino in term of SST mode (S-mode) or thermocline mode (T-mode) shows that most models are locked into a S-mode and that only a few models exhibit a hybrid mode, like in observations. It is concluded that several basic El Nino-mean state-seasonal cycle relationships proposed by either theory or analysis of observations seem to be reproduced by CGCMs. This is especially true for the amplitude of El Nino and is less clear for its frequency. Most of these relationships, first established for the pre-industrial control simulations, hold for the double and quadruple CO2 stabilized scenarios. The models that exhibit the largest El Nino amplitude change in these greenhouse gas (GHG) increase scenarios are those that exhibit a mode change towards a T-mode (either from S-mode to hybrid or hybrid to T-mode). This follows the observed 1976 climate shift in the tropical Pacific, and supports the-still debated-finding of studies that associated this shift to increased GHGs. In many respects, these models are also among those that best simulate the tropical Pacific climatology (ECHAM5/MPI-OM, GFDL-CM2.0, GFDL-CM2.1, MRI-CGM2.3.2, UKMO-HadCM3). Results from this large subset of models suggest the likelihood of increased El Nino amplitude in a warmer climate, though there is considerable spread of El Nino behaviour among the models and the changes in the subsurface thermocline properties that may be important for El Nino change could not be assessed. There are no clear indications of an El Nino frequency change with increased GHG.

Effects of solar wind magnetosphere coupling recorded at different geomagnetic latitudes: Separation of directly-driven and storage/release systems

The effect on geomagnetic activity of solar wind speed, compared with that of the strength of the interplanetary magnetic field, differs with geomagnetic latitude. In this study we construct a new index based on monthly standard deviations in the H-component of the geomagnetic field for all geomagnetic latitudes. We demonstrate that for this index the response at auroral regions correlates best with interplanetary coupling functions which include the solar wind speed while mid- and low-latitude regions respond to variations in the interplanetary magnetic field strength. These results are used to isolate the responsible geomagnetic current systems.

Problems in the coupling of eye and hand in the sequential movements of children with developmental coordination disorder

Background: Shifting gaze and attention ahead of the hand is a natural component in the performance of skilled manual actions. Very few studies have examined the precise co-ordination between the eye and hand in children with Developmental Coordination Disorder (DCD). Methods This study directly assessed the maturity of eye-hand co-ordination in children with DCD. A double-step pointing task was used to investigate the coupling of the eye and hand in 7-year-old children with and without DCD. Sequential targets were presented on a computer screen, and eye and hand movements were recorded simultaneously. Results There were no differences between typically developing (TD) and DCD groups when completing fast single-target tasks. There were very few differences in the completion of the first movement in the double-step tasks, but differences did occur during the second sequential movement. One factor appeared to be the propensity for the DCD children to delay their hand movement until some period after the eye had landed on the target. This resulted in a marked increase in eye-hand lead during the second movement, disrupting the close coupling and leading to a slower and less accurate hand movement among children with DCD. Conclusions In contrast to skilled adults, both groups of children preferred to foveate the target prior to initiating a hand movement if time allowed. The TD children, however, were more able to reduce this foveation period and shift towards a feedforward mode of control for hand movements. The children with DCD persevered with a look-then-move strategy, which led to an increase in error. For the group of DCD children in this study, there was no evidence of a problem in speed or accuracy of simple movements, but there was a difficulty in concatenating the sequential shifts of gaze and hand required for the completion of everyday tasks or typical assessment items.

A framework towards multi-modal fingerprinting scheme for multimedia assets

Fingerprinting is a well known approach for identifying multimedia data without having the original data present but what amounts to its essence or ”DNA”. Current approaches show insufficient deployment of three types of knowledge that could be brought to bear in providing a finger printing framework that remains effective, efficient and can accommodate both the whole as well as elemental protection at appropriate levels of abstraction to suit various Foci of Interest (FoI) in an image or cross media artefact. Thus our proposed framework aims to deliver selective composite fingerprinting that remains responsive to the requirements for protection of whole or parts of an image which may be of particularly interest and be especially vulnerable to attempts at rights violation. This is powerfully aided by leveraging both multi-modal information as well as a rich spectrum of collateral context knowledge including both image-level collaterals as well as the inevitably needed market intelligence knowledge such as customers’ social networks interests profiling which we can deploy as a crucial component of our Fingerprinting Collateral Knowledge. This is used in selecting the special FoIs within an image or other media content that have to be selectively and collaterally protected.

A framework towards a multi-modal fingerprinting scheme for multimedia assets

Fingerprinting is a well known approach for identifying multimedia data without having the original data present but instead what amounts to its essence or 'DNA'. Current approaches show insufficient deployment of various types of knowledge that could be brought to bear in providing a fingerprinting framework that remains effective, efficient and can accommodate both the whole as well as elemental protection at appropriate levels of abstraction to suit various Zones of Interest (ZoI) in an image or cross media artefact. The proposed framework aims to deliver selective composite fingerprinting that is powerfully aided by leveraging both multi-modal information as well as a rich spectrum of collateral context knowledge including both image-level collaterals and also the inevitably needed market intelligence knowledge such as customers' social networks interests profiling which we can deploy as a crucial component of our fingerprinting collateral knowledge.

Compositional technique for synthesising multi-phase regular arrays

We describe a high-level design method to synthesize multi-phase regular arrays. The method is based on deriving component designs using classical regular (or systolic) array synthesis techniques and composing these separately evolved component design into a unified global design. Similarity transformations ar e applied to component designs in the composition stage in order to align data ow between the phases of the computations. Three transformations are considered: rotation, re ection and translation. The technique is aimed at the design of hardware components for high-throughput embedded systems applications and we demonstrate this by deriving a multi-phase regular array for the 2-D DCT algorithm which is widely used in many vide ocommunications applications.