Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent

Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.

Performance of the OPA/ARPEGE-T21 global ocean-atmosphere coupled model

The climatology of the OPA/ARPEGE-T21 coupled general circulation model (GCM) is presented. The atmosphere GCM has a T21 spectral truncation and the ocean GCM has a 2°×1.5° average resolution. A 50-year climatic simulation is performed using the OASIS coupler, without flux correction techniques. The mean state and seasonal cycle for the last 10 years of the experiment are described and compared to the corresponding uncoupled experiments and to climatology when available. The model reasonably simulates most of the basic features of the observed climate. Energy budgets and transports in the coupled system, of importance for climate studies, are assessed and prove to be within available estimates. After an adjustment phase of a few years, the model stabilizes around a mean state where the tropics are warm and resemble a permanent ENSO, the Southern Ocean warms and almost no sea-ice is left in the Southern Hemisphere. The atmospheric circulation becomes more zonal and symmetric with respect to the equator. Once those systematic errors are established, the model shows little secular drift, the small remaining trends being mainly associated to horizontal physics in the ocean GCM. The stability of the model is shown to be related to qualities already present in the uncoupled GCMs used, namely a balanced radiation budget at the top-of-the-atmosphere and a tight ocean thermocline.

Gene transfection of HEK cells on supermacroporous polyacrylamide monoliths: a comparison of transient and stable recombinant protein expression in perfusion culture

Transient and continuous recombinant protein expression by HEK cells was evaluated in a perfused monolithic bioreactor. Highly porous synthetic cryogel scaffolds (10ml bed volume) were characterised by scanning electron microscopy and tested as cell substrates. Efficient seeding was achieved (94% inoculum retained, with 91-95% viability). Metabolite monitoring indicated continuous cell growth, and endpoint cell density was estimated by genomic DNA quantification to be 5.2x108, 1.1x109 and 3.5x1010 at day 10, 14 and 18. Culture of stably transfected cells allowed continuous production of the Drosophila cytokine Spätzle by the bioreactor at the same rate as in monolayer culture (total 1.2 mg at d18) and this protein was active. In transient transfection experiments more protein was produced per cell compared with monolayer culture. Confocal microscopy confirmed homogenous GFP expression after transient transfection within the bioreactor. Monolithic bioreactors are thus shown to be a flexible and powerful tool for manufacturing recombinant proteins.

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.

On the discourse of construction competitiveness

It is contended that competitiveness is better understood as a discourse rather than as a characteristic that is supposedly possessed. The discourse of competitiveness derives its legitimacy from the enterprise culture that came to dominance during the 1980s. Current popularized theories of competitiveness are constituent parts of this broader discourse, which has had significant material implications for the UK construction sector. The dominant discourse of competitiveness amongst contracting firms is shaped by the need to achieve structural flexibility to cope with fluctuations in demand. Fashionable espoused improvement recipes such as total quality management, business process re-engineering, and lean construction legitimize and reinforce the material manifestations of the enterprise culture. In consequence, the UK industry is characterized by a plethora of hollowed-out firms that have failed to invest in their human capital. While the adopted model may be rational for individual firms, the systemic effect across the sector as a whole equates to a form of anorexia. However, the discourse of competitiveness is by no means monolithic and continues to be contested locally. There have also been numerous counter-discourses that have been mobilized in response to the undesirable externalities of unbridled enterprise. Currently, important counter-discourses promote the ideas of sustainability and corporate social responsibility.

Structure and magnetic properties of an unprecedented syn-antiμ-nitrito-1κO:2κO′ bridged Mn(iii)-salen complex and its isoelectronic and isostructural formate analogue

The preparation, crystal structures and magnetic properties of two new isoelectronic and isomorphous formate-and nitrite-bridged 1D chains of Mn(III)-salen complexes, [Mn(salen)(HCOO)](n) (1) and [Mn(salen)(NO2)](n) (2), where salen is the dianion of N,N'-bis(salicylidene)-1,2-diaminoethane, are presented. The structures show that the salen ligand coordinates to the four equatorial sites of the metal ion and the formate or nitrite ions coordinate to the axial positions to bridge the Mn(III)-salen units through a syn-anti mu-1 kappa O:2 kappa O' coordination mode. Such a bridging mode is unprecedented in Mn(III) for formate and in any transition metal ion for nitrite. Variable-temperature magnetic susceptibility measurements of complexes 1 and 2 indicate the presence of ferromagnetic exchange interactions with J values of 0.0607 cm(-1) (for 1) and 0.0883 cm(-1) (for 2). The ac measurements indicate negligible frequency dependence for 1 whereas compound 2 exhibits a decrease of chi(ac)' and a concomitant increase of chi(ac)'' on elevating frequency around 2 K. This finding is an indication of slow magnetization reversal characteristic of single-chain magnets or spin-glasses. The mu-nitrito-1 kappa O:2 kappa O' bridge seems to be a potentially superior magnetic coupler to the formate bridge for the construction of single-molecule/-chain magnets as its coupling constant is greater and the chi(ac)' and chi(ac)'' show frequency dependence.

Linguistic epistemology and the notion of monolingualism

This article has several interrelated goals, all of which relate to an attempt at understanding why monolingualism is taken to be the default norm in linguistic inquiry (from sociolinguistics to formal linguistic theorizing). With others, I will take the position that comparing instances of multilingualism to so-called monolingualism is an unfair and inevitably inaccurate comparison since, among other variables, the social environments and access to input of multilinguals compared to monolinguals is most often unavoidably different (cf. Cruz-Ferreira 2006; Edwards 2004). Additionally, I will attempt to demonstrate that even so-called monolinguals have access to a variety of grammars related to different registers of speech and, therefore, are not truly monolingual in the sense that they poses one monolithic grammatical competence. Taken together, the present discussion questions both the default status of monolingualism as well as the functional adequacy of the term monolingualism.

Azide monoliths as convenient flow reactors for efficient Curtius rearrangement reactions

The preparation and use of an azide-containing monolithic reactor is described for use in a flow chemistry device and in particular for conducting Curtius rearrangement reactions via acid chloride inputs.

Regionally coupled atmosphere-ocean-sea ice-marine biogeochemistry model ROM: 1. Description and validation

The general circulation models used to simulate global climate typically feature resolution too coarse to reproduce many smaller-scale processes, which are crucial to determining the regional responses to climate change. A novel approach to downscale climate change scenarios is presented which includes the interactions between the North Atlantic Ocean and the European shelves as well as their impact on the North Atlantic and European climate. The goal of this paper is to introduce the global ocean-regional atmosphere coupling concept and to show the potential benefits of this model system to simulate present-day climate. A global ocean-sea ice-marine biogeochemistry model (MPIOM/HAMOCC) with regionally high horizontal resolution is coupled to an atmospheric regional model (REMO) and global terrestrial hydrology model (HD) via the OASIS coupler. Moreover, results obtained with ROM using NCEP/NCAR reanalysis and ECHAM5/MPIOM CMIP3 historical simulations as boundary conditions are presented and discussed for the North Atlantic and North European region. The validation of all the model components, i.e., ocean, atmosphere, terrestrial hydrology, and ocean biogeochemistry is performed and discussed. The careful and detailed validation of ROM provides evidence that the proposed model system improves the simulation of many aspects of the regional climate, remarkably the ocean, even though some biases persist in other model components, thus leaving potential for future improvement. We conclude that ROM is a powerful tool to estimate possible impacts of climate change on the regional scale.

Participatory Development

Participatory development is a process of taking into account peoples’ agency in development by involving people in decision-making over planning processes that affect their lives. This permits people to achieve basic human needs but also to exercise their ability to challenge the established values and institutions that reproduce the monolithic enterprise of capitalism. Against de-territorialised and universal solutions put forward by development experts, participation raises the central issue of reflexivity, while suggesting how different forms of knowledge, power and agency relate to one another in actors’ diverse spheres of life to achieve degrees of social and environmental justice; this configures the notion of participation in processes of development.