Pairwise assembly of organopalladium(II) units with cyanurato(3-) and trithiocyanurato(3-) ligands: formation of chiral Pd12, Pd10 and Pd9 cage-molecules

The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which twelve organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally-arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structures derived from the corresponding Pd12 cages by replacing one pair of organopalladium centers with two protons, have also been isolated. Reaction of [Pd{2-phenylpyridine(-H)}-μ-Cl]2 with trithiocyanuric acid gives an entirely different and more open type of cage-complex, comprising only nine organopalladium centers and three thiocyanurato(3-) ligands: cage-closure in this latter system appears to be inhibited by steric crowding of the thiocarbonyl groups.

Variability and trends in stratospheric NO2 in Antarctic summer, and implications for stratospheric NOy

NO2 measurements during 1990–2007, obtained from a zenith-sky spectrometer in the Antarctic, are analysed to determine the long-term changes in NO2. An atmospheric photochemical box model and a radiative transfer model are used to improve the accuracy of determination of the vertical columns from the slant column measurements, and to deduce the amount of NOy from NO2. We find that the NO2 and NOy columns in midsummer have large inter-annual variability superimposed on a broad maximum in 2000, with little or no overall trend over the full time period. These changes are robust to a variety of alternative settings when determining vertical columns from slant columns or determining NOy from NO2. They may signify similar changes in speed of the Brewer-Dobson circulation but with opposite sign, i.e. a broad minimum around 2000. Multiple regressions show significant correlation with solar and quasi-biennial-oscillation indices, and weak correlation with El Nino, but no significant overall trend, corresponding to an increase in Brewer-Dobson circulation of 1.4±3.5%/decade. There remains an unexplained cycle of amplitude and period at least 15% and 17 years, with minimum speed in about 2000.

Changes in reactive stratospheric gases due to a change in Brewer–Dobson circulation: results from a simple model

Amounts of source gases with stratospheric sinks (CFCs, N2O, CH4) are affected by changes in Brewer–Dobson circulation. Source gases and their degradation products are important for atmospheric chemistry and climate. With a simple model, we examine how amounts and lifetimes of source gases and products depend on speed of the circulation. Transient results differ from steady-state and stratospheric results differ from those for stratosphere plus troposphere. Increases in speed increase the stratospheric burden of source gases, but reduce products and reduce total burdens and lifetimes of source gases

Time valued life cycle greenhouse gas emissions from buildings

The UK has adopted legally binding carbon reduction targets of 34% by 2020 and 80% by 2050 (measured against the 1990 baseline). Buildings are estimated to be responsible for more than 50% of greenhouse gas (GHG) emissions in the UK. These consist of both operational, produced during use, and embodied, produced during manufacture of materials and components, and during construction, refurbishments and demolition. A brief assessment suggests that it is unlikely that UK emission reduction targets can be met without substantial reductions in both Oc and Ec. Oc occurs over the lifetime of a building whereas the bulk of Ec occurs at the start of a building’s life. A time value for emissions could influence the decision making process when it comes to comparing mitigation measures which have benefits that occur at different times. An example might be the choice between building construction using low Ec construction materials versus building construction using high Ec construction materials but with lower Oc, although the use of high Ec materials does not necessarily imply a lower Oc. Particular time related issues examined here are: the urgency of the need to achieve large emissions reductions during the next 10 to 20 years; the earlier effective action is taken, the less costly it will be; future reduction in carbon intensity of energy supply; the carbon cycle and relationship between the release of GHG’s and their subsequent concentrations in the atmosphere. An equation is proposed, which weights emissions according to when they occur during the building life cycle, and which effectively increases Ec as a proportion of the total, suggesting that reducing Ec is likely to be more beneficial, in terms of climate change, for most new buildings. Thus, giving higher priority to Ec reductions is likely to result in a bigger positive impact on climate change and mitigation costs.

Syntheses, spectroelectrochemical studies, and molecular and electronic structures of ferrocenyl ene-diynes

The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCHC(CCR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV−vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCHC(CCC6H4NH2-4)2]+ and [FcCHC(CCC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCHC(CCC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCHC(CCC6H4NO2- 4)2]2− could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.

Postmodernism, culture and feminism: the aesthetics of space and performance in Rock Follies and Rock Follies of '77

This article discusses the aesthetic and spatial representational strategies of the popular studio-based musical television drama serials Rock Follies and Rock Follies of ’77. It analyses how the texts’ themes relating to women and the entertainment industry are mediated through their postmodern ironic mode and representation of fantastic spaces. Rock Follies’ distinctive stylised aesthetic and mode of caricature are analysed with reference to the visual intentions and ‘voice’ of the writer, Howard Schuman. Through considering the programmes’ various spatial strategies, the article draws attention to the importance of visual and performance style in their postmodern discourse on culture, fantasy, gender and subjectivity. Analysis of the spaces of musical performance, characters’ domestic environments and simulated entertainment spaces reveals how a dialectic is established between the escapist imaginative pleasures of fantasy and the manipulative and exploitative practices of the culture industry. The shift from the optimism of the first series, when the LittleLadies first form, to the darker mood of the second series, in which they are increasingly divided by industry pressures, is traced through changes in the aesthetics of space and characterisation. As a space of artifice, performance and electronic visual manipulation that facilitates the texts’ reflexive representation of culture and feminised fantasy, the studio’s unique aesthetic strengths emerge through this case study.

Influence of UV radiation on chlorophyll, and antioxidant enzymes of wetland plants in different types of constructed wetland

A surface- and vertical subsurface-flow-constructed wetland were designed to study the response of chlorophyll and antioxidant enzymes to elevated UV radiation in three types of wetland plants (Canna indica, Phragmites austrail, and Typha augustifolia). Results showed that (1) chlorophyll content of C. indica, P. austrail, and T. augustifolia in the constructed wetland was significantly lower where UV radiation was increased by 10 and 20 % above ambient solar level than in treatment with ambient solar UV radiation (p < 0.05). (2) The malondialdehyde (MDA) content, guaiacol peroxidase (POD), superoxide dismutase (SOD), and catalase (CAT) activities of wetland plants increased with elevated UV radiation intensity. (3) The increased rate of MDA, SOD, POD, and CAT activities of C. indica, P. australis, and T. angustifolia by elevated UV radiation of 10 % was higher in vertical subsurface-flow-constructed wetland than in surface-flow-constructed wetland. The sensitivity of MDA, SOD, POD, and CAT activities of C. indica, P. austrail, and T. augustifolia to the elevated UV radiation was lower in surface-flow-constructed wetland than in the vertical subsurface-flow-constructed wetland, which was related to a reduction in UV radiation intensity through the dissolved organic carbon and suspended matter in the water. C. indica had the highest SOD and POD activities, which implied it is more sensitive to enhanced UV radiation. Therefore, different wetland plants had different antioxidant enzymes by elevated UV radiation, which were more sensitive in vertical subsurface-flow-constructed wetland than in surface-flow-constructed wetland.

Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of noncovalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on π-electron-rich pyrenyl residues and π-electron-deficient, chain-folding aromatic diimides that interact through complementary π–π stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

Cocrystalline copolyimides of poly(ethylene 2,6-naphthalate)

Copolycondensation of N,N′-bis(2-hydroxyethyl)-biphenyl-3,4,3′,4′-tetracarboxylic diimide (5–25 mol %) with bis(2-hydroxyethyl)-2,6-naphthalate affords a series of cocrystalline, poly(ethylene 2,6-naphthalate) (PEN)-based poly(ester imide)s. The glass transition temperature rises with the level of comonomer, from 118 °C for PEN itself to 148 °C for the 25% diimide copolymer. X-ray powder and fiber diffraction studies show that, when 5 mol % or more of diimide is present, the α-PEN crystal structure is replaced by a new crystalline phase arising from isomorphic substitution of biphenyldiimide for PEN residues in the polymer crystal lattice. This new phase is provisionally identified as monoclinic, C2/m, with two chains per unit cell, a = 10.56, b = 6.74, c = 13.25 Å, and β = 143.0°.

Ring-opening polymerization in molten PEEK: transient reduction of melt-viscosity by macrocyclic aromatic thioetherketones

Blends of PEEK with macrocyclic thioether-ketones show initial melt-viscosities reduced by more than an order of magnitude relative to the polymer itself, enabling more facile processing and fabrication. On raising the temperature of the melt, however, the macrocycle undergoes spontaneous, entropically-driven ring-opening polymerization (ED-ROP), so that the properties of the final polymer should not, in principle, be compromised by the presence of low-MW macrocyclic material.

'Mental mobility’ in the digital age: entrepreneurs and the online home-based business

Home-based online business ventures are an increasingly pervasive yet under-researched phenomenon. The experiences and mindset of entrepreneurs setting up and running such enterprises require better understanding. Using data from a qualitative study of 23 online home-based business entrepreneurs, we propose the augmented concept of ‘mental mobility’ to encapsulate how they approach their business activities. Drawing on Howard P. Becker's early theorising of mobility, together with Victor Turner's later notion of liminality, we conceptualise mental mobility as the process through which individuals navigate the liminal spaces between the physical and digital spheres of work and the overlapping home/workplace, enabling them to manipulate and partially reconcile the spatial, temporal and emotional tensions that are present in such work environments. Our research also holds important applications for alternative employment contexts and broader social orderings because of the increasingly pervasive and disruptive influence of technology on experiences of remunerated work.

Design of a computerised treatment for short-term memory deficits in aphasia

The treatment of auditory-verbal short-term memory (STM) deficits in aphasia is a growing avenue of research (Martin & Reilly, 2012; Murray, 2012). STM treatment requires time precision, which is suited to computerised delivery. We have designed software, which provides STM treatment for aphasia. The treatment is based on matching listening span tasks (Howard & Franklin, 1990), aiming to improve the temporal maintenance of multi-word sequences (Salis, 2012). The person listens to pairs of word-lists that differ in word-order and decides if the pairs are the same or different. This approach does not require speech output and is suitable for persons with aphasia who have limited or no output. We describe the software and how its review from clinicians shaped its design.