Substituent and counterion effects on the formation of p-dimer dications of end-capped heptathienoacenes

We have investigated the impact of the functionalization and the chemical nature of counterions on the p-dimer dications formation in two end-capped heptathienoacenes. Radical cations of an a-substituted heptathienoacene with triisopropylsilyl groups do not p-dimerize, while those of an a,b-substituted heptathienoacene with four n-decyl side chains show a high propensity toward p-dimerization, increased by PF6 ÿ counterions.

A largely intolerable combination of two mainly unconnected texts: 1. Description of the Barefoot in the Head event, at BHQU, NY, 12/11/09; 2. Fictioning and the End

An evaluation of the 'Barefoot in the Head' performance event, I co-curated with Alun Rowlands and Mark Beasley, at Bruce High Quality Foundation University, New York, as part of Performa 09 New York, 12 November 2009 - an examination of my own performance and the other performances occurring simultaneously at the event.

Agricultural tenancy reform: the end of law; or a new popular culture?

This paper applies a reading of the postmodernisation of law to the incremental reform of agricultural holdings legislation over the last century. In charting the shifting legal basis of agricultural tenancies, from ‘black letter’ positivism to the cultural contextuality of sumptuary law, the paper theorises that the underlying political imperative has been allied to the changing significance of property ownership and use. Rather than reflecting the long-term official desire to maintain the let sector in British agriculture, however, the paper argues that this process has had other aims. In particular, it has been about an annexation of law to legitimise the retention of landowner power while presenting a rhetorical ‘democratisation’ of farming, away from its plutocratic associations and towards a new narrative of ‘depersonalised’ business.

Urban planning under Major: the end of Thatcherism?

This paper explores the urban planning legacy left by Mrs Thatcher. To what extent has Mr Major continued with her approach? Has he developed new directions? This broad question provides the background for an examination of the changes to the planning system since Mrs Thatcher left office. The main themes covered are the new plan-led emphasis, the increase in the coverage of environmental issues, the question of whether a more people oriented perspective has developed with Major's softer touch and the Citizen's Charter and the property-led approach to urban regeneration. The paper concludes that although the contradictions of Thatcherism have led to the relaxation of certain ideological stances to planning, the central themes of Thatcherism - individualism and centralisation - continue unabated.

PPG13 and the residential developer

This paper reviews the evidence in favour of the compact city and considers whether it is a viable policy option. Environmentalists, acadenics and politicians have all expressed strong support for the compact city as a basis for sustainable development. A review of the literature broadly confirms the claims made on its behalf, in particular that it is energy efficient and that it plays a crucial role in preventing rural land loss. It is further shown i) that there is nothing inevitable about the established pattern of urban dispersal, and ii) that although urban land is charaterised by a number of contstraints on development,it could in principle satisfy much of the projected demand for housing. Yet urban sprawl continues. Some of the reasons for this in the case of residential development are examined by comparing the residential development process with the principles of sustainable development. The general conclusion of the paper is that proposals for urban containment are likely to be strongly resisted by housebuilders.

The compact city and the residential developer

Although the compact city is widely promoted as a sustainable form of urban development, little attention has been paid to the feasilibity of its implementation in practice. This paper addresses this isse by presenting the findings of a questionnaire study into the viability of the compact city from the perspective of the volume housebuilder. The study shows that, although well aware of the inherent problems witht the compact city, most were generally positive about the need to redirect more development back into urban areas. In addition, they suggested a large number of strategies for change, including i) a role for public sector agencies in overcoming the condstraints on urban sites; ii) the need for an upward reveision of acceptable densities in local plans and design guides; and iii) the creation of a separate, or revised, Use Class Order to enable mixed use development to compete on a level playing field. It is concluded that the residential developer could be engaged in the process of urban containment provided proposals for implementing the compact city of devised. The need for continuing research to test the actual effects of specific schemes is emphasised.

Gut microbial catabolism of grape seed flavan-3-ols by human faecal microbiota. Targetted analysis of precursor compounds, intermediate metabolites and end-products.

In vitro batch culture fermentations were conducted with grape seed polyphenols and human faecal microbiota, in order to monitor both changes in precursor flavan-3-ols and the formation of microbial-derived metabolites. By the application of UPLC-DAD-ESI-TQ MS, monomers, and dimeric and trimeric procyanidins were shown to be degraded during the first 10 h of fermentation, with notable inter-individual differences being observed between fermentations. This period (10 h) also coincided with the maximum formation of intermediate metabolites, such as 5-(3′,4′-dihydroxyphenyl)-γ-valerolactone and 4-hydroxy-5-(3′,4′-dihydroxyphenyl)-valeric acid, and of several phenolic acids, including 3-(3,4-dihydroxyphenyl)-propionic acid, 3,4-dihydroxyphenylacetic acid, 4-hydroxymandelic acid, and gallic acid (5–10 h maximum formation). Later phases of the incubations (10–48 h) were characterised by the appearance of mono- and non-hydroxylated forms of previous metabolites by dehydroxylation reactions. Of particular interest was the detection of γ-valerolactone, which was seen for the first time as a metabolite from the microbial catabolism of flavan-3-ols. Changes registered during fermentation were finally summarised by a principal component analysis (PCA). Results revealed that 5-(3′,4′-dihydroxyphenyl)-γ-valerolactone was a key metabolite in explaining inter-individual differences and delineating the rate and extent of the microbial catabolism of flavan-3-ols, which could finally affect absorption and bioactivity of these compounds.

Shot by both sides: Punk, politics and the end of “Consensus”

This article examines the ways in which political organisations of the far left and far right responded to punk-informed youth culture in Britain during the late 1970s. It examines how both tried to understand punk within their own ideological framework, particularly in relation to the perceived socio-economic and political crises of the late 1970s, before then endeavouring to appropriate—or use—punk for their own ends. Ultimately, however, the article suggests that while punk may indeed be seen as a cultural response to the breakdown of what some have described as the post-war ‘consensus’ in the 1970s, the far left and far right's focus on cultural expression cut across the basic foundations on which they had been built. Consequently, neither left nor right proved able to provide an effective political conduit through which the disaffections expressed by punk could be channelled.

The large-scale circulation change at the end of the Baiu season in Japan as seen in ERA40 data

The time evolution of the circulation change at the end of the Baiu season is investigated using ERA40 data. An end-day is defined for each of the 23 years based on the 850 hPa θe value at 40˚Nin the 130-140˚E sector exceeding 330 K. Daily time series of variables are composited with respect to this day. These composite time-series exhibit a clearer and more rapid change in the precipitation and the large-scale circulation over the whole East Asia region than those performed using calendar days. The precipitation change includes the abrupt end of the Baiu rain, the northward shift of tropical convection perhaps starting a few days before this, and the start of the heavier rain at higher latitudes. The northward migration of lower tropospheric warm, moist tropical air, a general feature of the seasonal march in the region, is fast over the continent and slow over the ocean. By mid to late July the cooler air over the Sea of Japan is surrounded on 3 sides by the tropical air. It is suggestive that the large-scale stage has been set for a jump to the post-Baiu state, i.e., for the end of the Baiu season. Two likely triggers for the actual change emerge from the analysis. The first is the northward movement of tropical convection into the Philippine region. The second is an equivalent barotropic Rossby wave-train, that over a 10-day period develops downstream across Eurasia. It appears likely that in most years one or both mechanisms can be important in triggering the actual end of the Baiu season.

The expression of the end-Cenomanian oceanic anoxic event (OAE 2) in the Helvetic Alps

Upper Cenomanian pelagic sediments from the northern Alpine Helvetic fold-and-thrust belt (northern Tethyan margin) coeval with Oceanic Anoxic Event (OAE) 2 are characterized by the temporal persistence of micrite sedimentation and lack of organic carbon-rich layers. We studied an expanded section in the Chrummflueschlucht (east of Euthal, Switzerland), which encompasses the OAE 2 time interval. In order to identify the paleoceanographic and paleoenvironmental conditions during OAE 2 in this part of the northern Tethyan margin, and more specifically to trace eventual changes in nutrient levels and oxic conditions, we investigated the biostratigraphy (planktonic foraminifera), the bulk-rock mineralogy, and measured stable carbon- and oxygen-isotopes, total phosphorus (P) and redox-sensitive trace-element (RSTE) contents. We were able to determine – with some remaining uncertainties – the different planktonic foraminiferal biozones characteristic of the Cenomanian–Turonian boundary interval (Rotalipora cushmani, Whiteinella archaeocretacea and Helvetoglobotruncana helvetica zones). In the lower part of the section (R. cushmani total range zone), the bulk-rock δ13C record shows a long-term increase. Within sediments attributed to the W. archaeocretacea partial range zone, δ13C values reach a maximum of 3.3‰ (peak “a”). In the following the values decrease and increase again to arrive at a plateau with high δ13C values of around 3.1‰, which ends with a peak of 3.3‰ (peak “c”). At the top of the section, in sediments belonging to the H. helvetica total range zone, δ13C values decrease to post-OAE values of around 2.2‰. The last occurrence of R. cushmani is observed just above the positive δ13C shift characterizing OAE 2. P contents display small variations along the section with a long-term decreasing trend towards the top. Before the OAE 2 interval, P values show higher values and relatively good covariation with detrital input, indicating higher nutrient input before OAE 2. In sediments corresponding to the onset of the δ13C positive excursion, P content is marked by a sharp peak probably linked to a slowdown in sedimentation rates and/or the presence of a small hiatus, as is shown by the presence of glauconite and phosphatic grains. In the interval corresponding to OAE 2, P values remain low and increase slightly at the end of the positive shift in the δ13C record (in the H. helvetica total range zone). The average contents of RSTE (U, V, As, Co, Mo and Mn) remain low throughout the section and appreciable RSTE enrichments have not been observed for the sedimentary interval corresponding to OAE 2. No correlation is observed with stratigraphic trends in RSTE contents in organic-rich deeper-water sections. The presence of double-keeled planktonic foraminifera species during most of the Cenomanian/Turonian boundary event is another evidence of relatively well-oxygenated conditions in this part of the northern Tethyan outer shelf. Our results show that the Chrummflueschlucht section corresponds to one of the most complete section for the Cenomanian–Turonian boundary interval known from the Helvetic realm even if a small hiatus may be present at the onset of the δ13C record (peak “a”). The evolution of P contents suggests an increase in input of this nutritive element at the onset of OAE2. However, the trends in RSTE contents and the planktonic foraminifera assemblages show that the Helvetic realm has not been affected by strongly depleted oxygen conditions during OAE 2.