Photochromic dithienylethene derivatives containing Ru(II) or Os(II) metal units. Sensitized photocyclization from a triplet state

Efficient photocyclization from a low-lying triplet state is reported for a photochromic dithienylperfluorocyclopentene with Ru(bpy)(3) units attached via a phenylene linker to the thiophene rings. The ring-closure reaction in the nanosecond domain is sensitized by the metal complexes. Upon photoexcitation into the lowest Ru-to-bpy (MLCT)-M-1 state followed by intersystem crossing to emitting (MLCT)-M-3 states, photoreactive (IL)-I-3 states are populated by an efficient energy-transfer process. The involvement of these (IL)-I-3 states explains the quantum yield of the photocyclization, which is independent of the excitation wavelength but decreases strongly in the presence of dioxygen. This behavior differs substantially from the photocyclization of the nonemissive dithienylperfluorocyclopentene free ligand, which occurs from the lowest (IL)-I-1 state on a picosecond time scale and is insensitive to oxygen quenching. Cyclic voltammetric studies have also been performed to gain further insight into the energetics of the system. The very high photocyclization quantum yields, far above 0.5 in both cases, are ascribed to the strong steric repulsion between the bulky substituents on the dithienylperfluorocyclopentene bridge bearing the chelating bipyridine sites or the Ru(bpy)(3) moieties, forcing the system to adopt nearly exclusively the reactive antiparallel conformation. In contrast, replacement of both Ru(II) centers by Os(II) completely prevents the photocyclization reaction upon light excitation into the low-lying Os-to-bpy (MLCT)-M-1 state. The photoreaction can only be triggered by optical population of the higher lying (IL)-I-1 excited state of the central photochromic unit, but its yield is low due to efficient energy transfer to the luminescent lowest (MLCT)-M-3 state.

Chercher pour or chercher après: arguing the case for contact-induced linguistic innovation in different varieties of French

This paper provides evidence for the claim made in Baetens Beardsmore (1971) that the grammatical collocation "chercher après" «to look for», which is very frequent in Brussels French, is the result of transfer from the contact language, Brussels Dutch. A detailed quantitative analysis of this construction in different varieties of French which have more or less contact with a Germanic language was made to investigate the likelihood of influence from the Germanic substrate. The differences between the meaning of "chercher" and "chercher après" are also analysed in some depth, to find out whether or not the particle is redundant. According to Trudgill (2004) redundant constructions are more often found in contact situations involving long-term, stable contact and child bilingualism. The particle "après" was found to add a particular shade of meaning to "chercher", and is thus not redundant. Therefore no evidence could be obtained from the current data for Trudgill’s (2004) claim.

A framework for English? Or a vehicle for literacy? English teaching in England in the age of the Strategy

This article considers the evolution and impact on schools in England of the "Framework for English" since its introduction in 2001, a national initiative that follows on from the National Literacy Strategy, which focused on primary schools. Whilst acknowledging that the Framework is part of a whole school policy, "The Key Stage Three Strategy", I concentrate on its direct impact on the school subject "English" and on standards within that subject. Such a discussion must incorporate some consideration of the rise of "Literacy" as a dominant term and theme in England (and globally) and its challenge to a politically controversial and much contested curriculum area, i.e. "English". If the Framework is considered within the context of the Literacy drive since the mid-1990s then it can be see to be evolving within a much changed policy context and therefore likely to change substantially in the next few years. In a global context England has been regarded for some time as at the extreme edge of standards-driven policy and practice. It is hoped that the story of "English" in England may be salutary to educators from other countries.

Effect of triclosan or a phenolic farm disinfectant on the selection of antibiotic-resistant Salmonella enterica

Objective: To determine the effect of growth of five strains of Salmonella enterica and their isogenic multiply antibiotic-resistant (MAR) derivatives with a phenolic farm disinfectant or triclosan (biocides) upon the frequency of mutation to resistance to antibiotics or cyclohexane. Methods: Strains were grown in broth with or without the biocides and then spread on to agar containing ampicillin, ciprofloxacin or tetracycline each at 4x MIC or agar overlaid with cyclohexane. Incubation was for 24 and 48 h and the frequency of mutation to resistance was calculated for strains with and without prior growth with the biocides. MICs were determined and the presence of mutations in the acrR and marR regions was determined by sequencing and the presence of mutations in gyrA by light-cycler analysis, for a selection of the mutants that arose. Results: The mean frequency of mutation to antibiotic or cyclohexane resistance was increased similar to10- to 100-fold by prior growth with the phenolic disinfectant or triclosan. The increases were statistically significant for all antibiotics and cyclohexane following exposure to the phenolic disinfectant (P less than or equal to 0.013), and for ampicillin and cyclohexane following exposure to triclosan (P less than or equal to 0.009). Mutants inhibited by >1 mg/L ciprofloxacin arose only from strains that were MAR. Reduced susceptibility to ciprofloxacin (at 4x MIC for parent strains) alone was associated with mutations in gyrA. MAR mutants did not contain mutations in the acrR or marR region. Conclusions: These data renew fears that the use of biocides may lead to an increased selective pressure towards antibiotic resistance.

Mutation of toxB and a truncated version of the efa-1 gene in Escherichia coli O157 : H7 influences the expression and secretion of locus of enterocyte effacement-encoded proteins but not intestinal colonization in calves or sheep

Enterohemorrhagic Escherichia coli (EHEC) strains comprise a broad group of bacteria, some of which cause attaching and effacing (AE) lesions and enteritis in humans and animals. Non-O157:H7 EHEC strains contain the gene efa-1 (referred to in previous publications as efa1), which influences adherence to cultured epithelial cells. An almost identical gene in enteropathogenic E. coli (lifA) mediates the inhibition of lymphocyte proliferation and proinflammatory cytokine synthesis. We have shown previously that significantly lower numbers of EHEC 05 and 0111 efa-1 mutants are shed in feces following experimental infection in calves and that these mutants exhibit reduced adherence to intestinal epithelia compared with isogenic wild-type strains. E. coli O157:H7 strains lack efa-1 but encode a homolog on the pO157 plasmid (toxB/l7095) and contain a truncated version of the efa-1 gene (efa-1'/z4332 in O island 122 of the EDL933 chromosome). Here we report that E. coli O157:H7 toxB and efa-1' single and double mutants exhibit reduced adherence to cultured epithelial cells and show reduced expression and secretion of proteins encoded by the locus of enterocyte effacement (LEE), which plays a key role in the host-cell interactions of EHEC. The activity of LEE1, LEE4, and LEE5 promoters was not significantly altered in E. coli O157:H7 strains harboring toxB or efa-1' mutations, indicating that the effect on the expression of LEE-encoded secreted proteins occurs at a posttranscriptional level. Despite affecting type III secretion, mutation of toxB and efa-1' did not significantly affect the course of fecal shedding of E. coli O157:H7 following experimental inoculation of 10- to 14-day-old calves or 6-week-old sheep. Mutation of tir caused a significant reduction in fecal shedding of E. coli O157:H7 in calves, indicating that the formation of AE lesions is important for colonization of the bovine intestine.

All-or-none (or something in between) transition of DNA

DNA compaction can be caused by multivalent ions as condensing agents. Both discontinuous (all-or-none) and continuous (pearl-necklace structure) transitions have been observed in experiments as the concentration of the condensing agent was increased. We have investigated the DNA transition by analytical calculations in the infinite-chain limit. A mechanism for pearl-necklace structures could be a combinatorial entropy term, which favours a mixture of globules and coils in a single chain. However, when a surface term is taken into account, it gives rise to a discontinuous transition. We also consider the role of surface charges on the globule.

Integrating Sustainability into Brownfield Regeneration: Rhetoric or Reality? – An Analysis of the UK Development Industry

In the UK and elsewhere the use of the term ‘sustainable brownfield regeneration’ has resulted from the interweaving of two key policy themes, comprising ‘sustainable development’ and ‘brownfield regeneration’. This paper provides a critical overview of brownfield policy within the context of the emerging sustainable development agenda in the UK, and examines the development industry's role and attitudes towards key aspects of sustainable development and brownfield regeneration. The paper analyses results from a survey of commercial and residential developers carried out in mid‐2004, underpinned by structured interviews with eleven developers in 2004–2005, which form part of a two‐and‐half‐year EPSRC‐funded project. The results suggest that despite the increasing focus on sustainability in government policy, the development industry seems ill at ease with precisely how sustainable development can be implemented in brownfield schemes. These and other findings, relating to sustainability issues (including the impact of climate change on future brownfield development), have important ramifications for brownfield regeneration policy in the UK. In particular, the research highlights the need for better metrics and benchmarks to be developed to measure ‘sustainable brownfield regeneration’. There also needs to be greater awareness and understanding of alternative clean‐up technologies to ‘dig and dump’.