Hydrogen-bond assisted stabilization of the less favored conformation of a tridentate Schiff base ligand in dinuclear nickel(II) complex: an experimental and theoretical study

The Schiff base ligand, HL (2-[1-(3-methylamino-propylimino)-ethyl]-phenol), the 1:1 condensation product of 2-hydroxy acetophenone and N-methyl-1,3-diaminopropane, has been synthesized and characterized by X-ray crystallography as the perchlorate salt [H2L]ClO4 (1). The structure consists of discrete [H2L](+) cations and perchlorate anions. Two dinuclear Ni-II complexes, [Ni2L2(NO2)(2)] (2), [Ni2L2(NO3)(2)] (3) have been synthesized using this ligand and characterized by single crystal X-ray analyses. Complexes 2 and 3 are centrosymmetric dimers in which the Ni-II ions are in distorted fac- and mer-octahedral environments, respectively, bridged by two mu(2)-phenolate ions of deprotonated ligand, L. The plane of the phenyl rings and the Ni2O2 basal plane are nearly coplanar in 2 but almost perpendicular in 3. We have studied and explained this different behavior using high level DFT calculations (RI-BP86/def2-TZVP level of theory). The conformation observed in 3, which is energetically less favorable, is stabilized via intermolecular non-covalent interactions. Under the excitation of ultraviolet light, characteristic fluorescence of compound 1 was observed; by comparison fluorescence intensity decreases in case of compound 3 and completely quenched in compound 2.

Out of the ivory tower: the impact of wider social contact on the values, religious beliefs and identities of Chinese postgraduate students in the UK

This article explores the impact of wider social contact on the experience of Chinese postgraduate students of adaptation to life in the UK. Focus group and individual interviews were conducted with a group of 11 Chinese students on an MA programme at a university in southern England and individual interviews with three representatives of a local volunteer group (LVG) offering support to the Chinese students. Although it was perceived that the students’ support needs were not adequately met by the University, the additional support offered outside the University was unanimously valued and considered as enriching their cultural and linguistic experiences and meeting their expectations. However, frequent social contact with the LVG, whose members were mostly Christians, also had an impact on their values, religious beliefs and identities. In a discussion framed within the sociological perspective of proselytization or religious conversion and the broad framework of international education and globalization, the different responses to this contact are described in terms of believers, doubters, empathisers and commentators. Implications are considered for universities, people involved in providing social support for international students, and sponsors of international students.

Direct contact membrane distillation

This review looks at the work carried out over the past 15 years on membrane distillation and reports the conditions utilized for research. The process is still used mainly at the laboratory scale, but a few pilot plants have been built across the world, mostly for desalination and the production of potable water. Studies into membrane distillation have been concerned with the effect of mass transfer, heat transfer, and stirring rate, but the most important effect that has to be considered with this process is temperature polarization. A section on temperature polarization and the effect of boundary layers is included in this review.

Impact Assessment in the EU: a tool for better regulation, less regulation or less bad regulation?

Impact Assessments (IAs) were introduced at the EU level under the rhetorical facade of ‘better regulation’. The actual aim was to improve not only the quality but also the reputation of EU regulation before stakeholders. However, evidence brought forward by a number of evaluations pointed out that IAs are yet to achieve acceptable quality standards. The paper offers an overview of different disciplinary approaches for looking at IAs. It suggests that risk regulation encompasses the theoretical foundations to help understand the role of IAs in the EU decisionmaking process. The analysis of 60 early days preliminary IAs provides empirical evidence regarding policy alternatives, methodology of consultation and use of quantitative techniques. Findings suggest that dawn period IAs were used mainly to provide some empirical evidence for regulatory intervention in front of stakeholders. The paper concludes with assumptions about the future role of IAs at EU level.

Suitability of pesticide risk indicators for less developed countries: a comparison

Pesticide risk indicators provide simple support in the assessment of environmental and health risks from pesticide use, and can therefore inform policies to foster a sustainable interaction of agriculture with the environment. For their relative simplicity, indicators may be particularly useful under conditions of limited data availability and resources, such as in Less Developed Countries (LDCs). However, indicator complexity can vary significantly, in particular between those that rely on an exposure–toxicity ratio (ETR) and those that do not. In addition, pesticide risk indicators are usually developed for Western contexts, which might cause incorrect estimation in LDCs. This study investigated the appropriateness of seven pesticide risk indicators for use in LDCs, with reference to smallholding agriculture in Colombia. Seven farm-level indicators, among which 3 relied on an ETR (POCER, EPRIP, PIRI) and 4 on a non-ETR approach (EIQ, PestScreen, OHRI, Dosemeci et al., 2002), were calculated and then compared by means of the Spearman rank correlation test. Indicators were also compared with respect to key indicator characteristics, i.e. user friendliness and ability to represent the system under study. The comparison of the indicators in terms of the total environmental risk suggests that the indicators not relying on an ETR approach cannot be used as a reliable proxy for more complex, i.e. ETR, indicators. ETR indicators, when user-friendly, show a comparative advantage over non-ETR in best combining the need for a relatively simple tool to be used in contexts of limited data availability and resources, and for a reliable estimation of environmental risk. Non-ETR indicators remain useful and accessible tools to discriminate between different pesticides prior to application. Concerning the human health risk, simple algorithms seem more appropriate for assessing human health risk in LDCs. However, further research on health risk indicators and their validation under LDC conditions is needed.

Technological change and the challenges for regional development: building social capital in less-favoured regions

The relevance of regional policy for less favoured regions (LFRs) reveals itself when policy-makers must reconcile competitiveness with social cohesion through the adaptation of competition or innovation policies. The vast literature in this area generally builds on an overarching concept of ‘social capital’ as the necessary relational infrastructure for collective action diversification and policy integration, in a context much influenced by a dynamic of industrial change and a necessary balance between the creation and diffusion of ‘knowledge’ through learning. This relational infrastructure or ‘social capital’ is centred on people’s willingness to cooperate and ‘envision’ futures as a result of “social organization, such as networks, norms and trust that facilitate action and cooperation for mutual benefit” (Putnam, 1993: 35). Advocates of this interpretation of ‘social capital’ have adopted the ‘new growth’ thinking behind ‘systems of innovation’ and ‘competence building’, arguing that networks have the potential to make both public administration and markets more effective as well as ‘learning’ trajectories more inclusive of the development of society as a whole. This essay aims to better understand the role of ‘social capital’ in the production and reproduction of uneven regional development patterns, and to critically assess the limits of a ‘systems concept’ and an institution-centred approach to comparative studies of regional innovation. These aims are discussed in light of the following two assertions: i) learning behaviour, from an economic point of view, has its determinants, and ii) the positive economic outcomes of ‘social capital’ cannot be taken as a given. It is suggested that an agent-centred approach to comparative research best addresses the ‘learning’ determinants and the consequences of social networks on regional development patterns. A brief discussion of the current debate on innovation surveys has been provided to illustrate this point.

Large is fast, small is tight: determinants of speed and affinity in subunit capture by a periplasmic chaperone

The chaperone/usher pathway assembles surface virulence organelles of Gram-negative bacteria, consisting of fibers of linearly polymerized protein subunits. Fiber subunits are connected through 'donor strand complementation': each subunit completes the immunoglobulin (Ig)-like fold of the neighboring subunit by donating the seventh β-strand in trans. Whereas the folding of Ig domains is a fast first-order process, folding of Ig modules into the fiber conformation is a slow second-order process. Periplasmic chaperones separate this process in two parts by forming transient complexes with subunits. Interactions between chaperones and subunits are also based on the principle of donor strand complementation. In this study, we have performed mutagenesis of the binding motifs of the Caf1M chaperone and Caf1 capsular subunit from Yersinia pestis and analyzed the effect of the mutations on the structure, stability, and kinetics of Caf1M-Caf1 and Caf1-Caf1 interactions. The results suggest that a large hydrophobic effect combined with extensive main-chain hydrogen bonding enables Caf1M to rapidly bind an early folding intermediate of Caf1 and direct its partial folding. The switch from the Caf1M-Caf1 contact to the less hydrophobic, but considerably tighter and less dynamic Caf1-Caf1 contact occurs via the zip-out-zip-in donor strand exchange pathway with pocket 5 acting as the initiation site. Based on these findings, Caf1M was engineered to bind Caf1 faster, tighter, or both faster and tighter. To our knowledge, this is the first successful attempt to rationally design an assembly chaperone with improved chaperone function.

Fitness and dissemination of disinfectant-selected multiple-antibiotic-resistant (MAR) strains of Salmonella enterica serovar Typhimurium in chickens

Objectives: The aims of this study were to determine whether strains of Salmonella enterica serovar Typhimurium which had acquired low-level multiple antibiotic resistance (MAR) through repeated exposure to farm disinfectants were able to colonize and transmit between chicks as easily as the parent strain and, if such strains were less susceptible to fluoroquinolones, would high-level resistance be selected after fluoroquinolone treatment. Methods: Two mutants were compared with the isogenic parent. In the first experiment, day-old chicks were co-infected with both the parent and a mutant to determine their relative fitness. In the second experiment, parent and mutant strains (in separate groups of chicks) were assessed for their ability to transmit from infected (contact) to non-infected (naive) birds and with respect to their susceptibility to fluoroquinolone treatment. Birds were regularly monitored for the presence of Salmonella in caecal contents. Replica plating was used to monitor for the selection of antibiotic-resistant strains. Results: The parent strain was shown to be significantly fitter than the two mutants and was more rapidly disseminated to naive birds. Antibiotic treatment did not preferentially select for the two mutants or for resistant strains. Conclusions: The disinfectant-exposed strains, although MAR, were less fit, less able to disseminate than the parent strain and were not preferentially selected by therapeutic antibiotic treatment. As such, these strains are unlikely to present a greater problem than other salmonellae in chickens.

Placentation and maternal investment in mammals

The mammalian placenta exhibits striking interspecific morphological variation, yet the implications of such diversity for reproductive strategies and fetal development remain obscure. More invasive hemochorial placentas, in which fetal tissues directly contact the maternal blood supply, are believed to facilitate nutrient transfer, resulting in higher fetal growth rates, and to be a state of relative fetal advantage in the evolution of maternal-offspring conflict. The extent of interdigitation between maternal and fetal tissues has received less attention than invasiveness but is also potentially important because it influences the surface area for exchange. We show that although increased placental invasiveness and interdigitation are both associated with shorter gestations, interdigitation is the key variable. Gestation times associated with highly interdigitated labyrinthine placentas are 44% of those associated with less interdigitated villous and trabecular placentas. There is, however, no relationship between placental traits and neonatal body and brain size. Hence, species with more interdigitated placentas produce neonates of similar body and brain size but in less than half the time. We suggest that the effects of placental interdigitation on growth rates and the way that these are traded off against gestation length may be promising avenues for understanding the evolutionary dynamics of parentoffspring conflict. Keywords: placenta, parent-offspring conflict, life history, brain evolution, reproductive strategies, gestation.

Contact angle of a hemispherical bubble: an analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace’s equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity.

Borrowing and shift-induced interference: contrasting patterns in French-Germanic contact in Brussels and Strasbourg

The main aim of the present article is to test hypotheses derived from the model for contact- induced language change as formulated in Thomason and Kaufman (1988 et seq.). As the model correctly predicts the asymmetries between the mutual influences of the Germanic and the Romance varieties in Brussels and Strasbourg it is a very powerful tool for describing the contact patterns in these cities. The analysis shows that the contact patterns are very similar, both from a quantitative and from a qualitative point of view, despite important differences in the sociolinguistic situation of both cities. The striking similarities in the outcome of language contact seem to find a plausible explanation in the fact that the language contact situations in both cities are similar from a typological point of view: in each city a variety of French is in contact with a Germanic variety (Alsatian and Brussels Dutch). Thus, the claim of the present article is that the structure of the languages plays a more prominent role in the outcome of language contact than the sociolinguistic history of the speakers.

The role of transfer in language variation and change: Evidence from contact varieties of French

In this Special Issue, the focus is on contact-induced language variation and change in situations of societal bilingualism that involve long-term contact between French and another language. As is well known, when two or more languages are spoken by groups of speakers in the same geographical area, over time, features from one language can be transferred to the other language, especially when the languages in question are unequal in terms of prestige, institutional support and demographic factors. The process that leads to the adoption of such features in the contact languages is generally known as INTERFERENCE or TRANSFER, and these terms are also used to describe the features in question (i.e. the end product of the process of transfer). In this issue we prefer to use the term TRANSFER over the use of the notion INTERFERENCE, as the former has fewer negative connotations than the latter.