Dinuclear copper and zinc complexes of a hexaazamacrocycle containing p-xylyl spacers and bridging anions: theoretical and spectroscopic studies

The hexaazamacrocycle 7,22-dimethyl-3,7,11,18,22,26-hexaazatricyclo[26.2.2.2(13,16)] tetratriaconta-1(30), 13,15,28,31,33- hexaene (Me-2[30] pbz(2)N(6)) was synthesized and characterised by single crystal X-ray diffraction. The macrocycle adopts a conformation with the two aromatic rings almost parallel at a distance of ca. 4.24 Angstrom, but displaced relative to each other by ca. 1.51 Angstrom. The protonation constants of this compound and the stability constants of its complexes with Cu2+ and Zn2+, were determined in water - methanol (9 : 1 v/v) at 25 degreesC with ionic strength 0.10 mol dm(-3) in KCl. The potentiometric and spectroscopic studies (NMR of zinc, cadmium and lead complexes, and EPR of the copper complexes) indicate the formation of only dinuclear complexes. The association constants of the dinuclear copper complex with anions ( thiocyanate, terephthalate and glyphosate) and neutral molecules (1,4-benzenedimethanol, p-xylylenediamine and terephthalic acid) were determined at 20 degreesC in methanol. The structural preferences of this ligand and of its dinuclear copper(II) complex with a variety of bridging ligands were evaluated theoretically by molecular mechanics calculations (MM) and molecular dynamics (MD) using quenching techniques.

Protonation of phenylboronic acid: comparison of G3B3 and G2MP2 methods

G3B3 and G2MP2 calculations using Gaussian 03 have been carried out to investigate the protonation preferences for phenylboronic acid. All nine heavy atoms have been protonated in turn. With both methodologies, the two lowest protonation energies are obtained with the proton located either at the ipso carbon atom or at a hydroxyl oxygen atom. Within the G3B3 formalism, the lowest-energy configuration by 4.3 kcal . mol(-1) is found when the proton is located at the ipso carbon, rather than at the electronegative oxygen atom. In the resulting structure, the phenyl ring has lost a significant amount of aromaticity. By contrast, calculations with G2MP2 show that protonation at the hydroxyl oxygen atom is favored by 7.7 kcal . mol(-1). Calculations using the polarizable continuum model (PCM) solvent method also give preference to protonation at the oxygen atom when water is used as the solvent. The preference for protonation at the ipso carbon found by the more accurate G3B3 method is unexpected and its implications in Suzuki coupling are discussed. (C) 2006 Wiley Periodicals, Inc.

Separation of lanthanides and actinides(III) using tridentate benzimidazole, benzoxazole and benzothiazole ligands

The ability of new hydrophobic tridentate ligands based on 2,6-bis(benziinidazol-2-yl)pyridine, 2,6-bis(benzoxazol-2-yl)pyridine and 2,6-bis(benzothiazol-2-yl)pyridine to selectively extract americium(III) from europium(III) was measured. The most promising ligand-2,6-bis(benzoxazol-2-yl)-4-(2-decyl-1-tetradecyloxy)pyridine L-9 was found to give separation factors (SFAm/Eu) of up to 70 when used to extract cations from 0.02-0.10 M HNO3 into TPH in synergy with 2-bromodecanoic acid. Six structures of lanthanide complexes with 2,6-bis(benzoxazol-2-yl)pyridine L-6 were then determined to evaluate the types of species that are likely to be involved in the separation process. Three structural types were observed, namely [LnL(6)(NO3)(3)(H2O)2], 11-coordinate only for La, [LnL(6) (NO3)(3) (CH3CN)], 10-coordinate for Pr, Nd and Eu and [LnL(6) (NO3)(3)(H2O)], L 10-coordinate for Eu and Gd. Quantum Mechanics calculations were carried out on the tridentate ligands to elucidate the conformational preferences of the ligands in the free state and protonated and diprotonated forms and to assess the electronic properties of the ligands for comparison with other terdentate ligands used in lanthanide/actinide separation processes.

A conceptual design of a wireless sensor actuator system for optimising energy and well-being in a building

This article presents a prototype model based on a wireless sensor actuator network (WSAN) aimed at optimizing both energy consumption of environmental systems and well-being of occupants in buildings. The model is a system consisting of the following components: a wireless sensor network, `sense diaries', environmental systems such as heating, ventilation and air-conditioning systems, and a central computer. A multi-agent system (MAS) is used to derive and act on the preferences of the occupants. Each occupant is represented by a personal agent in the MAS. The sense diary is a new device designed to elicit feedback from occupants about their satisfaction with the environment. The roles of the components are: the WSAN collects data about physical parameters such as temperature and humidity from an indoor environment; the central computer processes the collected data; the sense diaries leverage trade-offs between energy consumption and well-being, in conjunction with the agent system; and the environmental systems control the indoor environment.

Exploring teachers' knowledge of children's literature

In the context of the current debate about teaching reading, research to ascertain primary teachers' personal and professional reading practices was undertaken. The study explored teachers' reading habits and preferences, investigated their knowledge of children's literature, and documented their reported use of such texts and involvement with library services. Questionnaire responses were gathered from 1200 teachers. The data were analysed and connections made between the teachers' own reading habits and preferences, their knowledge of children's literature, their accessing practices and pedagogic use of literature in school. This paper reports on part of the dataset and focuses on teachers' knowledge of children's literature; it reveals that primary professionals lean on a narrow repertoire of authors, poets and picture fiction creators. It also discusses teachers' personal reading preferences and considers divergences and connections between these as well as the implications of the teachers' limited repertoires on the reading development of young learners.

Carbohydrate preference, acid tolerance and bile tolerance in five strains of Bifidobacterium

Aims: To assess the suitability of bifidobacteria for inclusion in synbiotic products on the basis of carbohydrate preference, acid and bile tolerance. Methods and Results: Five strains of Bifidobacterium were analysed for their carbohydrate preference from 12 substrates. Maximum growth rates were used to compare substrate preferences. Galacto-oligosaccharides and isomalto-oligosaccharides were well utilized by all the test species. Most bacteria tested could also utilize at least one type of fructan molecule. To determine transit tolerance of potentially probiotic bifidobacteria, acid and bile resistance was tested. A wide range acid resistance was found. Bile tolerance also varied. Conclusions: GOS and IMO were generally well utilized by the tested species. Other substrates were used to different degrees by the different species. Most bifidobacteria are poorly resistant to strongly acidic conditions with the exception of Bifidobacterium lactis Bb12. Bile tolerances were widely variable and it was shown that caution should be exercised when using colorimetric methods to assess bile tolerance. Significance and Impact of Study: The study allows the comparison of the properties of bifidobacteria, allowing a cost effective screen for the best species for use in synbiotic products to allow better survival and efficacy.

The acceptability of isoflavones as a treatment of menopausal symptoms: a European survey among postmenopausal women

Objective: To investigate determinants of the acceptability of isoflavone products among postmenopausal women with regard to social and lifestyle factors, dietary habits, health concerns, food beliefs, menopausal symptoms and therapies, and to elucidate preferences for specific products. Methods: A consumer survey was conducted among postmenopausal women in four European countries (Germany, Denmark, Italy and the UK), including a total of 465 respondents. Results: The declared acceptability of isoflavones was highest in Germany (80%), followed by Italy (75%), the UK (59%) and Denmark (55%; p < 0.001). Among other factors, prior information about isoflavones (odds ratio (OR) 2.64, 95% confidence interval (CI) 1.54-4.51, p < 0.001) and belief that foods can be used to treat medical conditions (OR 2.18, 95% CI 1.17-4.05, p=0.014) were the strongest predictors of potential acceptability. The preferred forms in which isoflavones might be taken differed markedly between countries. Conclusions: Information about the health effects of isoflavones and health-diet links should be considered the most important factors in attempts to influence the potential acceptability of isoflavone products. Foods enriched with isoflavones need to be developed with regard to specific cultural demands in order to assure consumer acceptance on the marketplace.

Comparative analysis of four beta-galactosidases from Bifidobacterium bifidum NCIMB41171: purification and biochemical characterisation

Four different beta-galactosidases (previously named BbgI, BbgII, BbgIII and BbgIV) from Bifidobacterium bifidum NCIMB41171 were overexpressed in Escherichia coli, purified to homogeneity and their biochemical properties and substrate preferences comparatively analysed. BbgI was forming a hexameric protein complex of 875 kDa, whereas BbgII, BbgIII and BbgIV were dimers with native molecular masses of 178, 351 and 248 kDa, respectively. BbgII was the only enzyme that preferred acidic conditions for optimal activity (pH 5.4-5.8), whereas the other three exhibited optima in more neutral pH ranges (pH 6.4-6.8). Na+ and/or K+ ions were prerequisite for BbgI and BbgIV activity in Bis-Tris-buffered solutions, whereas Mg++ was strongly activating them in phosphate-buffered solutions. BbgII and BbgIII were slightly influenced from the presence or absence of cations, with Mg++, Mn++ and Ca++ ions exerting the most positive effect. Determination of the specificity constants (k(cat)/K-m) clearly indicated that BbgI (6.11 x 10(4) s(-1) M-1), BbgIII (2.36 x 10(4) s(-1) M-1) and especially BbgIV (4.01 x 10(5) s(-1) M-1) are highly specialised in the hydrolysis of lactose, whereas BbgII is more specific for beta-D-(1 -> 6) galactobiose (5.59 x 10(4) s(-1) M-1) than lactose (1.48 x 10(3) s(-1) M-1). Activity measurements towards other substrates (e. g. beta-D-(1 -> 6) galactobiose, beta-D-(1 -> 4) galactobiose, beta-D-(1 -> 4) galactosyllactose, N-acetyllactosamine, etc.) indicated that the beta-galactosidases were complementary to each other by hydrolysing different substrates and thus contributing in a different way to the bacterial physiology.

The effect of the functional attributes of objects within the caged environment on interaction time in laboratory rats

Determining rat preferences for, and behaviour towards, environmental enrichment objects allows us to provide evidence-based information about how the caged environment may be enriched. In recent years there have been many studies investigating the preferences of laboratory rodents for a wide variety of environmental enrichment objects and materials. While these have provided important information regarding the animals' perception of the items, very few studies have attempted to systematically investigate the precise attributes that constitute a preferred object and the behaviour that these objects afford. We have designed a research program to systematically study rats' motivation to interact with enrichment objects. Here we present the results from two experiments which examined the time rats spent with objects that only differed in size. This showed that rats spent longer with large objects rather than small ones, even though objects were presented individually. We also investigated the rats' behaviour with the objects in an open field and found that rats spent longer climbing on top of the large object. This behaviour continued when the large objects were laid on their sides instead of placed upright in the arena, suggesting that the rats were not simply climbing on the objects to investigate the top of the arena and thus an escape route, but instead were genuinely motivated to climb. This suggests that rat welfare could be enhanced by the addition to their cages of objects that permit climbing. (C) 2009 Elsevier B.V. All rights reserved.

Picture book exposure elicits positive visual preferences in toddlers

Although the relationship between "mere exposure" and attitude enhancement is well established in the adult domain, there has been little similar work with children. This article examines whether toddlers' visual attention toward pictures of foods can be enhanced by repeated visual exposure to pictures of foods in a parent-administered picture book. We describe three studies that explored the number and nature of exposures required to elicit positive visual preferences for stimuli and the extent to which induced preferences generalize to other similar items. Results show that positive preferences for stimuli are easily and reliably induced in children and, importantly, that this effect of exposure is not restricted to the exposed stimulus per se but also applies to new representations of the exposed item. (C) 2009 Elsevier Inc. All rights reserved.

Divided attention, selective attention and drawing: processing preferences in Williams syndrome are dependent on the task administered

The visuo-spatial abilities of individuals with Williams syndrome (WS) have consistently been shown to be generally weak. These poor visuo-spatial abilities have been ascribed to a local processing bias by some [R. Rossen, E.S. Klima, U. Bellugi, A. Bihrle, W. Jones, Interaction between language and cognition: evidence from Williams syndrome, in: J. Beitchman, N. Cohen, M. Konstantareas, R. Tannock (Eds.), Language, Learning and Behaviour disorders: Developmental, Behavioural and Clinical Perspectives, Cambridge University Press, New York, 1996, pp. 367-392] and conversely, to a global processing bias by others [Psychol. Sci. 10 (1999) 453]. In this study, two identification versions and one drawing version of the Navon hierarchical processing task, a non-verbal task, were employed to investigate this apparent contradiction. The two identification tasks were administered to 21 individuals with WS, 21 typically developing individuals, matched by non-verbal ability, and 21 adult participants matched to the WS group by mean chronological age (CA). The third, drawing task was administered to the WS group and the typically developing (TD) controls only. It was hypothesised that the WS group would show differential processing biases depending on the type of processing the task was measuring. Results from two identification versions of the Navon task measuring divided and selective attention showed that the WS group experienced equal interference from global to local as from local to global levels, and did not show an advantage of one level over another. This pattern of performance was broadly comparable to that of the control groups. The third task, a drawing version of the Navon task, revealed that individuals with WS were significantly better at drawing the local form in comparison to the global figure, whereas the typically developing control group did not show a bias towards either level. In summary, this study demonstrates that individuals with WS do not have a local or a global processing bias when asked to identify stimuli, but do show a local bias in their drawing abilities. This contrast may explain the apparently contrasting findings from previous studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

A longitudinal study of perceptual grouping by proximity, luminance and shape in infants at two, four and six months

Grouping by luminance and shape similarity has previously been demonstrated in neonates and at 4 months, respectively. By contrast, grouping by proximity has hitherto not been investigated in infancy. This is also the first study to chart the developmental emergence of perceptual grouping longitudinally. Sixty-one infants were presented with a matrix of local stimuli grouped horizontally or vertically by luminance, shape or proximity at 2, 4, and 6 months. Infants were exposed to each set of stimuli for three presentation durations. Grouping was demonstrated for luminance similarity at the earliest testing age, 2 months, by shape similarity at 4 months, but was not observed for grouping by proximity. Grouping by shape similarity showed a distinctive pattern of grouping ability across exposure durations, which reflected familiarity preferences followed by novelty preferences. This remained stable across age. No link was found between the emergence of perceptual grouping ability and the exposure duration required to elicit grouping. We conclude by stressing the importance of longitudinal studies of infant development in furthering our understanding of human cognition, rather than relying on assumptions from the adult endstate.

An ontological modelling of user requirements for personalised information provision

The knowledge economy offers opportunity to a broad and diverse community of information systems users to efficiently gain information and know-how for improving qualifications and enhancing productivity in the work place. Such demand will continue and users will frequently require optimised and personalised information content. The advancement of information technology and the wide dissemination of information endorse individual users when constructing new knowledge from their experience in the real-world context. However, a design of personalised information provision is challenging because users’ requirements and information provision specifications are complex in their representation. The existing methods are not able to effectively support this analysis process. This paper presents a mechanism which can holistically facilitate customisation of information provision based on individual users’ goals, level of knowledge and cognitive styles preferences. An ontology model with embedded norms represents the domain knowledge of information provision in a specific context where users’ needs can be articulated and represented in a user profile. These formal requirements can then be transformed onto information provision specifications which are used to discover suitable information content from repositories and pedagogically organise the selected content to meet the users’ needs. The method is provided with adaptability which enables an appropriate response to changes in users’ requirements during the process of acquiring knowledge and skills.

the implication of social cognition for experimental economics From the issue entitled "Special issue on Experimental economics and the social embedding of economic behavior and cognition"

Can human social cognitive processes and social motives be grasped by the methods of experimental economics? Experimental studies of strategic cognition and social preferences contribute to our understanding of the social aspects of economic decisions making. Yet, papers in this issue argue that the social aspects of decision-making introduce several difficulties for interpreting the results of economic experiments. In particular, the laboratory is itself a social context, and in many respects a rather distinctive one, which raises questions of external validity.

Effect of molecule branching and glycosidic linkage on the degradation of polydextrose by gut microbiota.

Polydextrose is a randomly linked complex glucose oligomer that is widely used as a sugar replacer, bulking agent, dietary fiber and prebiotic. Polydextrose is poorly utilized by the host and, during gastrointestinal transit, it is slowly degraded by intestinal microbes, although it is not known which parts of the complex molecule are preferred by the microbes. The microbial degradation of polydextrose was assessed by using a simulated model of colonic fermentation. The degradation products and their glycosidic linkages were measured by combined gas chromatography and mass spectrometry, and compared to those of intact polydextrose. Fermentation resulted in an increase in the relative abundance of non-branched molecules with a concomitant decrease in single-branched glucose molecules and a reduced total number of branching points. A detailed analysis showed a preponderance of 1,6 pyranose linkages. The results of this study demonstrate how intestinal microbes selectively degrade polydextrose, and provide an insight into the preferences of gut microbiota in the presence of different glycosidic linkages.