Transition metal-directed self-assembly of calix[4]arene based dithiocarbamate ligands

The transition metal-directed self-assembly of dithiocarbamate ligand functionalised upper and lower rim calix[4]arenes affords novel dimeric bimetallic bis(calix[4]arene) species as determined by a combination of analytical methods including X-ray crystallography. An exception is a zinc(II) dithiocarbamate upper rim calix[4]arene assembly which is monomeric in nature. Electrochemical investigations reveal the bimetallic copper(II) bis(calix[4]arene) systems can electrochemically sense dihydrogen phosphate and carboxylate anions via significant cathodic perturbations of the respective copper(II)/(III) dithiocarbamate oxidation wave.

Tuning the self-assembly of the bioactive dipeptide L-carnosine by incorporation of a bulky aromatic substituent

The dipeptide L-carnosine has a number of important biological properties. Here, we explore the effect of attachment of a bulky hydrophobic aromatic unit, Fmoc [N-(fluorenyl-9-methoxycarbonyl)] on the self-assembly of Fmoc-L-carnosine, i.e., Fmoc-Beta-alanine-histidine (Fmoc-BetaAH). It is shown that Fmoc-BetaAH forms well-defined amyloid fibril containing Beta sheets above a critical aggregation concentration, which is determined from pyrene and ThT fluorescence experiments. Twisted fibrils were imaged by cryogenic transmission electron microscopy. The zinc-binding properties of Fmoc-BetaAH were investigated by FTIR and Raman spectroscopy since the formation of metal ion complexes with the histidine residue in carnosine is well-known, and important to its biological roles. Observed changes in the spectra may reflect differences in the packing of the Fmoc-dipeptides due to electrostatic interactions. Cryo-TEM shows that this leads to changes in the fibril morphology. Hydrogelation is also induced by addition of an appropriate concentration of zinc ions. Our work shows that the Fmoc motif can be employed to drive the self-assembly of carnosine into amyloid fibrils.

Motivation in second language acquisition in Chinese research students in the UK

The present study sets out to examine motivation to learn English by Chinese research students in an informal setting. Data were collected, using semi-structured interviews, from four research students at two points in time during their first year in the UK. The main findings are: they believed that learning English was important; their main goal orientations were instrumental and extrinsic; they set learning goals and persisted to attain them; they valued their current learning environment in general and saw it as supportive of their goals; they held both positive and negative attitudes towards the British, which had differential effects on their motivation; their self-perceived support seemed to have a positive impact on their motivation and the development of self-confidence; they tended to attribute their success to stable causes such as the environment and failure to unstable but controllable causes such as effort. It is concluded that qualitative data of this kind may complement insights from quantitative research. Implications for target country institutions in the provision of support are discussed.

Determination of orientations of aromatic groups in self-assembled peptide fibrils by polarised Raman spectroscopy

In this paper we describe a novel combination of Raman spectroscopy, isotope editing and X-ray scattering as a powerful approach to give detailed structural information on aromatic side chains in peptide fibrils. The orientation of the tyrosine residues in fibrils of the peptide YTIAALLSPYS with respect to the fibril axis has been determined from a combination of polarised Raman spectroscopy and X-ray diffraction measurements. The Raman intensity of selected tyrosine bands collected at different polarisation geometries is related to the values and orientation of the Raman tensor for those specific vibrations. Using published Raman tensor values we solved the relevant expressions for both of the two tyrosine residues present in this peptide. Ring deuteration in one of the two tyrosine side chains allowed for the calculation to be performed individually for both, by virtue of the isotopic shift that eliminates band overlapping. Sample disorder was taken into account by obtaining the distribution of orientations of the samples from X-ray diffraction experiments. The results provide previously unavailable details about the molecular conformation of this peptide, and demonstrate the value of this approach for the study of amyloid fibrils.

Self-assembly and bioactivity of a polymer/peptide conjugate containing the RGD cell adhesion motif and PEG

The self-assembly and bioactivity of the peptide–polymer conjugate DGRFFF–PEG3000 containing the RGD cell adhesion motif has been examined, in aqueous solution. The conjugate is designed to be amphiphilic by incorporation of three hydrophobic phenylalanine residues as well as the RGD unit and a short poly(ethylene glycol) (PEG) chain of molar mass 3000 kg mol-1. Above a critical aggregation concentration, determined by fluorescence measurements, signals of b-sheet structure are revealed by spectroscopic measurements, as well as X-ray diffraction. At high concentration, a self-assembled fibril nanostructure is revealed by electron microscopy. The fibrils are observed despite PEG crystallization which occurs on drying. This suggests that DGRFFF has an aggregation tendency that is sufficiently strong not to be prevented by PEG crystallization. The adhesion, viability and proliferation of human corneal fibroblasts was examined for films of the conjugate on tissue culture plates (TCPs) as well as low attachment plates. On TCP, DGRFFF–PEG3000 films prepared at sufficiently low concentration are viable, and cell proliferation is observed. However, on low attachment surfaces, neither cell adhesion nor proliferation was observed, indicating that the RGD motif was not available to enhance cell adhesion. This was ascribed to the core–shell architecture of the self-assembled fibrils with a peptide core surrounded by a PEG shell which hinders access to the RGD unit.

The ideal self at play: the appeal of video games that let you be all you can be

Video games constitute a popular form of entertainment that allows millions of people to adopt virtual identities. In our research, we explored the idea that the appeal of games is due in part to their ability to provide players with novel experiences that let them “try on” ideal aspects of their selves that might not find expression in everyday life. We found that video games were most intrinsically motivating and had the greatest influence on emotions when players’ experiences of themselves during play were congruent with players’ conceptions of their ideal selves. Additionally, we found that high levels of immersion in gaming environments, as well as large discrepancies between players’ actual-self and ideal-self characteristics, magnified the link between intrinsic motivation and the experience of ideal-self characteristics during play.

The role of context in forming young learners' attitudes and motivation to learning French

Despite the wealth of valuable information that has been generated by motivation studies to date, there are certain limitations in the common approaches. Quantitative and psychometric approaches to motivation research that have dominated in recent decades provided epiphenomenal descriptions of learner motivation within different contexts. However, these approaches assume homogeneity within a given group and often mask the variation between learners within the same, and different, contexts. Although these studies have provided empirical data to form and validate theoretical constructs, they have failed to recognise learners as individual ‘people’ that interact with their context. Learning context has become increasingly explicit in motivation studies, (see Coleman et al. 2007 and Housen et al. 2011), however it is generally considered as a background variable which is pre-existing and external to the individual. Stemming from the recent ‘social turn’ (Block 2003) in SLA research from a more cognitive-linguistic perspective to a more context-specific view of language learning, there has been an upsurge in demand for a greater focus on the ‘person in context’ in motivation research (Ushioda 2011). This paper reports on the findings of a longitudinal study of young English learners of French as they transition from primary to secondary school. Over 12 months, the study employed a mixed-method approach in order to gain an in-depth understanding of how the learners’ context influenced attitudes to language learning. The questionnaire results show that whilst the learners displayed some consistent and stable motivational traits over the 12 months, there were significant differences for learners within different contexts in terms of their attitudes to the language classroom and their levels of self-confidence. A subsequent examination of the qualitative focus group data provided an insight into how and why these attitudes were formed and emphasised the dynamic and complex interplay between learners and their context.

Mood and recall of autobiographical memory: the effect of focus of self-knowledge

Mood state facilitates recall of affectively congruent memories (i.e., mood-congruent recall). Mood state may also promote motivation to alleviate a negative affective state, leading to retrieval of affectively incongruent memories (i.e., mood incongruent recall). The present study demonstrates that the focus of self-knowledge influences the occurrence of both mood-congruent recall and mood-incongruent recall. Three experiments found that mood-congruent recall occurred when participants recalled their experiences from a self-aspect that was related to the elicitor of moods, whereas mood-incongruent recall occurred when they recalled their experiences from a self-aspect that was unrelated to the elicitor of moods. These results suggest that the nature of the self-aspect from which persons recall their experiences determines whether mood-congruent or mood-incongruent recall occurs.

Effects of structure of self-knowledge on mood-incongruent effect

Some people recall more positive memories in negative moods than in neutral moods, which is called mood-incongruent effect. Although previous research suggested that structure of self-knowledge influences mood-incongruent effect (Sakaki, 2004), it is possible that motivation for mood-regulation mediates relation between structure of self-knowledge and mood-incongruent effect. The present study aimed at exploring this possibility by using self-complexity. In Study 1, participants with higher self-complexity, whose self-knowledge has more self-aspects with a higher level of differentiation, recalled more positive memories in negative moods (compared to neutral moods) than participants with lower self-complexity, whose self-knowledge has a fewer self-aspects with larger overlap. Study 1 also revealed that these effects hold even when the motivation for mood-regulation was partialed out. Study 2 examined mood-incongruent effect under positive moods, in which participants are unlikely motivated to alter their moods, and it was found that participants with higher self-complexity recalled more negative memories in positive moods (compared to neutral moods) than participants with lower self-complexity.

Why children differ in motivation to learn: insights from 13,000 twins from 6 countries

Little is known about why people differ in their levels of academic motivation. This study explored the etiology of individual differences in enjoyment and self-perceived ability for several school subjects in nearly 13,000 twins aged 9 to 16 from 6 countries. The results showed a striking consistency across ages, school subjects, and cultures. Contrary to common belief, enjoyment of learning and children’s perceptions of their competence were no less heritable than cognitive ability. Genetic factors explained approximately 40% of the variance and all of the observed twins’ similarity in academic motivation. Shared environmental factors, such as home or classroom, did not contribute to the twin’s similarity in academic motivation. Environmental influences stemmed entirely from individual specific experiences.

Impression management and achievement motivation: investigating substantive links

In the present research we investigate impression management (IM) as a substantive personality variable by linking it to differentiated achievement motivation constructs, namely achievement motives (workmastery, competitiveness, fear of failure) and achievement goals (mastery-approach, mastery-avoidance, performance-approach, performance-avoidance). Study 1 revealed that IM was a positive predictor of workmastery and a negative predictor of competitiveness (with and without self-deceptive enhancement (SDE) controlled). Studies 2a and 2b revealed that IM was a positive predictor of mastery-approach goals and mastery-avoidance goals (without and, in Study 2b, with SDE controlled). These findings highlight the value of conceptualizing and utilizing IM as a personality variable in its own right, and shed light on the nature of the achievement motive and achievement goal constructs.

The doodle of a finitely determined map germ from R(2) to R(3)

Let f : U subset of R(2) -> R(3) be a representative of a finitely determined map germ f : (R(2), 0) -> (R(3), 0). Consider the curve obtained as the intersection of the image of the mapping f with a sufficiently small sphere s(epsilon)(2) centered at the origin in R(3), call this curve the associated doodle of the map germ f. For a large class of map germs the associated doodle has many transversal self-intersections. The topological classification of such map germs is considered from the point of view of the associated doodles. (C) 2009 Elsevier Inc. All rights reserved.

CONSTRUCTING QUANTUM OBSERVABLES AND SELF-ADJOINT EXTENSIONS OF SYMMETRIC OPERATORS. III. SELF-ADJOINT BOUNDARY CONDITIONS

This paper completes the review of the theory of self-adjoint extensions of symmetric operators for physicists as a basis for constructing quantum-mechanical observables. It contains a comparative presentation of the well-known methods and a newly proposed method for constructing ordinary self-adjoint differential operators associated with self-adjoint differential expressions in terms of self-adjoint boundary conditions. The new method has the advantage that it does not require explicitly evaluating deficient subspaces and deficiency indices (these latter are determined in passing) and that boundary conditions are of explicit character irrespective of the singularity of a differential expression. General assertions and constructions are illustrated by examples of well-known quantum-mechanical operators like momentum and Hamiltonian.

Childbirth self-efficacy inventory in Tanzania : a pilot study

Background. To give birth can be a stressful experience and women cope with thisstress in many different ways and have different personal outcomes. Self-efficacy orconfidence in ability to cope with labour can be considered as an important factoraffecting pregnant women’s motivation of normal childbirth and their interpretation ofthe childbirth event.The aim. The purpose of this study was to test the Chinese short form of theinstrument Childbirth self-efficacy instrument (CBSEI) in Tanzania, that measurepregnant women’s self-confidence and coping abilities during childbirth.Method. The Chinese short form of the CBSEI was used to pilot test the pregnantwomen’s confidence of childbirth to see if the questions were understood in theTanzanian culture. Besides this instrument socio-demographic data was collectedtogether with two open questions asking about attitudes and experiences of childbirth.The instrument was translated into Kiswahili. A sample of 60 pregnant women whowere visiting antenatal clinic (ANC) regularly were asked to participate and with helpfrom midwifes at two ANC places the questionnaires were filled out.Result. The result shows that the validity and reliability of the two subscales OE-16and EE-16 were established. The internal consistency reliability of the two subscaleswere high, suggesting that each of the subscale mean score provides a good overviewof self- reported belief in coping ability for childbirth.The results further show that the instrument, CBSEI in this pilot study is not able toidentify women who need extra support during childbirth.Conclusion. The reliability and validity of information presented in this pilot studysupport the use of the Chinese short form of the CBSEI as a research instrument in theTanzania culture. Further studies are recommended to get a wider understandingabout women’s coping abilities in a culture like Tanzania.

Möjligheter till motivation för fysisk aktivitet : En interventionsstudie avsedd att motivera elever till fysisk aktivitet genom självbestämmande

Syftet med studien var att under en femveckorsperiod undersöka möjligheterna till att förändra elevers motivation till fysisk aktivitet. Utifrån detta syfte formulerades följande frågeställning: Vad sker med elevers motivation till fysisk aktivitet om den praktiska undervisningen utformas efter self-determination theory? För att utforma den praktiska undervisningen efter self-determination theory valdes Engstöms praktiker som en grund och stöttepelare i planeringen och genomförandet av lektionerna. Vilket gav en underliggande frågeställning till den ovanstående: - Vilka praktiker finns representerade i underökningsgruppen? Studien har genomförts på en högstadieskola i mellersta Sverige, där två klasser i årskurs (åk) 8 valdes ut att delta i studien. I undersökningsgruppen blev urvalet 14 elever och i kontrollgruppen 9 elever. Undersökningsgruppen genomförde en praktikenkät innan interventionen, vilken låg till grund i planeringen och genomförandet av lektionerna. De två klasserna genomförde en motivationsenkät före och efter interventionen för att mäta motivationsnivån. Resultatet av interventionsstudien visar att det skedde en viss förändring i de olika motivationsnivåerna. Det fanns dock ingen statistisk signifikant skillnad mellan test ett och test två på någon av motivationsnivåerna, varken hos undersökningsgrupp eller hos kontrollgrupp.