Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

APORTACIONES DIDÁCTICAS EN LOS LIBROS DE TEXTO Y SU RELACIÓN CON LA ANSIEDAD ANTE EL APRENDIZAJE DE UNA LENGUA EXTRANJERA : Una exploración cualitativa de tres libros de texto de español como lengua extranjera paso 1 de educación secundaria

El objetivo de este trabajo es identificar qué competencias generales y qué competencias comunicativas, según el enfoque comunicativo, se promueven en tres libros de texto de español como lengua extranjera y determinar su relación con la variable afectiva de la ansiedad. Para alcanzar los planteamientos de nuestra investigación utilizamos una aproximación cualitativa, empleando el cuestionario de análisis NAKIBAR 2004 perteneciente al trabajo de investigación realizado por Joseba Ezeiza Ramos (2004). Los resultados muestran que los tres materiales didácticos satisfacen cada criterio del enfoque comunicativo en diversos grados. Sin embargo, ambos libros constituyen la exteriorización de dicho método, con el fin preciso de apoyar al estudiante en desarrollar la habilidad de poner en función los procesos de comunicación. Es por esto por lo que este tipo de actividades podrían potencialmente activar sentimientos de aprensión

Caries experience associated to social and preventive factors in children of a pastoral community from Limeira-SP

Aim: To evaluate caries experience and prevalence associated to social and preventive factors in 3-6-year-old children of a Pastoral Community from Limeira, Brazil. Methods: A cross-sectional study was carried out through an epidemiologic research about the oral conditions of 110 children registered at the Children's Pastoral Community from the city of Limeira, SP, Brazil. Intraoral examination was performed by a trained dentist and the parents/caregivers filled out a questionnaire in order to outline the children's profile with respect to gender, parental education and oral health. Results: Differences related to gender were not detected (p= 0.3404). The most frequent periods of breastfeeding were 0 to 2 months (36.36%) and 2 to 6 months (35.45%), corresponding to 71.81% of the cases. The time bottle feeding pointed to two most frequent categories: 1) more than 12 months (35.45%) and 2) between 2 and 6 months (22.63%). Regarding parental education, the majority of the sample has not completed primary school (38.32%). It was observed a larger number of decayed teeth in male children (63.39%). Caries experience was significantly higher in children who were breastfed for only 2 months of life (41.96%). Children that did not use baby bottle or did not use a baby bottle for more than 1 year presented a smaller dmft, corresponding to 29.17% and 28.33%, respectively. Time of use of bottle and pacifier presented a significant association (p<0.05). Conclusions: The implementation of adequate strategies and actions is needed to reinforce oral health conditions in risk groups.

O ensino de produção oral nos cursos de graduação em letras (inglês) de Belém-PA: uma abordagem por gêneros do discurso

Esta dissertação tem por objetivo investigar o ensino de produção oral de língua inglesa nos cursos de graduação em Letras de Belém-PA sob a perspectiva dos gêneros do discurso (Bakhtin, 1992; Bazerman, 2005). Para esse fim, foram realizadas observações de aula em turmas de duas instituições de ensino superior de Belém-Pará e foram coletados os livros didáticos utilizados nestas. Eles foram analisados focalizando-se as atividades de produção oral, verificando se elas incorporam, explícita ou implicitamente, a noção de gênero do discurso em sua formulação e o tratamento dado a linguagem oral presente nos mesmos a fim de comparar as propostas metodológicas desses manuais e o que efetivamente é realizado em sala de aula. Também foram aplicados questionários a professores e alunos das turmas observadas. A análise dos dados revela que a presença de uma concepção de língua como gênero ainda é incipiente na elaboração de atividades de oral e que há carência de uma variedade de gêneros orais como objeto de estudo durante a graduação, já que praticamente o único estudado é o diálogo didático.

Ultrafast charge-transfer in organic photovoltaic interfaces: geometrical and functionalization effects

Understanding the microscopic mechanisms of electronic excitation in organic photovoltaic cells is a challenging problem in the design of efficient devices capable of performing sunlight harvesting. Here we develop and apply an ab initio approach based on time-dependent density functional theory and Ehrenfest dynamics to investigate photoinduced charge transfer in small organic molecules. Our calculations include mixed quantum–classical dynamics with ions moving classically and electrons quantum mechanically, where no experimental external parameter other than the material geometry is required. We show that the behavior of photocarriers in zinc phthalocyanine (ZnPc) and C60 systems, an effective prototype system for organic solar cells, is sensitive to the atomic orientation of the donor and the acceptor units as well as the functionalization of covalent molecules at the interface. In particular, configurations with the ZnPc molecules facing on C60 facilitate charge transfer between substrate and molecules that occurs within 200 fs. In contrast, configurations where ZnPc is tilted above C60 present extremely low carrier injection efficiency even at longer times as an effect of the larger interfacial potential level offset and higher energetic barrier between the donor and acceptor molecules. An enhancement of charge injection into C60 at shorter times is observed as binding groups connect ZnPc and C60 in a dyad system. Our results demonstrate a promising way of designing and controlling photoinduced charge transfer on the atomic level in organic devices that would lead to efficient carrier separation and maximize device performance.

An experimental investigation of air flow and convective heat transfer in enclosures having large ventilative flow rates

The prediction of convective heat transfer in enclosures under high ventilative flow rates is primarily of interest for building design and simulation purposes. Current models are based on experiments performed forty years ago with flat plates under natural convection conditions.

The enactment of formative assessment in English language classrooms in two Chinese universities : teacher and student responses

The College English Curriculum Requirements (CECR), announced by the Chinese Ministry of Education in 2007, recommended the inclusion of formative assessment into the existing summative assessment framework of College English. This policy had the potential to fundamentally change the nature of assessment and its role in the teaching and learning of English in Chinese universities. In order to document and analyse these changes, case studies involving English language teachers and learners were undertaken in two Chinese Universities: one a Key university in the national capital; the other a non-Key university in a western province. The case study design incorporated classroom observations and interviews with English language teachers and their students. The type and focus of feedback and the engagement of students in assessment were analysed in the two contexts. Fundamental to the analysis was the concept of enactment, with the focus of this study on the ways that policy ideas and principles were enacted in the practices of the Chinese university classroom. Understandings of formative assessment as applied in contexts other than the predominantly Western, Anglophone contexts from where many of its principles derive, are offered.

Distinguishing between mathematics classrooms in Australia, China, Japan, Korea and the USA through the lens of the distribution of responsibility for knowledge generation : public oral interactivity and mathematical orality

The research reported in this paper examined spoken mathematics in particular well-taught classrooms in Australia, China (both Shanghai and Hong Kong), Japan, Korea and the USA from the perspective of the distribution of responsibility for knowledge generation in order to identify similarities and differences in classroom practice and the implicit pedagogical principles that underlie those practices. The methodology of the Learner’s Perspective Study (LPS) documented the voicing of mathematical ideas in public discussion and in teacher-student conversations and the relative priority accorded by different teachers to student oral contributions to classroom activity. Significant differences were identified among the classrooms studied, challenging simplistic characterisations of ‘the Asian classroom’ as enacting a single pedagogy, and suggesting that, irrespective of cultural similarities, local pedagogies reflect very different assumptions about learning and instruction. We have employed spoken mathematical terms as a form of surrogate variable, possibly indicative of the location of the agency for knowledge generation in the various classrooms studied (but also of interest in itself). The analysis distinguished one classroom from another on the basis of “public oral interactivity” (the number of utterances in whole class and teacher-student interactions in each lesson) and “mathematical orality” (the frequency of occurrence of key mathematical terms in each lesson). Classrooms characterized by high public oral interactivity were not necessarily sites of high mathematical orality. In particular, the results suggest that one characteristic that might be identified with a national norm of practice could be the level of mathematical orality: relatively high mathematical orality characterising the mathematics classes in Shanghai with some consistency, while lessons in Seoul and Hong Kong consistently involved much less frequent spoken mathematical terms. The relative contributions of teacher and students to this spoken mathematics provided an indication of how the responsibility for knowledge generation was shared between teacher and student in those classrooms. Specific analysis of the patterns of interaction by which key mathematical terms were introduced or solicited revealed significant differences. It is suggested that the empirical investigation of mathematical orality and its likely connection to the distribution of the responsibility for knowledge generation are central to the development of any theory of mathematics instruction.

Teacher aides and their pedagogical contributions in the underachieving Indigenous mathematics classroom

This study examines the pedagogical contributions made by teacher aides in underperforming Indigenous mathematics secondary classrooms. Three teaching teams, each consisting of a teacher and their teacher aide, responded to semi-structured interviews. Their mathematics classrooms were observed for details of pedagogical contributions to the mathematics lessons. It was found that the pedagogical contributions of the teacher aides varied from co-teaching contributions, to the provision of menial support and behaviour management. The techniques used by the teacher aides to provide student feedback, to support behaviour management and to undertake questioning vary greatly, and this variance is also evident in the classroom atmosphere. Teacher aides are providing pedagogical contributions, and are engaged in instructional interactions, and are in a sense “teaching”.

School libraries, teacher-librarians and their contribution to student literacy development in Gold Coast schools

This is the first research focusing on Gold Coast school libraries and teacher- librarians. It presents a detailed picture of library provision and staffing at a representative group of 27 government and non-government schools at the Gold Coast. It shows links between employment of a teacher-librarian and higher NAPLAN reading and writing scores. And it presents the principals’ generally positive views about teacher-librarians’ contribution to reading and literacy at their schools. The findings respond in part to the recent government inquiry’s call (House of Representatives, 2011) for research about the current staffing of school libraries in Australia, and the influence of school libraries and teacher-librarians on students’ literacy and learning outcomes. While the study has focused on a relatively small group of school libraries, it has produced a range of significant outcomes: • An extensive review of international and Australian research showing impacts of school libraries and teacher-librarians on students’ literacy and learning outcomes • Findings consistent with international research showing: - An inverse relationship between lower student to EFT library staff ratio and higher school NAPLAN scores for reading and writing - Schools that employ a teacher-librarian tend to achieve school NAPLAN scores for respective year levels that are higher than the national mean It is anticipated that the study’s findings will be of interest to education authorities, school leadership teams, teacher-librarians, teachers and researchers. The findings provide evidence to: • inform policy development and strategic planning for school libraries that respond to the literacy development needs of 21st century learners • inform school-based management of school libraries • inform curriculum development and teacher-librarian practice • support further collaborative research on a State or national level • enhance conceptual understandings about relationship(s) between school libraries, teacher-librarians and literacy/information literacy development • support advocacy about school libraries, teacher-librarians and their contribution to literacy development and student learning in Australian schools SLAQ President Toni Leigh comments: “It is heartening to see findings which validate the critical role teacher-librarians play in student literacy development and the positive correlation of higher NAPLAN scores and schools with a qualified teacher-librarian. Also encouraging is the high percentage of school principals who recognise the necessity of a well resourced school library and the positive influence of these libraries on student literacy”. This research arises from a research partnership between School Library Association of Queensland (SLAQ) and Children and Youth Research Centre, QUT. Lead researcher: Dr Hilary Hughes, Children and Youth Research Centre, QUT Research assistants: Dr Hossein Bozorgian, Dr Cherie Allan, Dr Michelle Dicinoski, QUT SLAQ Research Reference Group: Toni Leigh, Marj Osborne, Sally Fraser, Chris Kahl and Helen Reynolds Reference: House of Representatives. (2011). School libraries and teacher librarians in 21st century Australia. Canberra: Commonwealth of Australia. http://www.aph.gov.au/Parliamentary_Business/Committees/House_of_Representatives_Committees?url=ee/schoollibraries/report.htm

Learner strategy instruction and student uptake of strategies in a Japanese as a foreign language context

The Japanese language is recognised as being more difficult than European languages, needing three times more tuition time to reach comparable levels of proficiency. Encouraging Japanese as a Foreign Language (JFL) students to become aware of, and effectively use, learner strategies is one way to assist them become more controlled, effective learners leading to enhanced language learning. This thesis investigates the development and implementation of a JFL curriculum implemented in a university course for students learning JFL. The curriculum was developed specifically to assist beginner university students with the development of learner strategies appropriate for a JFL reading context. The theoretical underpinning of the study was informed by Educational Criticism (Eisner, 1998), which aims to describe, interpret and evaluate the processes of interaction between the teacher, the learner and the curriculum and the students' learning processes in a tertiary JFL classroom. The study investigated the effect on student learning processes of a JFL reading program that incorporated explicit learner strategy instruction and identified factors that enhanced or impeded the development of learner strategy knowledge. The participants in the study were 29 students enrolled in the course, 10 of whom volunteered to undertake additional tasks, and the two teachers who implemented the curriculum. Data collection involved a number of different strategies to observe the students' participation in the classroom and learning experiences. Learning processes were investigated through TOL protocols, classroom observations, course evaluations, interviews, and learner strategy use measurement instruments (SILL, SILK and SORS) to document student uptake of learner strategies. The design of the study and its applied focus recognised my expertise as a JFL teacher, curriculum writer and researcher, an approach that aligns with the purpose of a Professional Doctorate. Four general thematics, or principles, were identified in this study: „h Explicit learner strategy instruction provides the context for students to develop awareness of learner strategies and take control of their learning; „h Collaborative learning and interaction with teachers offers students the opportunity for shared knowledge construction; „h Reflection offers teachers and students the opportunity to reflect on their own learning style and strategy knowledge, and raises awareness of other available strategies; and „h Diverse cultural and linguistic backgrounds have an impact on curriculum implementation and student uptake of learner strategies. The study¡¦s methodological contribution is that it is one of the first in Australia to use Educational Criticism (Eisner, 1998) as a research methodology. The findings contribute to theoretical knowledge in the fields of Applied Linguistics, Second Language Teaching and Learning, Second Language Acquisition and JFL Teaching and Learning by offering new knowledge on the importance of learner strategies in the beginner JFL classroom, the potential of explicit strategy instruction, the value of reflection for both teachers and students, and the important role of the teacher in the process of curriculum implementation. The general principles identified and the findings of this in-depth study of a JFL classroom can be drawn upon to inform other teaching practice situations, and invite practitioners from not just Japanese, but from other language areas and other disciplines, to examine and improve their own practices, and suggest further research questions to pursue this line of enquiry.

Teacher and student readiness to use Facebook for learning in an adult vocational educational setting

The factors influencing both teacher and student readiness to use Facebook as part of their teaching and learning in a vocational educational institution were studied through a qualitative case study. Data included teacher and student questionnaire and focus group interviews. While it was found that the students demonstrated readiness and willingness to incorporate Facebook into their current learning, the teachers were more reluctant. Different perceptions around control of learning, time, and concerns around compartmentalisation of learning and social lives would need to be addressed before Facebook could be used as a formal learner engagement strategy.

Language and literacy in mathematics: stepping stones or stumbling blocks in accelerating junior-secondary students

The authors have collaborated in the development and initial evaluation of a curriculum for mathematics acceleration. This paper reports upon the difficulties encountered with documenting student understanding using pen-and-paper assessment tasks. This leads to a discussion of the impact of students’ language and literacy on mathematical performance and the consequences for motivation and engagement as a result of simplifying the language in the tests, and extending student work to algebraic representations. In turn, implications are drawn for revisions to assessment used within the project and the language and literacy focus included within student learning experiences.

Becoming a teacher: emerging teacher identity in mathematics teacher education

This research examines three aspects of becoming a teacher, teacher identity formation in mathematics teacher education: the cognitive and affective aspect, the image of an ideal teacher directing the developmental process, and as an on-going process. The formation of emerging teacher identity was approached in a social psychological framework, in which individual development takes place in social interaction with the context through various experiences. Formation of teacher identity is seen as a dynamic, on-going developmental process, in which an individual intentionally aspires after the ideal image of being a teacher by developing his/her own competence as a teacher. The starting-point was that it is possible to examine formation of teacher identity through conceptualisation of observations that the individual and others have about teacher identity in different situations. The research uses the qualitative case study approach to formation of emerging teacher identity, the individual developmental process and the socially constructed image of an ideal mathematics teacher. Two student cases, John and Mary, and the collective case of teacher educators representing socially shared views of becoming and being a mathematics teacher are presented. The development of each student was examined based on three semi-structured interviews supplemented with written products. The data-gathering took place during the 2005 2006 academic year. The collective case about the ideal image provided during the programme was composed of separate case displays of each teacher educator, which were mainly based on semi-structured interviews in spring term 2006. The intentions and aims set for students were of special interest in the interviews with teacher educators. The interview data was analysed following the modified idea of analytic induction. The formation of teacher identity is elaborated through three themes emerging from theoretical considerations and the cases. First, the profile of one s present state as a teacher may be scrutinised through separate affective and cognitive aspects associated with the teaching profession. The differences between individuals arise through dif-ferent emphasis on these aspects. Similarly, the socially constructed image of an ideal teacher may be profiled through a combination of aspects associated with the teaching profession. Second, the ideal image directing the individual developmental process is the level at which individual and social processes meet. Third, formation of teacher identity is about becoming a teacher both in the eyes of the individual self as well as of others in the context. It is a challenge in academic mathematics teacher education to support the various cognitive and affective aspects associated with being a teacher in a way that being a professional and further development could have a coherent starting-point that an individual can internalise.