Installation of internal electric fields by non-redox active cations in transition metal complexes.

Local electric fields contribute to the high selectivity and catalytic activity in enzyme active sites and confined reaction centers in zeolites by modifying the relative energy of transition states, intermediates and/or products. Proximal charged functionalities can generate equivalent internal electric fields in molecular systems but the magnitude of their effect and impact on electronic structure has been minimally explored. To generate quantitative insight into installing internal fields in synthetic systems, we report an experimental and computational study using transition metal (M1) Schiff base complexes functionalized with a crown ether unit containing a mono- or dicationic alkali or alkaline earth metal ion (M2). The synthesis and characterization of the complexes M1 = Ni(ii) and M2 = Na+ or Ba2+ are reported. The electronic absorption spectra and density functional theory (DFT) calculations establish that the cations generate a robust electric field at the metal, which stabilizes the Ni-based molecular orbitals without significantly changing their relative energies. The stabilization is also reflected in the experimental Ni(ii/i) reduction potentials, which are shifted 0.12 V and 0.34 V positive for M2 = Na+ and Ba2+, respectively, compared to a complex lacking a proximal cation. To compare with the cationic Ni complexes, we also synthesized a series of Ni(salen) complexes modified in the 5' position with electron-donating and -withdrawing functionalities (-CF3, -Cl, -H, -tBu, and -OCH3). Data from this series of compounds provides further evidence that the reduction potential shifts observed in the cationic complexes are not due to inductive ligand effects. DFT studies were also performed on the previously reported monocationic and dicatonic Fe(ii)(CH3CN) and Fe(iii)Cl analogues of this system to analyze the impact of an anionic chloride on the electrostatic potential and electronic structure of the Fe site

Getting to ‘know’ connectors? Evaluating data-driven learning in a writing skills course

This paper sets out to evaluate the effect on learners’ knowledge and use of language of one prominent technique in corpus pedagogy, the data-driven use of corpus concordances with learners as researchers, or Data-Driven Learning (DDL) (Johns 1988, 1991). More specifically, the paper attempts measurement of the effect of DDL on the achievement of the goal of appropriate production by learners of logical connectors, an important subskill in the context of the wider objective of the acquisition of basic academic writing skills in English. The evaluation uses learner corpora from experimental and control groups, supported by other methods. The conclusion is that DDL, applied in the context of the communicative teaching of writing skills, is moderately effective, and that there is potential both for the further development of learner corpora in an evaluative role, and for use of a wider range of instrumentation

Indirect Requests: A Comparative Study Of Explicit-Deductive And Explicit-Inductive Instruction Methods

This study compared the effects of explicit-deductive and explicit-inductive instruction methods on the participants’ request types. Specifically, the researcher explored the following questions: how Chinese university students’ English request types are affected by a ninety-minute explicit- deductive treatment or a ninety-minute explicit-inductive treatment; which request types are most frequently used prior to the treatments; which request types are most frequently used following the treatment; and how do the request type frequencies differ between the two treatment groups. The participants were undergraduate and graduate students from an urban university in China. Discourse Completion Tests (DCTs) were used to gather data from the participants before and after a ninety-minute treatment focusing on indirect request types. Initial findings showed how both groups changed their request types following the treatment and highlighted a preference for conventionally indirect requests, specifically reference to preparatory conditions requests. Finally, suggestions are provided for a future study built off the foundation laid by this one

Languages: Computation or communication? Gender issues in curricular foreign language acquisition

Do boys and girls learn differently? The perception of Modern Foreign Language learning appears to show that there is an increasing gap between the attainment of boys and girls. In this research I have chosen to focus on the secondary school context and particularly on two main questions: Do boys and girls display different aptitudes when learning a Modern Foreign Language? Does a difference in teaching style affect learning in a secondary school context, either when comparing boys and girls, or when comparing the learning of German or French in similar contexts? The first phase of my research involved conducting aptitude tests, initially using the MLAT-E, as developed by Carroll and Sapon. This test, conducted in English, was originally intended to demonstrate whether learners have an aptitude for learning a Foreign Language, by focussing on phonetic coding, grammar handling, rote memorization, inductive language learning ability. A test written and performed in English may provide some insights into students' aptitude for learning a foreign language, but in order to investigate differences in learning either French or German, I developed further tests, using the same principles, but which were conducted in French and German. In both of these tests there appears to be no significant difference between the performance of boys and girls in the specific context, and no significant difference between the two languages. It is often assumed that boys learn by breaking tasks down into clear cut rules, and girls learn by following examples. Using a range of inductive and deductive teaching strategies, students were taught how to use the simple future tense in French and German. Students were observed during the teaching phase, both during whole class activities, and in group work situations, and were interviewed after completing their final assessments, to ascertain how they managed the tasks. When comparing students' understanding and application of the simple future tense, I could again, observe no significant difference between boys and girls, or between the learning of German and French. This research has been conducted among a range of mixed ability classes in KS3 (age 11-14) in a comprehensive school. This action research is significant for teachers of Modern Foreign Languages in the secondary school, as we move forwards from the new KS2 MFL curriculum component. The questions remain, however, as to why there is still such a disparity in the results of boys and girls at GCSE and how teachers can encourage boys in their pursuit of language learning

Synthesis and Density Functional Theory Studies of Azirinyl and Oxiranyl Functionalized Isoindigo and (3Z,3’Z)-3,3’-(ethane-1,2-diylidene)bis(indolin-2-one) Derivatives

The design and synthesis of functionalized isoindigo compounds by reaction of isoindigo with (S)-glycidyl tosylate, epibromohydrin, 2-(bromomethyl)-1-(arylsulfonyl)aziridine, and 2-(bromomethyl)-1-(alkylsulfonyl)aziridine in the presence of MeONa proceed under mild conditions in moderate yields. (3Z,3’Z)-3,3’-(Ethane-1,2-diylidene)bis(1-(oxiran-2-ylmethyl)indolin-2-one), with an extended central olefin π-conjugated moiety was also reacted with methyl-oxiranes to give the corresponding N,N’-disubstituted derivative. Calculations with DFT and TD-DFT of hypothetical isoindigo-thiophene DA molecules with various electron withdrawing substituents, including aziridine, oxirane, nitrile, carbonyl, and sulfonate, indicated that the proximity and strength of the functional group have a significant effect on the HOMO, LUMO, vertical excitation energy, and oscillator strength of the π–π* transitions

Oral Presentations in English Courses: Effect of Instruction on Nonverbal Communication Competence

English education as part of university-level liberal arts curricula requires both academic English literacy education (which includes instruction in how to give an academic presentation) and instruction in practical English conversation (Nihongakujutsukaigi, 2010a, 2010b). To learn how to give a presentation, students must develop not only their knowledge of the target language, the organization of presentations, and the contents of their presentation; they also need to develop nonverbal communication skills. This study aimed to investigate the effect of nonverbal communication competence through three types of instruction: deductive, inductive, and a mix of both. The results showed that learners attained a good performance for posture. Inductive instruction was the most effective for making eye contact, and deductive instruction had the most impact on the performance of gesture. The mixed method ranked last for both eye contact and gesture. The results show that no matter what form instruction takes, it helps learners improve their nonverbal communication competence in oral presentations.高等教育機関である大学の教養英語教育では、実用的な会話能力の教授だけでなく、アカデミック・プレゼンテーションの教授を核とするリテラシー教育が求められている（日本学術院 , 2010a, 2010b）。本稿では、プレゼンテーションのより効果的教育方法を探るため、非言語コミュニケーションの明示的教授、非明示的教授、両者を取り入れた教授を比較した。姿勢ではどの教授方法も達成度が高かった。アイコンタクトでは非明示的教授、身ぶりでは明示的教授の効果が一番高く、両者を取り入れた教授の効果は共に最下位であった。入り交じった結果が得られたが、何らかの形で教授をすることにより、学習者の非言語コミュニケーション能力の向上を期待できることが分かった

The Impact Of The Question-Driven Technique On Developing Efl Jordanian Seventh Graders' Grammatical Competence

This research paper is aimed to examine the impact of the question-driven technique on developing EFL Jordanian seventh graders' grammatical competence. To this end, the researcher has redesigned the targeted grammatical material and constructed a grammar test focusing mainly on those grammatical themes given in the seventh grade textbook. The researcher has selected two sections (A & B) of the seventh grade; section A was assigned as a control group, the other one was assigned as an experimental group. The results of the study revealed that the students who have been taught inductively through the Questioning technique had gained better scores than those who have been taught deductively. It has also shown that the majority of the experimental group had more willingness and desire to participate in the class discussion. Also, it can be noticed that the use of the questioning technique is suitable for all types of learning styles and proficiency levels. Another important aspect to which the results of this study could be attributed is the adequate number of opportunities given for students to practice the targeted grammatical rules. In this regard, it sounds important to raise the strong effect of the scaffolding and modelling strategies in facilitating and easing the implementation of the questioning technique while teaching grammar

The dynamic emergence of cooperative norms in a social dilemma

This paper addresses the formation of social norms of cooperation through interaction in repeated Public Goods Games, using novel multilevel techniques. Cooperation has traditionally been understood as the interplay of static factors such as shared social identity and pre-existing norms. This study investigates the dynamic emergence of cooperative norms in the presence or absence of social categorization. A small effect of categorization was found: Categorization helps initiate and maintain higher levels of cooperation. However, the differences in emergent cooperation between small groups were much stronger than the differences between the Categorization and Non-Categorization conditions. Using explorative analyses, three distinct classes of groups were found. Within groups, group members follow nearly identical rules for their choice of cooperative behavior. We argue that individual behavior converged because of the social interactions within these groups. Overall, the development of cooperation is best predicted by the process of norm formation that occurs when social identities emerge.</p

Представления учителей биологии средней школы о науке, технике, технике и математике (STEM) Тенденция в образовании и уровень самоэффективности обучения

This paper attempts to identify the perceptions of secondary school biology teachers on Science, Technology, Engineering and Math (STEM) educational trend and the related teaching requirements. Being conducted with 37 secondary school biology teachers in AlKharj Governorate in Saudi Arabia, the study also measures their level of teaching self-efficacy in the light of that STEM educational trend. A test and a questionnaire were prepared for this purpose. The data that were collected via the survey and the given test were analyzed. Pearson Correlation Coefficient was used to validate the internal consistency of the questionnaire. The statistical stability of the test and the questionnaire were calculated according to Alpha-Cronbach Coefficient. The results of the study show that there is a weakness in the teachers' knowledge of the STEM trend. Their opinions and answers reveal that their perceptions of this kind of education and the related teaching requirements is weak. The results also show that the level of teaching self-efficacy in the light of the STEM educational trend ranges from medium to high. In addition, while there are no statistically significant differences in three different variables, there are statistically significant differences in other two variables in the study. The study ends with some recommendations that can help in developing the teachers' perceptions on STEM education and their teaching self-efficacy.Este artículo intenta identificar las percepciones de los maestros de biología de la escuela secundaria sobre la tendencia educativa de Ciencia, Tecnología, Ingeniería y Matemáticas (STEM) y los requisitos de enseñanza relacionados. Realizado con 37 profesores de biología de la escuela secundaria en la gobernación de AlKharj en Arabia Saudita, el estudio también mide su nivel de autoeficacia docente a la luz de esa tendencia educativa STEM. Se preparó una prueba y un cuestionario para este propósito. Se analizaron los datos que se recopilaron a través de la encuesta y la prueba dada. El coeficiente de correlación de Pearson se utilizó para validar la consistencia interna del cuestionario. La estabilidad estadística de la prueba y el cuestionario se calcularon de acuerdo con el coeficiente de Alpha-Cronbach. Los resultados del estudio muestran que existe una debilidad en el conocimiento de los docentes sobre la tendencia STEM. Sus opiniones y respuestas revelan que sus percepciones de este tipo de educación y los requisitos de enseñanza relacionados son débiles. Los resultados también muestran que el nivel de autoeficacia docente a la luz de la tendencia educativa STEM varía de medio a alto. Además, aunque no existen diferencias estadísticamente significativas en tres variables diferentes, existen diferencias estadísticamente significativas en otras dos variables en el estudio. El estudio finaliza con algunas recomendaciones que pueden ayudar a desarrollar las percepciones de los maestros sobre la educación STEM y su autoeficacia docente.В этой статье предпринята попытка определить восприятие учителей биологии в средней школе в области науки, технологий, техники и математики (STEM) и связанных с ними требований к преподаванию. В исследовании, проводимом вместе с 37 учителями биологии в средней школе в провинции Аль-Хардж в Саудовской Аравии, также измеряется уровень их самообучаемости в свете этой образовательной тенденции STEM. Для этого были подготовлены тест и анкета. Данные, которые были собраны с помощью опроса и данного теста были проанализированы. Коэффициент корреляции Пирсона был использован для проверки внутренней согласованности вопросника. Статистическая устойчивость теста и вопросник были вычислены в соответствии с альфа-Кронбах коэффициента. Результаты исследования показывают, что существует недостаток в знаниях учителей тенденции STEM. Их мнения и ответы показывают, что их восприятие такого рода образование и связанные с ними требования обучения является слабым. Результаты также показывают, что уровень обучения самоэффективность в свете STEM образовательного тренда в диапазоне от среднего до высокого. Кроме того, в то время как нет никаких статистически значимых различий в трех различных переменных, существуют статистически значимые различия в двух других переменных в исследовании. Исследование заканчивается с некоторыми рекомендациями, которые могут помочь в разработке представлений учителей на STEM образования и их преподавание самоэффективности

Pros and Cons of Deductive and Inductive Grammar Teaching in Adults

The main purpose of this study was to investigate what method of teaching grammar is more effective at B1 level of proficiency, arguing that explicit-deductive design of instruction could have an advantage in adult learners. Another purpose was to explore the differences between the two instructional treatments with respect to implicit and explicit knowledge of learners as well as the interface between the types of knowledge. The research has found that the deductive group outperformed the participants with the inductive instructional method, strengthening the idea that the teacher-centred teaching approach could be an appealing alternative to TBA