An estimate of the solar cyclic variation of the Martian upper atmosphere

Mathematical model for estimating probable cyclic variations in Martian atmosphere during solar activit

Inverting Small Molecule-Protein Recognition by the Fluorine Gauche Effect: Selectivity Regulated by Multiple H→F Bioisosterism

Fluorinated motifs have a venerable history in drug discovery, but as C(sp3 )@F-rich 3D scaffolds appear with increasing frequency, the effect of multiple bioisosteric changes on molecular recognition requires elucidation. Herein we demonstrate that installation of a 1,3,5-stereotriad, in the substrate for a commonly used lipase from Pseudomonas fluorescens does not inhibit recognition, but inverts stereoselectivity. This provides facile access to optically active, stereochemically well-defined organofluorine compounds (up to 98% ee). Whilst orthogonal recognition is observed with fluorine, the trend does not hold for the corresponding chlorinated substrates or mixed halogens. This phenomenon can be placed on a structural basis by considering the stereoelectronic gauche effect inherent to F@C@C@X systems (s!s*). Docking reveals that this change in selectivity (H versus F) with a common lipase results from inversion in the orientation of the bound substrate being processed as a consequence of conformation. This contrasts with the stereochemical interpretation of the biogenetic isoprene rule, whereby product divergence from a common starting material is also a consequence of conformation, albeit enforced by two discrete enzymes

Regioselective, catalytic 1,1-difluorination of enynes

Fluorinated small molecules are prevalent across the functional small-molecule spectrum, but the scarcity of naturally occurring sources creates an opportunity for creative endeavour in developing routes to access these important materials. Iodine(I)/iodine(III) catalysis has proven to be particularly well-suited to this task, enabling abundant alkene substrates to be readily intercepted by in situ-generated λ3-iodanes and processed to high-value (di)fluorinated products. These organocatalysis paradigms often emulate metal-based processes by engaging the π bond and, in the case of styrenes, facilitating fluorinative phenonium-ion rearrangements to generate difluoromethylene units. Here we demonstrate that enynes are competent proxies for styrenes, thereby mitigating the recurrent need for aryl substituents, and enabling highly versatile homopropargylic difluorides to be generated in an operationally simple manner. The scope of the method is disclosed, together with application in target synthesis (>30 examples, up to >90% yield)

Potential-based achievement goals

Background Self-based achievement goals use one's own intrapersonal trajectory as a standard of evaluation, and this intrapersonal trajectory may be grounded in one's past (past-based goals) or one's future potential (potential-based goals). Potential-based goals have been overlooked in the literature to date. Aims The primary aim of the present research was to address this oversight within the context of the 3 × 2 achievement goal framework. Samples The Study 1 sample was 381 US undergraduates; the Study 2 sample was 310 US undergraduates. Methods In Study 1, we developed scales to assess potential-approach and potential-avoidance goals and tested their factorial validity with exploratory and confirmatory factor analyses. In Study 2, we used confirmatory factor analysis to test both the separability of past-based and potential-based goals and their higher order integration within the self-based category. Results Study 1 supported the factorial validity of the potential-approach and potential-avoidance goal scales. Study 2 supported the separability of past-based and potential-based goals, as well as their higher order integration within the self-based category. Conclusions This research documents the utility of the proposed distinction and paves the way for subsequent work on antecedent and consequences of potential-approach and potential-avoidance goals. It highlights the importance of focusing on distinct types of growth-based goals in the achievement goal literature

Measuring students' emotions in the early years: The Achievement Emotions Questionnaire-Elementary School (AEQ-ES)

This article reports about the development and validation of a measurement instrument assessing elementary school students' achievement emotions (Achievement Emotions Questionnaire-Elementary School, AEQ-ES). Specifically, the instrument assesses students' enjoyment, anxiety, and boredom pertaining to three types of academic settings (i.e., attending class, doing homework, and taking tests and exams). Scale construction was based on Pekrun's (2006) control-value theory of achievement emotions. The instrument was tested using samples from German and American elementary school classrooms. The results of Study 1 (German sample) corroborate the reliability and structural validity of the new emotion measure. Moreover, they show that students' achievement emotions were linked with their control and value appraisals as well as their academic performance, thus supporting the external validity of the measure as well as propositions of Pekrun's (2006) control-value theory of achievement emotions. Study 2 (American sample) corroborated the cross-cultural equivalence of the measure and the generalizability of findings across the German and American samples. Implications for research on achievement emotions and educational practice are discussed

Predicting long-term growth in students' mathematics achievement: The unique contributions of motivation and cognitive strategies

This research examined how motivation (perceived control, intrinsic motivation, and extrinsic motivation), cognitive learning strategies (deep and surface strategies), and intelligence jointly predict long-term growth in students' mathematics achievement over 5 years. Using longitudinal data from six annual waves (Grades 5 through 10; Mage = 11.7 years at baseline; N = 3,530), latent growth curve modeling was employed to analyze growth in achievement. Results showed that the initial level of achievement was strongly related to intelligence, with motivation and cognitive strategies explaining additional variance. In contrast, intelligence had no relation with the growth of achievement over years, whereas motivation and learning strategies were predictors of growth. These findings highlight the importance of motivation and learning strategies in facilitating adolescents' development of mathematical competencies

Achievement Emotions and Academic Performance: Longitudinal Models of Reciprocal Effects

A reciprocal effects model linking emotion and achievement over time is proposed. The model was tested using five annual waves of the Project for the Analysis of Learning and Achievement in Mathematics (PALMA) longitudinal study, which investigated adolescents’ development in mathematics (Grades 5–9; N = 3,425 German students; mean starting age = 11.7 years; representative sample). Structural equation modeling showed that positive emotions (enjoyment, pride) positively predicted subsequent achievement (math end-of-the-year grades and test scores), and that achievement positively predicted these emotions, controlling for students’ gender, intelligence, and family socioeconomic status. Negative emotions (anger, anxiety, shame, boredom, hopelessness) negatively predicted achievement, and achievement negatively predicted these emotions. The findings were robust across waves, achievement indicators, and school tracks, highlighting the importance of emotions for students’ achievement and of achievement for the development of emotions