Modulating Chalcogen Bonding and Halogen Bonding Sigma-Hole Donor Atom Potency and Selectivity for Halide Anion Recognition.

A series of acyclic anion receptors containing chalcogen bond (ChB) and halogen bond (XB) donors integrated into a neutral 3,5-bis-triazole pyridine scaffold are described, in which systematic variation of the electronic-withdrawing nature of the aryl substituents reveal a dramatic modulation in sigma-hole donor atom potency for anion recognition. Incorporation of strongly electron-withdrawing perfluorophenyl units appended to the triazole heterocycle telluro- or iodo- donor atoms, or directly linked to the tellurium donor atom dramatically enhances the anion binding potency of the sigma-hole receptors, most notably for the ChB and XB receptors displaying over thirty-fold and eight-fold increase in chloride anion affinity, respectively, relative to unfluorinated analogues. Linear free energy relationships for a series of ChB based receptors reveal the halide anion recognition behaviour of the tellurium donor is highly sensitive to local electronic environments. This is especially the case for those directly appended to the Te centre (3⋅ChB), where a remarkable enhancement of strength of binding and selectivity for the lighter halides is observed as the electron-withdrawing ability of the Te-bonded aryl group increases, highlighting the exciting opportunity to fine-tune anion affinity and selectivity in ChB-based receptor systems.

Click-level Learning Analytics in an Online Medical Education Learning Platform.

THEORY: Learning in digital environments allows the collection of inexpensive, fine-grained process data across a large population of learners. Intentional design of the data collection can enable iterative testing of an instructional design. In this study, we propose that across a population of learners the information from multiple choice question responses can help to identify which design features are associated with positive learner engagement. Hypothesis: We hypothesized that, within an online module that presents serial knowledge content, measures of click-level behavior will show sufficient, but variable, association with a test-measure so as to potentially guide instructional design. Method: The Aquifer online learning platform employs interactive approaches to enable effective learning of health professions content. A multidisciplinary focus group of experts identified potential learning analytic measures within an Aquifer learning module, including: hyperlinks clicked (yes/no), magnify buttons clicked (yes/no), expert advice links clicked (yes/no), and time spent on each page (seconds). Learning analytics approaches revealed which click-level data was correlated with the subsequent relevant Case MCQ. We report regression coefficients where the dependent variable is student accuracy on the Case MCQ as a general indicator of successful engagement. Results: Clicking hyperlinks, magnifying images, clicking "expert" links, and spending >100 seconds on each page were learning analytic measures and were positively correlated with Case MCQ success; rushing through pages (<20 seconds) was inversely correlated with success. Conversely, for some measures, we failed to find expected associations. Conclusions: In online learning environments, the wealth of process data available offers insights for instructional designers to iteratively hone the effectiveness of learning. Learning analytic measures of engagement can provide feedback as to which interaction elements are effective.

Short-Term Intervention Effects of the PATHS Curriculum in Young Low-Income Children: Capitalizing on Plasticity.

Deficits in behavioral and cognitive regulation are prevalent in children reared in poverty relative to more affluent children due to the effects of adverse conditions on the developmental underpinnings of these skills. Despite evidence to suggest that these emergent processes are susceptible to environmental inputs, research documenting short-term intervention program influences on these regulatory domains in young impoverished children is limited. We sought to determine the proximal effects of a universal school-based intervention (the PATHS Curriculum) on social, emotional, relational, and cognitive outcomes in urban poor kindergarten children. Four schools in high-poverty neighborhoods with similar demographic characteristics were randomly assigned to either PATHS or an attentional control. Teacher-reported measures of behavior (e.g., attention, concentration, aggression), peer nominations (e.g., likability, aggression, acceptance), and tasks gauging inhibitory control were administered in the fall of kindergarten and again in the spring after one academic year (about 6 months) of PATHS. Children who received PATHS exhibited significantly greater improvements than control students across all teacher-rated behavioral measures of social competence (i.e., emotion regulation, prosocial behavior, peer relations) and behavioral problems (i.e., aggression, internalizing behaviors, impulsivity and hyperactivity) at post-test as well as improvements in motor inhibition. This line of research constitutes an important frontier for prevention research given the implications for improving ultimate outcomes for otherwise disadvantaged children.

Associations Between Environmental Conditions and Executive Cognitive Functioning and Behavior During Late Childhood: A Pilot Study.

Numerous studies have established the influence of detrimental home conditions on child cognition and behavior; however, fewer have assessed these outcomes in the context of relatively "normal" range of home environmental conditions. Given the exquisite sensitivity to the environment of the neural substrates that undergird executive functioning (EF) and behavioral self-regulation in children, it is possible that a range of conditions within the home, even in the absence of maltreatment or economic deprivation, may impact these outcomes. The purpose of the present exploratory investigation was to further define the relationship between features of the home environment using the HOME inventory (a structured interview and observation of parent and child) and several dimensions of child EF and behavioral problems. In addition, this study sought to elucidate potentially differential associations between home and parent-reported neighborhood conditions-a hypothetically less direct influence on cognition in this age group-and level of child functioning. A battery of EF performance tasks and a widely-used checklist of behavioral problems were administered to 66 children, 8-11 years old from a lower middle income, working class sample. Results showed significant relationships between the home environment and several dimensions of EF and behavioral problems. In contrast, neighborhood conferred additional effects only on rule-breaking and aggression, not cognition, which is consistent with evidence that externalizing behavior in this age group becomes increasingly oriented toward outside influences. These findings warrant follow-up studies to establish causality. A broader program of research designed to delve further into the relationship between nuanced influences from the home and child cognition and behavior has implications for parenting strategies that foster healthy development. Neighborhood contexts should also be considered during early and mid-adolescent years based on existing studies and findings reported herein suggesting that this period of newfound autonomy and the heightened significance of peer relationships may influence externalizing behaviors, with implications for protective courses of action.

Otolith shape variability and associated body growth differences in giant grenadier, Albatrossia pectoralis.

Fish stocks can be defined by differences in their distribution, life history, and genetics. Managing fish based on stock structure is integral to successful management of a species because fishing may affect stocks disproportionately. Genetic and environmental differences can affect the shape and growth of otoliths and these differences may be indicative of stock structure. To investigate the potential for speciation or stock structure in giant grenadier, Albatrossia pectoralis, we quantified the shape of female giant grenadier otoliths and compared body growth rates for fish with three otolith shapes; shape types were classified visually by an experienced giant grenadier age reader, and were not defined by known distribution or life history differences. We found extreme variation in otolith shape among individuals; however, the shapes were a gradation and not clearly defined into three groups. The two more extreme shapes, visually defined as "hatchet" and "comb", were discernable based on principal component analyses of elliptical Fourier descriptors, and the "mixed" shape overlapped both of the extreme shapes. Fish with hatchet-shaped otoliths grew faster than fish with comb-shaped otoliths. A genetic test (cytochrome c oxidase 1 used by the Fish Barcode of Life Initiative) showed almost no variability among samples, indicating that the samples were all from one species. The lack of young specimens makes it difficult to link otolith shape and growth difference to life history. In addition, shape could not be correlated with adult movement patterns because giant grenadiers experience 100% mortality after capture and, therefore, cannot be tagged and released. Despite these limitations, the link between body growth and otolith shape indicates measurable differences that deserve more study.