No abstract

Psychology researchers have long attempted to identify educational practices that improve student learning. However, experimental research on these practices is often conducted in laboratory contexts or in a single course, which threatens the external validity of the results. In this article, we establish an experimental paradigm for evaluating the benefits of recommended practices across a variety of authentic educational contexts—a model we call ManyClasses. The core feature is that researchers examine the same research question and measure the same experimental effect across many classes spanning a range of topics, institutions, teacher implementations, and student populations. We report the first ManyClasses study, in which we examined how the timing of feedback on class assignments, either immediate or delayed by a few days, affected subsequent performance on class assessments. Across 38 classes, the overall estimate for the effect of feedback timing was 0.002 (95% highest density interval = [−0.05, 0.05]), which indicates that there was no effect of immediate feedback compared with delayed feedback on student learning that generalizes across classes. Furthermore, there were no credibly nonzero effects for 40 preregistered moderators related to class-level and student-level characteristics. Yet our results provide hints that in certain kinds of classes, which were undersampled in the current study, there may be modest advantages for delayed feedback. More broadly, these findings provide insights regarding the feasibility of conducting within-class randomized experiments across a range of naturally occurring learning environments.

The susceptibility of a prototypical hydrogen phosphonate to undergo P-H activation upon treatment with alkynylgold complexes has been studied. Dynamic solution behavior was observed during reactions involving triphenylphosphine ligated substrates and was attributed to rapid phosphine exchange between the alkynylgold starting material and the gold phosphonate product. The use of bulky biaryldialkylphosphine ligands eliminated the fluxional behavior, but did not significantly slow the rate of P-H activation. Similarly, changing the supporting ligand to an N-heterocyclic carbene did not significantly slow the rate of the reaction. Despite a number of reports outlining the functionalization of propargyl alcohols using gold catalysts, incorporating these groups into the architecture of the alkynylgold substrates did not alter the product distributions. Although the chemistry tolerated a range of supporting ligands, incorporating electron donating groups into the alkyne increased the rate of the reaction while electron-withdrawing groups slowed the reaction. A possible mechanism for the process includes a transition state containing significant pi-contribution from the alkyne. Due to the high yields of gold phosphonates obtained in this chemistry as well as the mild conditions of the reactions, the interception of intermediates/catalysts by substrates or ligands containing labile P-H donors is an issue that must be circumvented when designing or developing a gold catalyzed reaction that proceeds through alkynylgold intermediates.

) for Cu(PyED)·2Cl, indicating three nitrogens and a chloride in the psuedo-equatorial plane with the remaining pyridine nitrogen and solvent in axial positions. EPR spectra of the Cu(II) complexes exhibit an axially elongated octahedron. This spectroscopic evidence, together with density functional theory computed geometries, suggest six-coordinate structures for Cu(II) and Fe(II) complexes and a five-coordinate environment for Zn(II) analogs. Bergman cyclization via thermal activation of these constructs yields benzannulated product indicative of diradical generation in all complexes within 3 h at 37°C. A significant metal dependence on the rate of the reaction is observed [Cu(II) > Fe(II) > Zn(II)], which is mirrored in in vitro DNA-damaging outcomes. Whereas in situ chelation of PyED leads to considerable degradation in the presence of all metals within 1 h under hyperthermia conditions, Cu(II) activation produces >50% compromised DNA within 5 min. Additionally, Cu(II) chelated PyED outcompetes DNA polymerase I to successfully inhibit template strand extension. Exposure of HeLa cells to Cu(PyBD)·SO 4 (IC 50 = 10 μM) results in a G2/M arrest compared with untreated samples, indicating significant DNA damage. These results demonstrate metal-controlled radical generation for degradation of biopolymers under physiologically relevant temperatures on short timescales. metal-mediated radicals | DNA degradation | polymerase inhibition | enediyne | Bergman cyclization

We demonstrate that ligand–metal–Aβ interaction with subsequent radical generation is a relatively rapid mechanism for influencing Aβ structural integrity and thus, the aggregation pathway.