Towards a resolution of some outstanding issues in transitive research: an empirical test on middle childhood

Transitive Inference (deduce B > D from B > C and C > D) can help us to understand other areas of sociocognitive development. Across three experiments, learning, memory, and the validity of two transitive paradigms were investigated. In Experiment 1 (N = 121), 7-year-olds completed a three-term nontraining task or a five-term task requiring extensive-training. Performance was superior on the three-term task. Experiment 2 presented 5–10-year-olds with a new five-term task, increasing learning opportunities without lengthening training (N = 71). Inferences improved, suggesting children can learn five-term series rapidly. Regarding memory, the minor (CD) premise was the best predictor of BD-inferential performance in both task-types. However, tasks exhibited different profiles according to associations between the major (BC) premise and BD inference, correlations between the premises, and the role of age. Experiment 3 (N = 227) helped rule out the possible objection that the above findings simply stemmed from three-term tasks with real objects being easier to solve than computer-tasks. It also confirmed that, unlike for five-term task (Experiments 1 & 2), inferences on three-term tasks improve with age, whether the age range is wide (Experiment 3) or narrow (Experiment 2). I conclude that the tasks indexed different routes within a dual-process conception of transitive reasoning: The five-term tasks indexes Type 1 (associative) processing, and the three-term task indexes Type 2 (analytic) processing. As well as demonstrating that both tasks are perfectly valid, these findings open up opportunities to use transitive tasks for educability, to investigate the role of transitivity in other domains of reasoning, and potentially to benefit the lived experiences of persons with developmental issues

Empirical DFT Model to Predict Triplet Quantum Yield Through Singlet Oxygen Yields

Triplet photosensitizers can be used for a variety of applications, including photocatalysis, OLEDs, and photodynamic therapy. Excited triplet states can be quenched by triplet oxygen to make singlet oxygen. Often the singlet oxygen quantum yield (Φ▵) is used as a lower approximation for the triplet yield. Unpredictable effects of even minor structural changes can drastically alter the Φ▵ and complicate the design of new triplet photosensitizers. The most common strategy to increase Φ▵ is to incorporate heavy atoms, promoting the “heavy atom effect”. However, the position and the identity of the heavy atom greatly influences the Φ▵. We have created a predictive model that correlates calculated natural atomic orbital composition of the heavy atom(s) contributing to the frontier molecule orbitals of a photosensitizer with the experimental Φ▵. The model, derived from several fluorescein derivatives, provides a calculated Φ▵ in agreement with the experimental values for a variety of well-known photosensitizers, including rhodamine dyes, fluorescein derivatives, and octahedral metal complexes

Simplification of the Potassium Ferrioxalate Actinometer Through Carbon Dioxide Monitoring

Abstract Chemical actinometry can be used to determine photons absorbed for a photochemical reaction, which is required to calculate the quantum yield. A photochemical reaction with a known quantum yield can be used as a relative standard for the determination of an unknown quantum yield for a light-driven reaction. Herein, we have developed a simplified approach to using the popular potassium ferrioxalate actinometer. Traditionally, the photoreduction of Fe(III) to Fe(II) is monitored by following the absorbance of Fe(II) by reacting aliquots of the actinometry solution with 9,10-phenanthroline to form a red colored complex. The multiple steps for this method make it tedious and vulnerable to errors, especially inadvertent light exposure. In lieu of spectroscopic measurements of the Fe(II) concentration, the production of CO2 was measured to determine the number of photons absorbed over time. CO2 production was measured in two different ways: by the pressure increase in a sealed system and the volume change by trapping the CO2. Both methods were considerably less laborious and showed agreeable results compared with the traditional spectroscopic method