The λ 3 -phosphinine derivatives 2,6-diphenyl-4-(p-tolyl)phosphinine and 2-(2Ј-pyridyl)-4,6-diphenylphosphinine were quantitatively converted into the corresponding λ 4 -phosphinine anions by reaction with phenyllithium. Systematic hydrolysis experiments with H 2 O and MeOH show that a subtle interplay between the pK a values of the generated 1,2-dihydrophosphinine derivatives and the pK b value of the formed bases, LiOH and LiOCH 3 , respectively, leads either to the kinetic or thermodynamic product. The coordination[a]
Heterogeneous catalytic oxidation of 5-hydroxymethylfurfural (HMF) with molecular oxygen to 2,5-diformylfuran (DFF) was performed on aluminium oxide-supported ruthenium catalysts (Ru/Al 2 O 3 ). The ruthenium catalysts were analyzed by pH and Brunauer-Emett-Teller (BET) measurement, and potential side products measured by HPLC-UV. High catalyst activity with near-quantitative DFF yield (> 99.9 %) was achieved in toluene under moderate reaction conditions (90 °C, 0.2 MPa O 2 ). Various Al 2 O 3 supports were screened for optimal catalyst activity and selectivity for DFF, and the most effective was chosen for a Design of Experiments (DoE). With a central composite design based on a response-surface model, the effects of reaction parameters (i. e., catalyst amount, oxygen pressure and temperature) on the reaction rate were investigated, and the selected model tested by analysis of variance (ANOVA). The modeling showed that catalyst amount had the highest relative impact on the reaction rate, and afforded in-depth knowledge about the chemical space investigated.
Diagnostic assessments for dementia include the evaluation of subjective memory impairment, dementia worries, or depressive symptoms. Data on the predictive value of these factors remain unclear, and varying help-seeking behavior may contribute to this finding. We investigate whether differentiating help-seeking motivation from other psychological factors associated with cognitive impairment would enhance the prediction of diagnostic outcomes in a memory clinic. We obtained information on help-seeking motivation from 171 patients who underwent routine diagnostic assessments. Utilizing a discriminant correspondence analysis, our results indicate that extrinsic motivation increases the likelihood of receiving a dementia diagnosis, whereas depression or the duration of deficits carries discriminatory information to further guide the differentiation of prodromal dementia. Recognizing motivational aspects of help-seeking behavior can complement the clinical evaluation of cognitive performance.
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