The visible-light-accelerated oxo-azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap) ]Cl or [Cu(dap)Cl ] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. Cu is proposed as the catalytically active species, which upon coordinating azide will undergo light-accelerated homolysis to form Cu and azide radicals. This activation principle (Cu -X→Cu +X ) opens up new avenues for copper-based photocatalysis.

The authors conjecture that to understand normal stress regulation, including cortisol stress reactivity, it is important to understand why these biomarkers are released and what they function to accomplish within the individual. This perspective holds that high (or rising) cortisol has advantages and disadvantages that must be understood within a context to understand how individual differences unfold. This perspective is juxtaposed with a popular vantage point of this stress hormone or of stress exposure that emphasizes the deleterious consequences or problems of this hormone. While the costs and benefits of cortisol are emphasized for normal stress regulation, this dynamic context-dependent purpose of stress hormones should extend to the development of psychopathology as well. This functional and dynamic view of cortisol is helpful for interpreting why Tackett and colleagues (2014) appear to observe advantageous cortisol recovery from stress in individuals with elevated personality disorder symptoms.

The NHC-catalysed benzoin condensation has been studied mechanistically by a combination of experimental and computational chemistry. The presented EPR-spectroscopic and computational data provide evidence for a radical pair as a potential second key-intermediate that is derived from the Breslow-intermediate via an SET process.

In steam-assisted gravity drainage (SAGD) operations, the produced fluids are complex water-in-oil-in-water (W/O/W) emulsions. A diluent is often added to reduce the density and viscosity of the heavy crude oil. However, the quality and composition of the diluents may in some cases increase emulsion stability and cause the dehydration of the oil to be more difficult because there are more surface-active agents added to the oil coming from the diluent streams. Thus, this work was aimed at studying the effect of three different diluents on interfacial film formation of a Canadian heavy oil. Interfacial elasticity and compressibility were evaluated, and the results were then correlated with emulsion stability. The wettability of the systems was also studied. The systems studied behaved as if a bidimensional gel near its gelation point had organized at the interface, in which adsorbed amphiphilic materials, such as asphaltenes and resins, self-aggregated at the interface, forming a network that acts as a stabilizing mechanism for produced emulsions. When the interface was aged, its gel strength was much higher than the fresh interface, suggesting an explanation as to why aged emulsions are more difficult to treat. Unlike elasticity and interfacial tension measurements, it was demonstrated that compressibility measurements can predict emulsion stability under different conditions. The higher the crumpling film ratio and the lower the compressibility, the more stable the emulsion. This test method gives more insights into the mechanisms of emulsion stabilization caused by diluents and asphaltenes and can potentially be employed to study the structure and demulsifying performance relationships of emulsion breakers (EBs) and reverse emulsion breakers (REBs).

Background Given the established relation between testosterone and aging in older adults, we tested whether buccal telomere length (TL), an established cellular biomarker of aging, was associated with testosterone levels in youth. Methods Children, mean age 10.2 years, were recruited from the greater New Orleans area and salivary testosterone was measured during both an acute stressor and diurnally. Buccal TL was measured using monochrome multiplex quantitative real-time PCR (MMQ-PCR). Testosterone and telomere length data was available on 77 individuals. The association between buccal TL and testosterone was tested using multivariate Generalized Estimating Equations (GEE) to account for clustering of children within families. Results Greater peak testosterone levels (β=-0.87, p < 0.01) and slower recovery (β=-0.56, p < 0.01) and reactivity (β = -1.22, p < 0.01) following a social stressor were significantly associated with shorter buccal TL after controlling for parental age at conception, child age, sex, sociodemographic factors and puberty. No association was initially present between diurnal measurements of testosterone or morning basal testosterone levels and buccal TL. Sex significantly moderated the relation between testosterone reactivity and buccal TL. Conclusions The association between testosterone and buccal TL supports gonadal maturation as a developmentally sensitive biomarker of aging within youth. As stress levels of testosterone were significantly associated with buccal TL, these findings are consistent with the growing literature linking stress exposure and accelerated maturation. The lack of association of diurnal testosterone or morning basal levels with buccal TL bolsters the notion of a shared stress-related maturational mechanism between cellular stress and the hypothalamic pituitary gonadal (HPG) axis. These data provide novel evidence supporting the interaction of aging, physiologic stress and cellular processes as an underlying mechanism linking negative health outcomes and early life stress.