Catalytic Mechanism of Fatty Acid Photodecarboxylase: On the Detection and Stability of the Initial Carbonyloxy Radical Intermediate

In fatty acid photodecarboxylase (FAP), light-induced formation of the primary radical product RCOO⋅ from fatty acid RCOO⁻ occurs in 300 ps, upon which CO₂ is released quasi-immediately. Based on the hypothesis that aliphatic RCOO⋅ (spectroscopically uncharacterized because unstable) absorbs in the red similarly to aromatic carbonyloxy radicals such as 2,6-dichlorobenzoyloxy radical (DCB⋅), much longer-lived linear RCOO⋅ has been suggested recently. We performed quantum chemical reaction pathway and spectral calculations. These calculations are in line with the experimental DCB⋅ decarboxylation dynamics and spectral properties and show that in contrast to DCB⋅, aliphatic RCOO⋅ radicals a) decarboxylate with a very low energetic barrier and on the timescale of a few ps and b) exhibit little red absorption. A time-resolved infrared spectroscopy experiment confirms very rapid, ≪300 ps RCOO⋅ decarboxylation in FAP. We argue that this property is required for the observed high quantum yield of hydrocarbons formation by FAP.     

Synthesis and evaluation of new phosphonated δ-lactam and glutarimide derivatives as angiotensin converting enzyme inhibitors

An efficient synthesis of new γ,δ-insaturated δ-lactam and glutarimide derivatives bearing a phosphonomethyl group from a common allylphosphonate precursor is described. Our approach is based on a two-step procedure involving the preparation of phosphonated-1,5-ketoester and −1,5-diester followed by an amidation–heterocyclization sequence. The first step proceeds via Michael's addition of ethyl acetoacetate and diethyl malonate on an allylphosphonate starting material. The second step consists of a base-promoted intramolecular amidation-cyclization sequence with primary amines, which accounts for the construction of δ-lactams and glutarimide skeletons. We performed the evaluation of angiotensin I-converting enzyme (ACE) inhibition using an in vitro enzyme assay on six new compounds. Five compounds showed potent ACE inhibitory activity, with IC₅₀ values ranging from 0.02 to 0.27 mg/ml. Compared with Captopril, used as a reference drug, two new glutarimide derivatives exhibited higher efficiency ACE inhibition activity.     

Anion-π Interaction for Molecular Recognition of Anions: Focus on Cooperativity with Hydrogen Bonding

Anion recognition represents an active area of research in supramolecular chemistry. The last two decades have been marked by spectacular advances in the design of new anion receptors. Moreover, the development of approaches combining experimental and theoretical studies has proved to be particularly relevant, allowing for a better understanding and rationalization of the phenomena involved in anion complexation processes. In this context, the combination of weak interactions within the same receptor and their synergistic effects, called cooperativity, has attracted increasing interest within the scientific community. This Review focuses on the combination of anion-π and hydrogen bonds and the emerging concept of cooperativity. The most relevant anion-π donor families are presented. The concept of cooperativity is illustrated using the most recent examples present in current literature.     

Imaging the Footprint of Nanoscale Electrochemical Reactions for Assessing Synergistic Hydrogen Evolution

This work proposes a novel method for measuring the intrinsic activity of single metal-based nanoparticles towards water reduction in neutral media at industrially relevant current densities. Instead of using gas nanobubbles as proxy, the method uses optical microscopy to track the local footprint of the reaction through the precipitation of metal hydroxide, which is associated to the local pH increase during electrocatalysis. The results show the electrocatalytic activities of different types of metal nanoparticles and bifunctionnal core-shell nanostructures made of Ni and Pt, and demonstrate the importance of metal hydroxide nano-shells in enhancing electrocatalysis. This method should be generalizable to any electrocatalytic reaction involving pH changes such as nitrate or CO₂ reduction.     

The Playground Shade Index: A New Design Metric for Measuring Shade and Seasonal Ultraviolet Protection Characteristics of Parks and Playgrounds

Current shading strategies used to protect outdoor playgrounds from harmful solar radiation include the placement of artificial cloth weaves or permanent roofing over a playground site, planting trees in proximity to playground equipment, and using vegetation or surface texture variations to cool playground surfaces. How and where an artificial shade structure is placed or a tree is planted to maximize the shade protection over specific playground areas, requires careful assessment of local seasonal sun exposure patterns. The Playground Shade Index (PSI) is introduced here as a design metric to enable shade and solar ultraviolet exposure patterns to be derived in an outdoor space using conventional aerial views of suburban park maps. The implementation of the PSI is demonstrated by incorporating a machine learning design tool to classify the position of trees from an aerial image, thus enabling the mapping of seasonal shade and ultraviolet exposure patterns within an existing 7180 m² parkland. This is achieved by modeling the relative position of the sun with respect to nearby buildings, shade structures, and the identified evergreen and deciduous tree species surrounding an outdoor playground.