Nationality distribution in tests A and B.

<p>Nationality distribution in tests A and B.</p

Average CI95 of each test.

<p>Average CI95 of each test.</p

Test sample conditions.

<p>Test sample conditions.</p

Training a Constitutional Dynamic Network for Effector Recognition: Storage, Recall, and Erasing of Information

Constitutional dynamic libraries (CDLs) of hydrazones, acylhydrazones, and imines undergo reorganization and adaptation in response to chemical effectors (herein metal cations) via component exchange and selection. Such CDLs can be subjected to training by exposition to given effectors and keep memory of the information stored by interaction with a specific metal ion. The long-term storage of the acquired information into the set of constituents of the system allows for fast recognition on subsequent contacts with the same effector(s). Dynamic networks of constituents were designed to adapt orthogonally to different metal cations by up- and down-regulation of specific constituents in the final distribution. The memory may be erased by component exchange between the constituents so as to regenerate the initial (statistical) distribution. The libraries described represent constitutional dynamic systems capable of acting as information storage molecular devices, in which the presence of components linked by reversible covalent bonds in slow exchange and bearing adequate coordination sites allows for the adaptation to different metal ions by constitutional variation. The system thus performs information storage, recall, and erase processes

Heterogeneous Electrochemical Ammonia Oxidation with a Ru-bda Oligomer Anchored on Graphitic Electrodes via CH−π Interactions

Molecular catalysts can promote ammonia oxidation, providing mechanistic insights into the electrochemical N2 cycle for a carbon-free fuel economy. We report the ammonia oxidation activity of carbon anodes functionalized with the oligomer {[RuII(bda-κ-N2O2)(4,4′-bpy)]10(4,4′-bpy)}, Rubda-10, where bda is [2,2′-bipyridine]-6,6′-dicarboxylate and 4,4′-bpy is 4,4′-bipyridine. Electrocatalytic studies in propylene carbonate demonstrate that the Ru-based hybrid anode used in a 3-electrode configuration transforms NH3 to N2 and H2 in a 1:3 ratio with near-unity faradaic efficiency at an applied potential of 0.1 V vs Fc+/0, reaching turnover numbers of 7500. X-ray absorption spectroscopic analysis after bulk electrolysis confirms the molecular integrity of the catalyst. Based on computational studies together with electrochemical evidence, ammonia nucleophilic attack is proposed as the primary pathway that leads to critical N–N bond formation