High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene

A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings.     

Predicting New Ugi–Smiles Couplings: A Combined Experimental and Theoretical Study

Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles.     

On the Formation of a Protic Ionic Liquid in Nature

The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid‐based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed‐cation ammonium formate milieu has properties consistent with its classification as a protic IL.     

Formation of a Single-Crystal Aluminum-Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure-Directing Agents

An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.     

Reversible Assembly of Microgels by Metallo-Supramolecular Chemistry

The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi-versatile colloidal assemblies. Hereafter, terpyridine-functionalized poly(N-isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble–freeze–disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter-particle metal–terpyridine bis-complexes upon addition of the metallic cation (such as Fe^II, Co^II). By oxidation of the metal–terpyridine bis-complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.     

What's Hot,What's Not: The Trends of the Past 20 Years in the Chemistry of Odorants

This review is the sequel to the 2000 report on the recent advances in the chemistry of odorants and it summarizes the developments in fragrance chemistry over the past 20 years. Following the olfactory spectrum set out in that report, trendsetting so‐called captive odorants (patent‐protected ingredients unavailable to the market) are presented according to the main odor families: “fruity”, “marine”, “green”, “floral”, “spicy”, “woody”, “amber”, and “musky”. The design of odorants, their chemical synthesis, and their use in modern perfumery are illustrated with prominent examples. Featured are new fruity odorants that provide signature in the top note, as well as precursor technology. In the green domain, focus is on leafy notes and green pear. New benzodioxepines and benzodioxoles have modernized the marine family and required a revision of the existing olfactophore models. The replacement of Lilial and Lyral kept the industry busy in the floral domain with a plethora of new “muguets”. There was continued activity in the domain of rose odorants, especially in the area of rose ketones. Biotechnology became significant, for example, with Clearwood and Ambrofix, and the principal odorants of vetiver oil in the woody family have been found. Fourth and fifth families of musk odorants were also discovered and populated. Thus, new avenues for further explorations into fragrance chemistry have been opened.     

Diffusion of Gold Nanoparticles in Inverse Opals Probed by Heterodyne Dynamic Light Scattering

The diffusive behavior of nanoparticles inside porous materials is attracting a lot of interest in the context of understanding, modeling, and optimization of many technical processes. A very powerful technique for characterizing the diffusive behavior of particles in free media is dynamic light scattering (DLS). The applicability of the method in porous media is considered, however, to be rather difficult due to the presence of multiple sources of scattering. In contrast to most of the previous approaches, the DLS method was applied without ensuring matching refractive indices of solvent and porous matrix in the present study. To test the capabilities of the method, the diffusion of spherical gold nanoparticles within the interconnected, periodic nanopores of inverse opals was analyzed. Despite the complexity of this system, which involves many interfaces and different refractive indices, a clear signal related to the motion of particles inside the porous media was obtained. As expected, the diffusive process inside the porous sample slowed down compared to the particle diffusion in free media. The obtained effective diffusion coefficients were found to be wave vector-dependent. They increased linearly with increasing spatial extension of the probed particle concentration fluctuations. On average, the slowing-down factor measured in this work agrees within combined uncertainties with literature data.

     

Pump−probe experiments at the TEMPO beamline using the low‐α operation mode of Synchrotron SOLEIL

The SOLEIL synchrotron radiation source is regularly operated in special filling modes dedicated to pump–probe experiments. Among others, the low‐α mode operation is characterized by shorter pulse duration and represents the natural bridge between 50 ps synchrotron pulses and femtosecond experiments. Here, the capabilities in low‐α mode of the experimental set‐ups developed at the TEMPO beamline to perform pump–probe experiments with soft X‐rays based on photoelectron or photon detection are presented. A 282 kHz repetition‐rate femtosecond laser is synchronized with the synchrotron radiation time structure to induce fast electronic and/or magnetic excitations. Detection is performed using a two‐dimensional space resolution plus time resolution detector based on microchannel plates equipped with a delay line. Results of time‐resolved photoelectron spectroscopy, circular dichroism and magnetic scattering experiments are reported, and their respective advantages and limitations in the framework of high‐time‐resolution pump–probe experiments compared and discussed.     

Heavy flags undergo spontaneous oscillations in flowing water

By immersing a compliant yet self-supporting sheet into flowing water, we study a heavy, streamlined, and elastic body interacting with a fluid. We find that above a critical flow velocity a sheet aligned with the flow begins to flap with a Strouhal frequency consistent with animal locomotion. This transition is subcritical. Our results agree qualitatively with a simple fluid dynamical model that predicts linear instability at a critical flow speed. Both experiment and theory emphasize the importance of body inertia in overcoming the stabilizing effects of finite rigidity and fluid drag.