Ynamides: Versatile Tools in Organic Synthesis

Ynamides display an exceptionally fine balance between stability and reactivity. They also offer unique and multiple opportunities for the inclusion of nitrogen‐based functionalities into organic molecules, and are emerging as especially useful and versatile building blocks for organic synthesis. Recent breakthroughs in the preparation of these substrates have revitalized interest in nitrogen‐substituted alkynes, and the beginning of the 21st century has witnessed an ever‐increasing number of publications reporting the development of new reactions or synthetic sequences starting from ynamides. This Review highlights major developments in this area.     

Normal-mode-vortex interactions

Standing surface waves that interact with a confined, vertical, vorticity field with zero net circulation are studied both analytically and experimentally. The surface waves are generated by vertical vibration, and constant vorticity injection is achieved by a rotating disk flush mounted in the cell. Experimental results are indicative of a local wave-vortex interaction (no dislocation), and a simple theoretical model is able to explain them in quantitative detail.     

The Tausk Controversy on the Foundations of Quantum Mechanics: Physics, Philosophy, and Politics

In 1966 the Brazilian physicist Klaus Tausk (b. 1927) circulated a preprint from the International Centre for Theoretical Physics in Trieste, Italy, criticizing Adriana Daneri,Angelo Loinger,and Giovanni Maria Prosperi’s theory of 1962 on the measurement problem in quantum mechanics. A heated controversy ensued between two opposing camps within the orthodox interpretation of quantum theory, represented by Léon Rosenfeld and Eugene P.Wigner. The controversy went well beyond the strictly scientific issues, however, reflecting philosophical and political commitments within the context of the Cold War, the relationship between science in developed and Third World countries, the importance of social skills, and personal idiosyncrasies.     

Hopf group-coalgebras

We study algebraic properties of Hopf group-coalgebras, recently introduced by Turaev. We show the existence of integrals and traces for such coalgebras, and we generalize the main properties of quasitriangular and ribbon Hopf algebras to the setting of Hopf group-coalgebras.     

Action du N-bromosuccinimide sur les dioxolannes en série bicyclo [2.2.1 ]heptanique. Limitation des transpositions de wagner-meerwein

Vicinal benzoyloxy-trans-bicyclo [2.2.1] heptanic bromhydrins, otherwise difficult to obtain are formed from N-bromosuccinimide and norbornanes bearing a 2-aryl-1,3 dioxolane skeleton. The greater stability of the intermediate dioxolenium ion reduces the tendency towards both Wagner-Meerwein rearrangement and neighbouring group participation by chlorine, processes usually observed when a less stable intermediate is involved. Nevertheless, methoxycarbonyl neighbouring group participation and Wagner Meerwein rearrangment occur in methoxycarbonylbicyclo [2.2.1]heptane and in a bornanic compound respectively.     

Huge fluctuations in weight measurements at the bottom of a two-dimensional vertical sheet of grains

Weight measurements at the bottom of a quasi-2D vertical sheet of static cohesionless grains are carried out. The grains are held between two coaxial cylinders. This peculiar setup allows us to set either periodic or fixed lateral boundary conditions. Huge relative fluctuations in weight measurements appear in case of fixed lateral walls. This may be related to some indetermination in the mobilization state of friction forces on lateral walls. This argument would hold for any piling, but would lead to huge fluctuations in 2D systems only, because of averaging effects in 3D.     

Optical microrheology using rotating laser-trapped particles

We demonstrate an optical system that can apply and accurately measure the torque exerted by the trapping beam on a rotating birefringent probe particle. This allows the viscosity and surface effects within liquid media to be measured quantitatively on a micron-size scale using a trapped rotating spherical probe particle. We use the system to measure the viscosity inside a prototype cellular structure.     

General one-pot, three-step methodology leading to an extended class of N-heterocyclic cations: spontaneous nucleophilic addition, cyclization, and hydride loss

A new class of phenanthridinium derivative has been isolated from the reaction of 2-bromoethyl-phenanthridinium bromide with a range of primary amines in excellent yields. The reaction pathway is unprecedented and proceeds via three cascade steps: nucleophilic attack of a primary amine on the iminium moiety of a heteroaromatic ring system and cyclization to form a five-membered ring, followed by hydride loss to yield a rearomatized dihydro-1H-imidazo[1,2-f]phenanthridinium derivative. A range of NMR phase transfer experiments were carried out to elucidate the mechanistic pathway, and the methodology has been further developed by means of a biphasic system using N-bromosuccinimide as a co-oxidizing agent. The method has also been extended to other N-heterocyclic cation derivatives such as quinolinium and quinazolinium.     

Filtered optical feedback induced frequency dynamics in semiconductor lasers

We demonstrate experimentally and numerically that, by spectrally filtering the delayed optical feedback into a semiconductor laser, one can elicit novel dynamics in the frequency of the laser output light on a time scale that is set by the delay time of the feedback. In particular, we show that through a judicious choice of the filter bandwidth, and its frequency relative to that of the laser, one can produce controlled oscillations in the frequency of light from the laser.     

Adsorption of cobalt ions on the "electrolytic solution/gamma-alumina" interface studied by diffuse reflectance spectroscopy (DRS)

Diffuse reflectance spectroscopy was used for the first time to investigate the adsorption of the [Co(H2O)6]2+ ions on the interface developed between the surface of the gamma-alumina particles and the electrolytic aqueous solutions used for the preparation of cobalt-supported gamma-alumina catalysts by equilibrium deposition filtration. The formation of inner-sphere Co(II) surface complexes in which Co(II) is in octahedral symmetry was confirmed. A deconvolution peak centered at approximately 585 nm was attributed to the exchange of one aqua ligand with one AlxOHy (x = 1, 2, or 3; y = 0 or 1) negatively charged surface group resulting in the formation of mononuclear monosubstituted inner-sphere Co(II) complexes at a Co(II) surface concentration equal to 0.02 micromol of Co(II)/m2. It was inferred that as the surface Co(II) concentration increases the formation of disubstituted and/or trisubstituted surface complexes is favored with respect to the formation of monosubstituted Co(II) surface complexes. A deconvolution peak centered at approximately 640 nm was attributed to the exchange of one or more aqua ligands with bridging hydroxo ligands (Co-O-H). The relative magnitude of this peak increases with the Co(II) surface concentration, reflecting the increasing formation of binuclear, oligonuclear, and multinuclear Co(II) surface complexes and then the formation of the Co(II) surface precipitate.