Visible-Light Controlled Divergent Catalysis Using a Bench-Stable Cobalt(I) Hydride Complex

While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/-off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi-dimensional catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employed transformations, olefin migration and hydroboration, with visible light as the trigger.     

Generalization of Heron’s and Brahmagupta’s equalities to any cyclic polygon

Aequationes mathematicae - It is well known that Heron’s equality provides an explicit formula for the area of a triangle, as a symmetric function of the lengths of its edges. It has been...     

Comparison of Different Reweighting Approaches for the Calculation of Conformational Variability of Macromolecules from Molecular Simulations

Conformational variability and heterogeneity are crucial determinants of the function of biological macromolecules. The possibility of accessing this information experimentally suffers from severe under-determination of the problem, since there are a few experimental observables to be accounted for by a (potentially) infinite number of available conformational states. Several computational methods have been proposed over the years in order to circumvent this theoretically insurmountable obstacle. A large share of these strategies is based on reweighting an initial conformational ensemble which arises from, for example, molecular simulations of different qualities and levels of theory. In this work, we compare the outcome of three reweighting approaches based on radically different views of the conformational heterogeneity problem, namely Maximum Entropy, Maximum Parsimony and Maximum Occurrence, and we do so using the same experimental data. In this comparison we find both expected as well as unexpected similarities.     

Reaction of singlet oxygen with thioanisole in ionic liquid-acetonitrile binary mixtures

A study of the reaction of thioanisole with singlet oxygen in different ionic liquid-acetonitrile binary mixtures has shown that ILs are able to accelerate the thioanisole sulfoxidation when used as additives. With imidazolium ILs, the maximum efficiency is reached at x(IL) ～ 0.1-0.2, whereas for the pyrrolidinium IL a plateau is reached. These results are discussed in terms of the ILs' tendency to form ionic aggregates and of differences in sulfoxidation reaction mechanism.     

Direct assembly of polyarenes via C-C coupling Using PIFA/BF3·Et2O

Direct oxidative Kita-type coupling between naphthalene and substituted benzenes was found to proceed via four-component coupling, leading to a linear tetraarene with a binaphthalene core. The methodology was extendable to the coupling of unfunctionalized 1,1'-binaphthalene with mesitylene to give a linear hexaarene product in a remarkably chemoselective manner in 87% yield. The method represents an attractive alternative to the traditional syntheses of related oligonaphthalene products via a sequence of metal-catalyzed cross-coupling steps.     

Separation of variables for integrable spin–boson models

We formulate the functional Bethe ansatz for bosonic (infinite dimensional) representations of the Yang–Baxter algebra. The main deviation from the standard approach consists in a half infinite Sklyanin lattice made of the eigenvalues of the operator zeros of the Bethe annihilation operator. By a separation of variables, functional TQ-equations are obtained for this half infinite lattice. They provide valuable information about the spectrum of a given Hamiltonian model. We apply this procedure to integrable spin–boson models subject to both twisted and open boundary conditions. In the case of general twisted and certain open boundary conditions polynomial solutions to these TQ-equations are found and we compute the spectrum of both the full transfer matrix and its quasi-classical limit. For generic open boundaries we present a two-parameter family of Bethe equations, derived from TQ-equations that are compatible with polynomial solutions for Q. A connection of these parameters to the boundary fields is still missing.     

A nonperturbative foundation of the Euclidean–Minkowskian duality of Wilson-loop correlation functions

In this Letter we discuss the analyticity properties of the Wilson-loop correlation functions relevant to the problem of soft high-energy scattering, directly at the level of the functional integral, in a genuinely nonperturbative way. The strategy is to start from the Euclidean theory and to push the dependence on the relevant variables θ (the relative angle between the loops) and T (the half-length of the loops) into the action by means of a field and coordinate transformation, and then to allow them to take complex values. In particular, we determine the analyticity domain of the relevant Euclidean correlation function, and we show that the corresponding Minkowskian quantity is recovered with the usual double analytic continuation in θ and T inside this domain. The formal manipulations of the functional integral are justified making use of a lattice regularisation. The new rescaled action so derived could also be used directly to get new insights (from first principles) in the problem of soft high-energy scattering.     

Monoliths of aligned silica-polypeptide hexagonal platelets

Water soluble alpha-helical polypeptides were used to prepare silica coated hexagonal single crystal platelets in concentrated solutions. To our knowledge, there is no other instance where polymer single crystals, typically formed under high dilution, can be grown in a bulk material. This unprecedented self-assembly process relies on complex cooperative interactions where silica condensation mediates the growth of polypeptide crystals, which in turn template silica overgrowth. The helices were also used to align samples giving monoliths composed of highly oriented layers of platelets. Overall, this procedure allows preparation of composites with good structural order and complexity via a simple biomimetic process.