Intracellular Ruthenium‐Promoted (2+2+2) Cycloadditions

Metal‐mediated intracellular reactions are becoming invaluable tools in chemical and cell biology, and hold promise for strongly impacting the field of biomedicine. Most of the reactions reported so far involve either uncaging or redox processes. Demonstrated here for the first time is the viability of performing multicomponent alkyne cycloaromatizations inside live mammalian cells using ruthenium catalysts. Both fully intramolecular and intermolecular cycloadditions of diynes with alkynes are feasible, the latter providing an intracellular synthesis of appealing anthraquinones. The power of the approach is further demonstrated by generating anthraquinone AIEgens (AIE=aggregation induced emission) that otherwise do not go inside cells, and by modifying the intracellular distribution of the products by simply varying the type of ruthenium complex.     

Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases

The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed.     

Synthesis of Enantiomeric Pure E-Nor-15-azayohimbines

A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component.     

Influence of surface heterogeneity on hydrogen adsorption on activated carbons

This study presents an experimental and theoretical analysis of the effect of surface heterogeneity on the capacity of 20 commercial activated carbons to adsorb hydrogen at 77 and 258 K and for maximum pressures of 20 bar. Some of the samples have been subjected to surface modification by impregnation or by surface oxidation prior to the hydrogen adsorption measurements. All the activated carbons have been analyzed by N₂ adsorption at 77 K using the thermodynamic isotherm presented in a previous study. The hydrogen adsorption capacity of the activated carbons has been well correlated to the micropore volume and the characteristic m₂ parameter of the thermodynamic isotherm accounting for the energy heterogeneity of the material. On the basis of the model presented here, we discuss how surface heterogeneity, in addition to the adsorption strength, might affect the ability of activated carbons and related materials to adsorb hydrogen.     

Electromechanical phase transition in hexacyanometallate nanostructure (Prussian Blue)

This paper demonstrates the importance of the structural changeover in controlling the physical-chemical properties of hexacyanometalate-like materials (Prussian Blue). A meticulous in situ study of compositional variations using electroacoustic impedance techniques associated to electrogravimetric techniques in hexacyanoferrates containing K+ alkali metals reveals the existence of a nanostructural changeover coupled to a change of the magnetic properties of these electromagnetic materials. In the same way, the electroacoustic impedance techniques can be useful both in the understanding and in the in situ monitoring of the structural changeovers and the magnetic behavior of all kinds of materials.     

Coloring planar graphs in parallel

We present NC algorithms for vertex and edge coloring planar graphs. The vertex coloring algorithm 5 colors any planar graph, and the edge coloring algorithm Δ edge colors planar graphs with Δ ≥ 23 (and Δ + 1 edge colors planar graphs with Δ < 23), where Δ is the maximum degree in the graph.     

Single Higgs-boson production at a photon-photon collider: General 2HDM versus MSSM

We revisit the production of a single Higgs boson from direct γγ-scattering at a photon collider. We compute the total cross-section σ(γγ→h) (for h=h⁰,H⁰,A⁰), and the strength of the effective gh⁰γγ coupling normalized to the Standard Model (SM), for both the general Two-Higgs-Doublet Model (2HDM) and the Minimal Supersymmetric Standard Model (MSSM). In both cases the predicted production rates for the CP-even (odd) states render up to 10⁴ (10³) events per 500 fb⁻¹ of integrated luminosity, in full consistency with all the theoretical and phenomenological constraints. Depending on the channel the maximum rates can be larger or smaller than the SM expectations, but in most of the parameter space they should be well measurable. We analyze how these departures depend on the dynamics underlying each of the models, supersymmetric and non-supersymmetric, and highlight the possible distinctive phenomenological signatures. We demonstrate that this process could be extremely useful to discern non-supersymmetric Higgs bosons from supersymmetric ones. Furthermore, in the MSSM case, we show that γγ-physics could decisively help to overcome the serious impasse afflicting Higgs boson physics at the infamous “LHC wedge”.     

Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations

Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]₂^2? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]₂^2? dimers form dissociated ion pairs with the NBu₄⁺ counterions, and their first solvation shell comprises approximately 20 CH₂Cl₂ molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE ^{. ?} in solution at 175 K is ?5.5 kcal mol^?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.