Visible‐Light‐Driven Strain‐Increase Ring Contraction Allows the Synthesis of Cyclobutyl Boronic Esters

There are a limited number of ring‐contraction methodologies which convert readily available five‐membered rings into strained four‐membered rings. Here we report a photo‐induced radical‐mediated ring contraction of five‐membered‐ring alkenyl boronate complexes into cyclobutanes. The process involves the addition of an electrophilic radical to the electron‐rich alkenyl boronate complex, leading to an α‐boryl radical. Upon one‐electron oxidation, ring‐contractive 1,2‐metalate rearrangement occurs to give a cyclobutyl boronic ester. A range of radical precursors and vinyl boronates can be employed, and chiral cyclobutanes can be accessed with high levels of stereocontrol. The process was extended to the preparation of benzofused cyclobutenes and the versatility of the boronic ester was demonstrated by conversion to other functional groups.     

In Situ Observation of C−C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111)

The synthesis of high-value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X-ray photoelectron spectroscopy up to near-ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C−C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C−C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface.     

Synthesis of Soluble Quinacridone Photocatalysts for the Homogeneous Oxidation of Thioethers

Evaluation of quinacridone (QA) derivatives as homogeneous metal-free photocatalysts is here presented. QA derivatives were synthetized and systematically characterized, measuring their ground state and excited state redox potentials in dichloromethane (DCM) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), in order to understand how structural modifications influenced their photocatalytic properties. In particular, the effect of dicyanomethylene and nitro EWG groups was investigated, in order to develop a photocatalyst capable of promoting oxidative processes in the presence of molecular oxygen. Among the analyzed derivatives, 2,9-dinitro-N,N′-dibutylquinacridone (DNDBQA) was the one with the highest excited state reduction potential (E_red*=1.60 V in HFIP vs SCE), while N,N’-dibutylquinacridone (DBQA) showed valuable excited state redox potentials (E_red*=1.29 V; E_ox*=−1.28 V in HFIP vs SCE), making it suitable for bimodal applications in oxidative and reductive photocatalytic processes. Afterwards, the synthetized QA derivatives were examined as photocatalysts to promote the selective aerobic oxidation of thioether to sulfoxide. Promising results in thioanisole oxidation were achieved with all the QA derivatives tested as photocatalysts, in terms of yield and selectivity. Remarkably, DBQA showed the best performances, catalyzing the reaction in only 20 minutes, using 0.5 % of the photocatalyst, and showing excellent performances in the oxidation of several thioether derivatives.     

A comparison of reduced and unreduced KKT systems arising from interior point methods

This paper addresses the solution of a cardinality Boolean quadratic programming problem using three different approaches. The first transforms the original problem into six mixed-integer linear programming (MILP) formulations. The second approach takes one of the MILP formulations and relies on the specific features of an MILP solver, namely using starting incumbents, polishing, and callbacks. The last involves the direct solution of the original problem by solvers that can accomodate the nonlinear combinatorial problem. Particular emphasis is placed on the definition of the MILP reformulations and their comparison with the other approaches. The results indicate that the data of the problem has a strong influence on the performance of the different approaches, and that there are clear-cut approaches that are better for some instances of the data. A detailed analysis of the results is made to identify the most effective approaches for specific instances of the data.     

Relative stereochemistry of a diterpene from Salvia cinnabarina

The relative stereochemistry of 3,4-secoisopimara-4(18),7,15-triene-3-oic acid, a diterpenoid with antispasmodic, hypotensive and antibacterial activities isolated from Salvia cinnabarina, was determined by an X-ray diffraction analysis of a single crystal of a suitable crystalline derivative.     

Predicting the binding mode of known NCp7 inhibitors to facilitate the design of novel modulators

The HIV-1 nucleocapsid protein (NCp7) is an emerging target for antiretroviral therapy. Five hits have been reported to inhibit the NCp7-viral nucleic acids interaction at micromolar concentrations. We used two computationally refined structures of NCp7 as receptors to propose a reliable binding pose for these compounds, by means of computational methods. Theoretical binding modes are in agreement with available experimental data. Results lay the foundations for a rationale development of more effective NCp7 inhibitors.     

One-pot consecutive reactions based on the synthesis of conjugated enones by the re-catalysed meyer-schuster rearrangement

Re catalysis in one-pot reactions: An atom-economical, one-pot strategy that involves alkyne deprotonation and a subsequent rhenium(V)-catalysed Meyer-Schuster rearrangement of the alkynol to provide α,?-unsaturated enones in high yield has been developed. Subsequent in situ hydride reduction or Diels-Alder reaction of the enones provided products in good-to-high overall yields.     

Synchronization of moving chaotic agents

We consider a set of mobile agents in a two dimensional space, each one of them carrying a chaotic oscillator, and discuss the related synchronization issues under the framework of time-variant networks. In particular, we show that, as far as the time scale for the motion of the agents is much shorter than that of the associated dynamical systems, the global behavior can be characterized by a scaled all-to-all Laplacian matrix, and the synchronization conditions depend on the agent density on the plane.     

TOLOMEO,a Novel Machine Learning Algorithm to Measure Information and Order in Correlated Networks and Predict Their State

We present ToloMEo (TOpoLogical netwOrk Maximum Entropy Optimization), a program implemented in C and Python that exploits a maximum entropy algorithm to evaluate network topological information. ToloMEo can study any system defined on a connected network where nodes can assume N discrete values by approximating the system probability distribution with a Pottz Hamiltonian on a graph. The software computes entropy through a thermodynamic integration from the mean-field solution to the final distribution. The nature of the algorithm guarantees that the evaluated entropy is variational (i.e., it always provides an upper bound to the exact entropy). The program also performs machine learning, inferring the system’s behavior providing the probability of unknown states of the network. These features make our method very general and applicable to a broad class of problems. Here, we focus on three different cases of study: (i) an agent-based model of a minimal ecosystem defined on a square lattice, where we show how topological entropy captures a crossover between hunting behaviors; (ii) an example of image processing, where starting from discretized pictures of cell populations we extract information about the ordering and interactions between cell types and reconstruct the most likely positions of cells when data are missing; and (iii) an application to recurrent neural networks, in which we measure the information stored in different realizations of the Hopfield model, extending our method to describe dynamical out-of-equilibrium processes.