Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands

Tandem C?H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere C?H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.     

Experimental and Theoretical Investigation of the First‐Order Hyperpolarizability of Octupolar Merocyanine Dyes

Hyper‐Rayleigh scattering experiments and quantum chemical calculations are combined to investigate the second‐order nonlinear optical responses of a series of three‐arm merocyanine derivatives. They exhibit an octupolar hyperpolarizability response with lower amplitude than crystal violet due to a lower extent of the photoinduced charge transfer and reduced bond length alternation. Strong effects on the second‐order optical response measured close to the two‐photon absorption level are clearly evidenced; for example, the effective measured polarization ratio deviates below the ideal octupolar value of 3/2 even at very low excitation power. These effects are attributed to two‐photon absorption resonance, which we believe modifies dynamically the population of the ground state versus that of the excited state.     

Applying Text Analytics for Studying Research Trends in Dependability

The dependability of systems and networks has been the target of research for many years now. In the 1970s, what is now known as the top conference on dependability—The IEEE/IFIP International Conference on Dependable Systems and Networks (DSN)—emerged gathering international researchers and sparking the interest of the scientific community. Although it started in niche systems, nowadays dependability is viewed as highly important in most computer systems. The goal of this work is to analyze the research published in the proceedings of well-established dependability conferences (i.e., DSN, International Symposium on Software Reliability Engineering (ISSRE), International Symposium on Reliable Distributed Systems (SRDS), European Dependable Computing Conference (EDCC), Latin-American Symposium on Dependable Computing (LADC), Pacific Rim International Symposium on Dependable Computing (PRDC)), while using Natural Language Processing (NLP) and namely the Latent Dirichlet Allocation (LDA) algorithm to identify active, collapsing, ephemeral, and new lines of research in the dependability field. Results show a strong emphasis on terms, like ‘security’, despite the general focus of the conferences in dependability and new trends that are related with ’machine learning’ and ‘blockchain’. We used the PRDC conference as a use case, which showed similarity with the overall set of conferences, although we also found specific terms, like ‘cyber-physical’, being popular at PRDC and not in the overall dataset.     

Spectroelectrochemical Investigation of TPPMn(III/II)‐Driven Liquid | Liquid | Electrode Triple Phase Boundary Anion Transfer into 4‐(3‐Phenylpropyl)‐Pyridine: ClO4−, CO3H−, Cl−, and F−

The triple phase boundary transfer of anions from the aqueous into an organic phase can be driven electrochemically here with the tetraphenylporphyrinato‐Mn(III/II) (or TPPMn) redox system in 4‐(3‐phenylpropyl)‐pyridine) (or PPP). Anions investigated are perchlorate, chloride, fluoride, and bicarbonate. The bicarbonate and fluoride transfer processes are shown to be chemically more complex compared to the perchlorate and chloride cases with UV‐vis‐spectroelectrochemical measurements indicating a combination of HCO₃^?/CO₃^2? transfer processes and association of fluoride with TPPMn(III)⁺, respectively. In situ spectroelectrochemistry is developed for ion‐transfer voltammetry into sub‐microliter organic phase regions on mesoporous ITO conducting film electrodes.     

Simplification and analysis of a model of social interaction in voting

A recently proposed model of social interaction in voting is investigated by simplifyingit down into a version that is more analytically tractable and which allows a mathematicalanalysis to be performed. This analysis clarifies the interplay of the different elementspresent in the system – social influence, heterogeneity and noise – and leads to a betterunderstanding of its properties. The origin of a regime of bistability is identified. Theinsight gained in this way gives further intuition into the behaviour of the originalmodel.     

Imaging the neural circuitry and chemical control of aggressive motivation

Background  

With the advent of functional magnetic resonance imaging (fMRI) in awake animals it is possible to resolve patterns of neuronal activity across the entire brain with high spatial and temporal resolution. Synchronized changes in neuronal activity across multiple brain areas can be viewed as functional neuroanatomical circuits coordinating the thoughts, memories and emotions for particular behaviors. To this end, fMRI in conscious rats combined with 3D computational analysis was used to identifying the putative distributed neural circuit involved in aggressive motivation and how this circuit is affected by drugs that block aggressive behavior.     

Synthesis of a reaction intermediate analogue of biotin-dependent carboxylases via a selective derivatization of biotin

[formula: see text] An efficient and practical synthesis of 1, a unique reaction intermediate analogue of biotin-dependent carboxylases, is described. The synthesis features a selective acylation of the 1'-N of biotin. Target 1 inhibits the activity of the biotin carboxylase component of acetyl CoA carboxylase. It is the first known biotin-derived inhibitor of biotin carboxylase and should promote new kinetic and structural studies of the biotin-dependent carboxylases.     

Anna Johnson Pell Wheeler: Her life and work

This article describes the life, career, and research of the American mathematician Anna Johnson Pell Wheeler (1883–1966).