Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

Measuring technical and environmental efficiency in a state-contingent technology

Most developed countries support farming activities through policies that are tailored to meet their specific social, economic and environmental objectives. Economic and environmental efficiency have recently become relevant targets of most of these policies, whose sound implementation can be enhanced by monitoring farm performance from a multidimensional perspective. This paper proposes farm-level technical and environmental efficiency measures that recognize the stochastic conditions in which production takes place. A state-contingent framework is used to model production uncertainty. An implementable representation of the technology is developed using data envelopment analysis. The application focuses on a sample of Catalan arable crop farms. Results suggest that technical efficiency is slightly lower in bad than in good growing conditions. Nitrogen pollution can decrease substantially more under good than bad growing conditions.     

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.     

Spectral analysis of Pk Finite Element matrices in the case of Friedrichs–Keller triangulations via Generalized Locally Toeplitz technology

In the present article, we consider a class of elliptic partial differential equations with Dirichlet boundary conditions and where the operator is div(?a( x )?·), with a continuous and positive over $\stackrel{￣}{\mathrm{\Omega }}$, Ω being an open and bounded subset of ${\mathbb{R}}^d$, d≥1. For the numerical approximation, we consider the classical ${\mathbb{P}}_k$ Finite Elements, in the case of Friedrichs–Keller triangulations, leading, as usual, to sequences of matrices of increasing size. The new results concern the spectral analysis of the resulting matrix‐sequences in the direction of the global distribution in the Weyl sense, with a concise overview on localization, clustering, extremal eigenvalues, and asymptotic conditioning. We study in detail the case of constant coefficients on Ω=(0,1)² and we give a brief account in the more involved case of variable coefficients and more general domains. Tools are drawn from the Toeplitz technology and from the rather new theory of Generalized Locally Toeplitz sequences. Numerical results are shown for a practical evidence of the theoretical findings.     

From curing kinetics to network structure: A novel approach to the modeling of the network buildup of epoxy–anhydride thermosets

The curing kinetics and network buildup during curing of epoxy–anhydride formulations using tertiary amines as initiators are reviewed in this work. A mechanism‐based kinetic and structural model has been defined, showing better prediction capabilities than previous living polymerization and simple regeneration models. The curing kinetics have been analyzed using differential scanning calorimetry (DSC), and the gelation during curing has been determined by combined thermomechanical analysis and DSC. The effect of initiator content and epoxy equivalent weight are taken into account. The network buildup has been modeled using a stochastic network buildup model based on the random combination of primary chains generated by the kinetic model. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 61–75