Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.     

Essential oil from the leaves of Xylopia langsdorfiana (Annonaceae) as a possible spasmolytic agent

Xylopia langsdorfiana A. St.-Hil. &Tul. (Annonaceae) is popularly known in the northeast of Brazil as ‘pimenteira da terra’, and an essential oil (XL-OE) was extracted from its leaves. Since Xylopia species are cited in folk medicine and diterpenes from X. langsdorfiana have spasmolytic activity, this study aimed to investigate a possible spasmolytic action of XL-OE on smooth muscle models. XL-OE (243 and 729 μg/mL) showed low pharmacologic efficacy on guinea pig trachea and rat aorta and uterus. However, in guinea pig ileum, XL-OE (27–729 μg/mL) inhibited carbachol or histamine-induced phasic contractions (1 μM) in a significant and concentration-dependent manner. In addition, XL-OE (81 μg/mL) reduced fluorescence intensity in ileal myocytes stimulated by histamine, indicating a decrease in cytosolic calcium concentration, which could explain the spasmolytic activity. Thus, XL-OE proved to be a promising natural product to be used in gastrointestinal diseases acting by modulating the cytosolic calcium concentration.     

Temperature-Controlled Stereodivergent Synthesis of 2,2′-Biflavanones Promoted by Samarium Diiodide

In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments.     

MUC1 Aptamer-Capped Mesoporous Silica Nanoparticles for Navitoclax Resistance Overcoming in Triple-Negative Breast Cancer

Triple-negative breast cancer (TNBC) is the most aggressive breast cancer subtype. In the last years, navitoclax has emerged as a possible treatment for TNBC. Nevertheless, rapid navitoclax resistance onset has been observed thorough Mcl-1 overexpression. As a strategy to overcome Mcl-1-mediated resistance, herein we present a controlled drug co-delivery system based on mesoporous silica nanoparticles (MSNs) targeted to TNBC cells. The nanocarrier is loaded with navitoclax and the Mcl-1 inhibitor S63845 and capped with a MUC1-targeting aptamer ( apMUC1-MSNs(Nav/S63845) ). The apMUC1-capped nanoparticles effectively target TNBC cell lines and successfully induce apoptosis, overcoming navitoclax resistance. Moreover, navitoclax encapsulation protects platelets against apoptosis. These results point apMUC1-gated MSNs as suitable BH3 mimetics nanocarriers in the targeted treatment of MUC1-expressing TNBC.     

General decay of solutions of a wave equation with memory term and acoustic boundary condition

In this paper, the global solvability to the mixed problem involving the wave equation with memory term and acoustic boundary conditions for non‐locally reacting boundary is considered. Moreover, the general decay of the energy functionality is established by the techniques of Messaoudi. Copyright © 2016 John Wiley & Sons, Ltd.     

Heuristic solution approaches for the maximum minsum dispersion problem

The Maximum Minsum Dispersion Problem (Max-Minsum DP) is a strongly NP-Hard problem that belongs to the family of equitable dispersion problems. When dealing with dispersion, the operations research literature has focused on optimizing efficiency-based objectives while neglecting, for the most part, measures of equity. The most common efficiency-based functions are the sum of the inter-element distances or the minimum inter-element distance. Equitable dispersion problems, on the other hand, attempt to address the balance between efficiency and equity when selecting a subset of elements from a larger set. The objective of the Max-Minsum DP is to maximize the minimum aggregate dispersion among the chosen elements. We develop tabu search and GRASP solution procedures for this problem and compare them against the best in the literature. We also apply LocalSolver, a commercially available black-box optimizer, to compare our results. Our computational experiments show that we are able to establish new benchmarks in the solution of the Max-Minsum DP.     

On the convergence of a local third order shock capturing method for hyperbolic conservation laws

The Piecewise Polynomial Harmonic Method (PPHM) is a local third order accurate shock capturing method for hyperbolic conservation laws. In this paper, theoretical stability properties are presented. Using these properties, the convergence of the scheme for scalar conservation laws is obtained. A direct adaptation of these results should be used to derive the convergence of the PHM (Marquina, SIAM J. Sci. Comput. 15(4), 892–915, 1994). Finally, the method is tested in several classical problems in order to explore its numerical behavior.     

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C₆₀ and C₇₀, with remarkably large binding constants (ca. 10⁷ M⁻¹), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes.