One- and two-photon absorption and emission properties of a Zn(II) chemosensor

This paper presents the synthesis and two photon-induced absorption (TPA) properties of a functionalized distyrylbenzene (DSB) 1 containing a tetra-azacyclododecane (cyclen) receptor for Zn(II). The influence of Zn(II) on one- and two-photon absorption characteristics of 1 has been investigated in dimethyl sulfoxide. The experiments show that the TPA action spectrum of uncomplexed 1, at 750 nm employing nanosecond-long excitation pulses, is 5 times more intense than that of the complexed form. This moderate contrast between the bound and unbound species confirms, however, the potential of this design scheme for the development of molecular structures with enhanced sensitivity and contrast to be used as Zn(II) sensors through TPA-induced fluorescence microscopy.     

Comparing some operational approaches to the limit of detection

The limit of detection is one of the fundamental metrological characteristics of any chemical measurement systems but, even now, it is a highly controversial matter because of the existing differences in terminology, formulations and understanding. Even when limiting the analysis to those operational approaches that, because of their simplicity, are often suggested by the guidelines of some international bodies, the available approaches can return appreciably different estimates. In this paper, the matter is critically reconsidered, and the different approaches compared with the aid of some case studies.     

Downside risk in multiperiod tracking error models

The recent crisis made it evident that replicating the performance of a benchmark is not a sufficient goal to meet the expectations of usually risk-averse investors. The manager should also consider that the investors are seeking downside protection when the benchmark performs poorly and thus they should integrate a form of downside risk control. We propose a multiperiod double tracking error portfolio model which combines these two goals and provides enough flexibility. In particular, the control of the downside risk is carried out through the presence of a floor benchmark with respect to which we can accept different levels of shortfall. The choice of a proper measure for downside risk leads to different problem formulations and investment strategies which can reflect different attitudes towards risk. The proposed model is tested through a set of out-of-sample rolling simulations in different market conditions.     

A multi-scale enriched model for the analysis of masonry panels

A multi-scale model for the structural analysis of the in-plane response of masonry panels, characterized by periodic arrangement of bricks and mortar, is presented. The model is based on the use of two scales: at the macroscopic level the Cosserat micropolar continuum is adopted, while at the microscopic scale the classical Cauchy medium is employed. A nonlinear constitutive law is introduced at the microscopic level, which includes damage, friction, crushing and unilateral contact effects for the mortar joints. The nonlinear homogenization is performed employing the Transformation Field Analysis (TFA) technique, properly extended to the macroscopic Cosserat continuum. A numerical procedure is developed and implemented in a Finite Element (FE) code in order to analyze some interesting structural problems. In particular, four numerical applications are presented: the first one analyzes the response of the masonry Representative Volume Element (RVE) subjected to a cyclic loading history; in the other three applications, a comparison between the numerically evaluated response and the micromechanical or experimental one is performed for some masonry panels.     

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

The new amphiphilic peptide 1 is composed of alternating cyclohexyl side chains and guanidiniocarbonyl pyrrole (GCP) groups. In contrast to analogue 2 , which contains lysine instead of the GCP groups and only exists as a random coil owing to charge repulsion, peptide 1 forms a stable β‐sheet at neutral pH in aqueous medium. The weakly basic GCP groups (pK_a≈7) are key for secondary structure formation as they stabilize the β‐sheet through mutual interactions (formation of a “GCP zipper”). The β‐sheets further aggregate into left‐handed helically twisted fibers. However, β‐sheet formation is completely reversible as a function of pH. At low pH (ca. 4), peptide 1 is unstructured (random coil) as all GCP units are protonated. Only round colloidal particles are observed. The amyloid nature of the fibers formed at neutral pH was confirmed by staining experiments with Congo Red and thioflavin T. Furthermore, at millimolar concentrations, peptide 1 forms a stable hydrogel.     

Organizational dynamic embeddedness and external shocks: The impact of financial and recession crises in strategic networks of the global pharmaceutical industry

We analyze the global pharmaceutical industry network using a unique database that covers strategic transactions (i.e., alliance, financing and acquisition collaborations) for the top 90 global pharmaceutical firms and their ego‐network partnerships totaling 4735 members during 1991–2012. The article explores insights on dynamic embeddedness analysis under network perturbations by exploring core and full networks' behavior during the global financial crisis of 2007–2008 and the subsequent global and Eurozone recessions of 2009–2012. We introduce and test literature grounded hypotheses as well as report network visualizations and nonparametric tests that reveal important discrepancies in both network types before and after the financial crisis offset. We observe that firms in core and full networks behave differently, with smaller top pharmaceutical firms of core networks particularly being affected by the crises, potentially due to a collaboration reduction with bigger top pharmaceuticals. On the other hand, big pharmaceuticals in full networks maintain their centrality position as a possible consequence of their strategic collaborations not only with other similarly sized firms but also due to their connections with subsidiaries and other private entities present in the total sample. Our results confirm the significant dynamicity reduction during financial crisis and recession periods for core and full networks, and highlight the importance that exogenous factors as well as network types play in centrality‐based dynamic longitudinal network analysis. © 2016 Wiley Periodicals, Inc. Complexity 21: 602–621, 2016     

Partially hydroxylated polycrystalline ionic oxides: a new route toward electron-rich surfaces

Charge traps at the surface of oxide materials play a fundamental role in various chemical processes, such as the activation of supported metal clusters. In this study, combining electron paramagnetic resonance with cluster model DFT calculations, we show that excess electrons at the surface of MgO, CaO, and SrO polycrystalline materials can be generated by preparing weakly hydroxylated surfaces followed by deposition of small amounts of alkali metals. The residual OH groups present on specific sites of the partially dehydroxylated surface act as stable traps for electrons donated by the alkali metal (Na in this case) which forms a Na+ ion distant from the trapped electron. This process results in the formation of thermally stable (H+)(e-) color centers at the surface of the oxide. The procedure could be of interest for the stabilization and activation of supported metal nanoparticles with potential use in catalysis.     

Guiding in the visible with "colorful" solid-core Bragg fibers

We report on the fabrication and characterization of solid-core all-polymer Bragg fibers consisting of a large-diameter polymethyl methylacrylate (PMMA) core surrounded by 50 alternating PMMA/Polystyrene (PS) polymer layers. By modifying the reflector layer thickness we illustrate that bandgap position can be adjusted at will in the visible. Moreover, such fibers are intensely colored in both the transmission and the outside reflection modes. Potential applications of such fibers are discussed.