How different are two chemical structures?

We extend the scope of a recent method for superimposing two molecules ( J. Chem. Phys. 2009, 131, 124126-1-124126-10 ) to include the identification of chiral structures. This methodology is tested by applying it to several organic molecules and water clusters that were subjected to geometry optimization. The accuracy of four simpler, non-superimposing approaches is then analyzed by comparing pairs of structures for argon and water clusters. The structures considered in this work were obtained by a Markovian walk in the coordinate space. First, a random geometry is generated, and then, the iterative application of a mutation operator ensures the creation of increasingly dissimilar structures. The discriminating power of the non-superimposing approaches is tested by comparing the corresponding dissimilarity measures with the root-mean-square distance obtained from the superimposing method. Finally, we showcase the application of those methods to characterize the diversity of solutions in global geometry optimization by evolutionary algorithms.     

Generation and characterization of low‐energy structures in atomic clusters

Factors relevant for controlling the structures determined in the local optimization of argon clusters are investigated. In particular, the role of volume and shape for the box where initial structures are generated is assessed. A thorough characterization of the optimization is also presented, based on a nearest‐neighbor analysis, in clusters ranging from 30 to 55 atoms. This includes the assessment of the degree of preservation of aspects of the initial randomly generated structure in the final optimized counterpart, and the correlation between optimized energy and the number of nearest neighbors and average departure from the diatomic reference distance. The usefulness of this analysis to explore the energy landscape of atomic clusters is also highlighted. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

The Role of the Eu<Superscript>3+</Superscript> Concentration on the SrMoO<Subscript>4</Subscript>:Eu Phosphor Properties: Synthesis,Characterization and Photophysical Studies

SrMoO₄ doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr_1−xEu_xMoO₄ powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO₄:Eu³⁺ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 °C for 2 h, 2θ = 27.8° (100% peak). The excitation spectra of the SrMoO₄:Eu³⁺ (λ_Em. = 614 nm) presented the characteristic band of the Eu^3 + 5L₆ transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO₄ matrix. The emission spectra of the SrMoO₄:Eu³⁺ powders (λ_Exc. = 394 and 288 nm) show the group of sharp emission bands among 523–554 nm and 578–699 nm, assigned to the ⁵D₁→⁷F_{0,1and 2} and ⁵D₀→⁷F_{0,1,2,3 and 4}, respectively. The band related to the ⁵D₀→⁷F₀ transition indicates the presence of Eu³⁺ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the ⁵D₀→⁷F₂ transition is the most intense in the emission spectra.     

Moreau–Yosida Regularization of Maximal Monotone Operators of Type (D)

We propose a Moreau–Yosida regularization for maximal monotone operators of type (D), in non-reflexive Banach spaces. It generalizes the classical Moreau–Yosida regularization as well as Brezis–Crandall–Pazy’s extension of this regularization to strictly convex (reflexive) Banach spaces with strictly convex duals. Our main results are obtained by making use of recent results by the authors on convex representations of maximal monotone operators in non-reflexive Banach spaces.     

Enhancing the superconducting transition temperature of BaSi2 by structural tuning

We present a joint experimental and theoretical study of the superconducting phase of the layered binary silicide BaSi(2). Compared with the AlB(2) structure of graphite or diboridelike superconductors, in the hexagonal structure of binary silicides the sp(3) arrangement of silicon atoms leads to corrugated sheets. Through a high-pressure synthesis procedure we are able to modify the buckling of these sheets, enhancing the superconducting transition temperature from 6 to 8.9 K when the silicon planes flatten out. By performing ab initio calculations based on density-functional theory we explain how the electronic and phonon properties are strongly affected by changes in the buckling. This mechanism is likely present in other intercalated layered superconductors, opening the way to the tuning of superconductivity through the control of internal structural parameters.     

Integrated optical temporal Fourier transformer based on a chirped Bragg grating waveguide

We experimentally demonstrate the first integrated temporal Fourier transformer based on a linearly chirped Bragg grating waveguide written in silica glass with a femtosecond laser. The operation is based on mapping the energy spectrum of the input optical signal to the output temporal waveform by making use of first-order chromatic dispersion. The device operates in reflection, has a bandwidth of 10 nm, and can be used for incident temporal waveforms as long as 20 ps. Experimental results, obtained through both temporal oscilloscope traces and Fourier transform spectral interferometry, display a successful Fourier transformation of in-phase and out-of-phase pairs of input optical pulses, and demonstrate the correct functionality of the device for both amplitude and phase of the temporal output.     

Computing economies of vertical integration,economies of scope and economies of scale using partial frontier nonparametric methods

So far, in the nonparametric literature only full frontier nonparametric methods have been applied to search for economies of scope and scale, particularly the data envelopment analysis method (DEA). However, these methods present some drawbacks that might lead to biased results. This paper proposes a methodology based on more robust partial frontier nonparametric methods to look for scope and scale economies. Through this methodology it is possible to assess the robustness of these economies, and in particular to assess the influence that extreme data or outliers might have on them. The influence of the imposition of convexity on the production set of firms was also investigated. This methodology was applied to the water utilities that operated in Portugal between 2002 and 2008. There is evidence of economies of vertical integration and economies of scale in drinking water supply utilities and in water and wastewater utilities operating mainly in the retail segment. Economies of scale were found in water and wastewater utilities operating exclusively in the wholesale, and in some of these utilities diseconomies of scope were also found. The proposed methodology also allowed us to conclude that the existence of some smaller utilities makes the minimum optimal scales go down.     

Decoding the intricate network of molecular interactions of a hyperstable engineered biocatalyst

Computational design of protein catalysts with enhanced stabilities for use in research and enzyme technologies is a challenging task. Using force-field calculations and phylogenetic analysis, we previously designed the haloalkane dehalogenase DhaA115 which contains 11 mutations that confer upon it outstanding thermostability (T_m = 73.5 °C; ΔT_m > 23 °C). An understanding of the structural basis of this hyperstabilization is required in order to develop computer algorithms and predictive tools. Here, we report X-ray structures of DhaA115 at 1.55 Å and 1.6 Å resolutions and their molecular dynamics trajectories, which unravel the intricate network of interactions that reinforce the αβα-sandwich architecture. Unexpectedly, mutations toward bulky aromatic amino acids at the protein surface triggered long-distance (∼27 Å) backbone changes due to cooperative effects. These cooperative interactions produced an unprecedented double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates to the active site, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. Despite these spatial restrictions, experimental tracing of the access tunnels using krypton derivative crystals demonstrates that transport of ligands is still effective. Our findings highlight key thermostabilization effects and provide a structural basis for designing new thermostable protein catalysts.

Illustration of cooperative thermostabilization effects of the double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site.     

Bacterial cellulose–silica organic–inorganic hybrids

Bacterial cellulose (BC) hydrated membranes present nanometric reticulated structure that can be used as a template in the preparation of new organic–inorganic hybrids. BC–silica hybrids were prepared from BC membranes and tetraethoxysilane, (TEOS) at neutral pH conditions at room temperature. Macroscopically homogeneous membranes were obtained containing up to 66 wt.% of silica spheres, 20–30 nm diameter. Scanning electron micrographs clearly show the silica spheres attached to cellulose microfibrils. By removing the cellulose, the silica spheres can be easily recovered. The new hybrids are stable up to 300 °C and display a broad emission band under UV excitation assigned to oxygen-related defects at the silica particles surface. Emission color can be tuned by changing the excitation wavelength.     

On Inexact Relative-Error Hybrid Proximal Extragradient,Forward-Backward and Tseng’s Modified Forward-Backward Methods with Inertial Effects

Set-Valued and Variational Analysis - For solving monotone inclusion problems, we propose an inertial under-relaxed version of the relative-error hybrid proximal extragradient method. We study the...