Aromaticity and electronic delocalization in all-metal clusters with single, double, and triple aromatic character

A series of monocyclic planar inorganic compounds with single, double, and triple (anti)aromatic character has been studied. The electron delocalization and aromaticity of these compounds have been assessed by means of two-center and multicenter electronic delocalization indices and their ??-, ??-, and ??-components. Results show that these indices are excellent predictors of the ??-, ??-, and ??-aromatic character of all-metal and semimetal clusters.     

Investigation of high frequency noise generation in the near-nozzle region of a jet using large eddy simulation

This paper reports on the simulation of the near-nozzle region of an isothermal Mach 0.6 jet at a Reynolds number of 100,000 exhausting from a round nozzle geometry. The flow inside the nozzle and the free jet outside the nozzle are computed simultaneously by a high-order accurate, multi-block, large eddy simulation (LES) code with overset grid capability. The total number of grid points at which the governing equations are solved is about 50 million. The main emphasis of the simulation is to capture the high frequency noise generation that takes place in the shear layers of the jet within the first few diameters downstream of the nozzle exit. Although we have attempted to generate fully turbulent boundary layers inside the nozzle by means of a special turbulent inflow generation procedure, an analysis of the simulation results supports the fact that the state of the nozzle exit boundary layer should be characterized as transitional rather than fully turbulent. This is believed to be most likely due to imperfections in the inflow generation method. Details of the computational methodology are presented together with an analysis of the simulation results. A comparison of the far field noise spectrum in the sideline direction with experimental data at similar flow conditions is also carried out. Additional noise generation due to vortex pairing in the region immediately downstream of the nozzle exit is also observed. In a second simulation, the effect of the nozzle exit boundary layer thickness on the vortex pairing Strouhal frequency (based on nozzle diameter) and its harmonics is demonstrated. The limitations and deficiencies of the present study are identified and discussed. We hope that the lessons learned in this study will help guide future research activities towards resolving the pending issues identified in this work.

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Presented as AIAA Paper 2006-2499 at 12th AIAA/CEAS Aeroacoustics Conference, 8–10 May 2006, Cambridge, MA, USA.     

Determination of Effective Properties of MMC by Computational Homogenization

On the macrolevel Metal Matrix Composites (MMCs) resemble a homogeneous material. However, on the microlevel they show an inhomogeneous microstructure. This paper will have how heterogeneities affect the overall properties and the behaviour of a material (i. e. the effective properties). This is done using computational homogenization techniques. Finite element (FE) simulations were conducted in ABAQUS in connection with MATLAB, using material parameters for aluminium alloy AA2124 and SiC to develop a representative volume element (RVE) of the MMC AMC217xe. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enantioseparation of aromatic amino acids using CEC monolith with novel chiral selector,N‐methacryloyl‐l‐histidine methyl ester

A new type of polymethacrylate‐based monolithic column with chiral stationary phase was prepared for the enantioseparation of aromatic amino acids, namely d ,l ‐phenylalanine, d ,l ‐tyrosine, and d ,l ‐tryptophan by CEC. The monolithic column was prepared by in situ polymerization of butyl methacrylate (BMA), N‐methacryloyl‐l ‐histidine methyl ester (MAH), and ethylene dimethacrylate (EDMA) in the presence of porogens. The porogen mixture included DMF and phosphate buffer. MAH was used as a chiral selector. FTIR spectrum of the polymethacrylate‐based monolith showed that MAH was incorporated into the polymeric structure via in situ polymerization. Some experimental parameters including pH, concentration of the mobile phase, and MAH concentration with regard to the chiral CEC separation were investigated. Single enantiomers and enantiomer mixtures of the amino acids were separately injected into the monolithic column. It was observed that l ‐enantiomers of aromatic amino acids migrated before d ‐enantiomers. The reversal enantiomer migration order for tryptophan was observed upon changing of pH. Using the chiral monolithic column (100 μm id and 375 μm od), the best chiral separation was performed in 35:65% ACN/phosphate buffer (pH 8.0, 10 mM) with an applied voltage of 12 kV in CEC. SEM images showed that the chiral monolithic column has a continuous polymeric skeleton and large through‐pore structure.     

Exploring the Structural Details of Cu(I) Binding to α-Synuclein by NMR Spectroscopy

The aggregation of α-synuclein (AS) is selectively enhanced by copper in vitro, and the interaction is proposed to play a potential role in vivo. In this work, we report the structural, residue-specific characterization of Cu(I) binding to AS and demonstrate that the protein is able to bind Cu(I) with relatively high affinity in a coordination environment that involves the participation of Met1 and Met5 residues. This knowledge is a key to understanding the structural-aggregation basis of the copper-catalyzed oxidation of AS.     

First Highly Efficient and Photostable E and C Derivatives of 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) as Dye Lasers in the Liquid Phase,Thin Films,and Solid‐State Rods

A new library of E‐ and C‐4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives has been synthesized through a straightforward protocol from commercially available BODIPY complexes, and a systematic study of the photophysical properties and laser behavior related to the electronic properties of the B‐substituent group (alkynyl, cyano, vinyl, aryl, and alkyl) has been carried out. The replacement of fluorine atoms by electron‐withdrawing groups enhances the fluorescence response of the dye, whereas electron‐donor groups diminish the fluorescence efficiency. As a consequence, these compounds exhibit enhanced laser action with respect to their parent dyes, both in liquid solution and in the solid phase, with lasing efficiencies under transversal pumping up to 73 % in liquid solution and 53 % in a solid matrix. The new dyes also showed enhanced photostability. In a solid matrix, the derivative of commercial dye PM597 that incorporated cyano groups at the boron center exhibited a very high lasing stability, with the laser emission remaining at the initial level after 100 000 pump pulses in the same position of the sample at a 10 Hz repetition rate. Distributed feedback laser emission was demonstrated with organic films that incorporated parent dye PM597 and its cyano derivative. The films were deposited onto quartz substrates engraved with appropriate periodical structures. The C derivative exhibited a laser threshold lower than that of the parent dye as well as lasing intensities up to three orders of magnitude higher.     

X-ray investigations of Langmuir-Blodgett multilayer films of side-chain liquid crystal copolymers

X-ray reflectivity studies on Langmuir-Blodgett multilayer films of side-chain liquid crystal polymers are reported. The films have a high degree of lamellar order. The layer periodicity is independent of the type of monolayer deposition, implying a reorientation of the side group mesogens following the deposition process. X-ray reflectivity from thin films displays subsidiary maxima permitting a quantitative measure of the change in side-chain density between multilayer and monolayer. A unit cell density profile is calculated for thick films assuming a symmetric unit cell.     

Fixed points of non-Newtonian contraction mappings on non-Newtonian metric spaces

The study of non-Newtonian calculi was started in 1972 by Grossman and Katz. These calculi provide an alternative to the classical calculus and they include the geometric, anageometric and bigeometric calculi, etc. Recently, Çakmak and Ba?ar (2002) have studied the concept of non-Newtonian metric. Also they have given the triangle and Minkowski’s inequalities in the sense of non-Newtonian calculus. In this paper, we introduce a fixed point theory by defining some topological structures of the relevant non-Newtonian metric space.     

Site-specific interactions of Cu(II) with alpha and beta-synuclein: bridging the molecular gap between metal binding and aggregation

The aggregation of alpha-synuclein (AS) is a critical step in the etiology of Parkinson's disease (PD) and other neurodegenerative synucleinopathies. Protein-metal interactions play a critical role in AS aggregation and might represent the link between the pathological processes of protein aggregation and oxidative damage. Our previous studies established a hierarchy in AS-metal ion interactions, where Cu(II) binds specifically to the protein and triggers its aggregation under conditions that might be relevant for the development of PD. In this work, we have addressed unresolved structural details related to the binding specificity of Cu(II) through the design of site-directed and domain-truncated mutants of AS and by the characterization of the metal-binding features of its natural homologue beta-synuclein (BS). The structural properties of the Cu(II) complexes were determined by the combined application of nuclear magnetic resonance, electron paramagnetic resonance, UV-vis, circular dichroism spectroscopy, and matrix-assisted laser desorption ionization mass spectrometry (MALDI MS). Two independent, noninteracting copper-binding sites with significantly different affinities for the metal ion were detected in the N-terminal regions of AS and BS. MALDI MS provided unique evidence for the direct involvement of Met1 as the primary anchoring residue for Cu(II) in both proteins. Comparative spectroscopic analysis of the two proteins allowed us to deconvolute the Cu(II) binding modes and unequivocally assign the higher-affinity site to the N-terminal amino group of Met1 and the lower-affinity site to the imidazol ring of the sole His residue. Through the use of competitive chelators, the affinity of the first equivalent of bound Cu(II) was accurately determined to be in the submicromolar range for both AS and BS. Our results prove that Cu(II) binding in the C-terminal region of synucleins represents a nonspecific, very low affinity process. These new insights into the bioinorganic chemistry of PD are central to an understanding of the role of Cu(II) in the fibrillization process of AS and have implications for the molecular mechanism by which BS might inhibit AS amyloid assembly.     

Core-shell nanoparticles: characterization and study of their use for the encapsulation of hydrophobic fluorescent dyes

Core-shell nanocapsules intended to be used as drug scavengers were prepared using a surfactant mixture containing octadecyltrimethoxysilane (OTMS) as a reactive amphiphile, to form spherical templates. A siloxane shell was grown on the surface of the templates by reacting tetramethoxysilane (TMOS) with the silanol groups obtained after the hydrolysis and condensation of OTMS. Dynamic light scattering (DLS) showed that particles with diameters in the range of 100-200 nm were obtained, with core and shell sizes controlled by varying component compositions. Atomic force microscopy (AFM) was used to study the effect of the silica coating of the templates on their robustness after deposition on a substrate. Subsequently, we present studies on the encapsulation of two hydrophobic fluorescent dyes, which are sensors of polarity and rigidity. Steady-state fluorescence spectroscopy was used to examine the fluorescence response of the dyes before and after shell growth. Changes in the emission of the encapsulated dyes were related to changes in the polarity and rigidity of the microenvironment where the dyes were located and correlated to the AFM results. Finally, dye-free core-shell particles were used to sequester the dyes from aqueous suspensions. Fluorescence of the sequestered species was compared to the dye-loaded particles to determine the final fate of the fluorophores in the nanoparticles.