Registering the Amica electronic structure code in the extensible computational chemistry environment

We describe the integration and use of the Amica software package ("Atoms & Molecules In Chemical Accuracy") within the Extensible Computational Chemistry Environment (Ecce). Amica is capable of accurately solving the electronic Schrodinger equation of small atoms and molecules using terms that are linear in the interelectronic distances, r(12), on multireference level of theory, but it requires expert knowledge to configure and execute its algorithms. Ecce is a comprehensive suite of tools that support the computational chemistry research processes of computation setup, execution, and analysis through a convenient graphical user interface. Additionally, Ecce was architected with mechanisms to integrate alternative electronic structure codes. The successful integration of Amica within Ecce validates the architecture of the latter and brings the high-accuracy capabilities of Amica to a wider audience.     

Investigation of stress-velocity LSFEMs for the incompressible Navier-Stokes equations

In this contribution three mixed least-squares finite element methods (LSFEMs) for the incompressible Navier-Stokes equations are investigated with respect to accuracy and efficiency. The well-known stress-velocity-pressure formulation is the basis for two further div-grad least-squares formulations in terms of stresses and velocities (SV). Advantage of the SV formulations is a system with a smaller matrix size due to a reduction of the degrees of freedom. The least-squares finite element formulations, which are investigated in this contribution, base on the incompressible stationary Navier-Stokes equations. The first formulation under consideration is the stress-velocity-pressure formulation according to [1]. Secondly, an extended stress-velocity formulation with an additional residual is derived based on the findings in [1] and [5]. The third formulation is a pressure reduced stress-velocity formulation based on a condensation scheme. Therefore, the pressure is interpolated discontinuously, and eliminated on the discrete level without the need for any matrix inverting. The modified lid-driven cavity boundary value problem, is investigated for the Reynolds number Re = 1000 for all three formulations. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Adsorption of chlorhexidine on synthetic hydroxyapatite and in vitro biological activity

The kinetic of chlorhexidine digluconate (CHXDG) uptake from aqueous solution by hydroxyapatite (HA) was investigated by ultraviolet (UV) analysis performed in HA powder (UV-solid) after the CHX adsorption. Adsorption isotherm of chlorhexidine (CHX) uptake was modeled by a combination of Languimir and Langmuir-Freundlich mechanisms. Strong molecule-molecule interactions and positive cooperativity predominated in the surface when CHX concentration was above 8.6 μg(CHX)/mg(HA). UV-solid spectra (shape, intensity and band position) of CHX bound to HA revealed that long-range molecular structures, such as aggregates or micelles, started to be formed at low CHX concentrations (1.52 μg(CHX)/mg(HA)) and predominated at high concentrations. Grazing-incidence X-ray diffraction (GIXRD) analysis from synchrotron radiation discarded the formation of crystalline structures on HA surface or precipitation of CHX crystalline salts, as suggested in previous works. The effect of the HA/CHX association on HA in vitro bioactivity, cytotoxicity and CHX antimicrobial activity was evaluated. It was shown that CHX did not inhibit the precipitation of a poorly crystalline apatite at HA/CHX surface after soaking in simulating body fluid (SBF). Cell viability studies after exposure to extracts of HA and HA/CHX showed that both biomaterials did not present significant in vitro toxicity. Moreover, HA/CHX inhibited Enterococcus faecalis growth for up to 6 days, revealing that binding to HA did not affect antimicrobial activity of CHX and reduced bacterial adhesion. These results suggested that HA/CHX association could result in a potential adjuvant antimicrobial system for clinical use.     

A stress-velocity least-squares mixed finite element formulation for incompressible elastodynamics

In the framework of solving elastodynamic problems using a least-squares mixed finite element method (LSFEM) the implementation of a stress-velocity formulation for small strains is introduced and discussed in the present contribution. The element formulation is based on a first-order div – grad system, with the balance equation of momentum and the constitutive law as the governing equations. Application of the L₂-norm to the two residuals leads to a functional depending on stresses and velocities. Different time discretization schemes are considered, a scalar weighting is introduced and chosen in dependency of the different time discretization methods. In a numerical example the influence of the time integration method, the chosen time step width and the related weighing factor are investigated for a two-dimensional problem. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Subcellular Duplex DNA and G‐Quadruplex Interaction Profiling of a Hexagonal PtII Metallacycle

Metal‐driven self‐assembly afforded a multitude of fascinating supramolecular coordination complexes (SCCs) with applications as catalysts, host–guest, and stimuli‐responsive systems. However, the interest in the biological applications of SCCs is only starting to emerge and thorough characterization of their behavior in biological milieus is still lacking. Herein, we report on the synthesis and detailed in‐cell tracking of a Pt₂L₂ metallacycle. We show that our hexagonal supramolecule accumulates in cancer cell nuclei, exerting a distinctive blue fluorescence staining of chromatin resistant to UV photobleaching selectively in nucleolar G4‐rich regions. SCC co‐localizes with epitopes of the quadruplex‐specific antibody BG4 and replaces other well‐known G4 stabilizers. Moreover, the photophysical changes accompanying the metallacycle binding to G4s in solution (fluorescence quenching, absorption enhancement) also take place intracellularly, allowing its subcellular interaction tracking.     

Polyakov Soldering and Second-Order Frames: The Role of the Cartan Connection

The so-called ‘soldering’ procedure performed by Polyakov (Int J Math Phys A5, 833–842, 1990) for a -gauge theory is geometrically explained in terms of a Cartan connection on second-order frames of the projective space P¹. The relationship between a Cartan connection and the usual (Ehresmann) connection on a principal bundle allows to gain an appropriate insight into the derivation of the genuine ‘diffeomorphisms out of gauge transformations’ given by Polyakov himself. Unité Mixte de Recherche (UMR 6207) du CNRS et des Universités Aix-Marseille I, Aix-Marseille II et de l’Université du Sud Toulon-Var. Unité affiliée à la FRUMAM Fédération de Recherche 2291.     

Novel unsaturated sucrose ethers and their application as monomers

Novel unsaturated ethers were synthesised in good yields starting from sucrose,using a two-step mild and efficient procedure based on the Gassman method, which consists in forming a vinyl group by the elimination of ethanol from mixed acetals with trimethylsilyl trifluoromethanesulfonate in the presence of alkyl amines. Mixed acetals are readily obtained from the corresponding alcohols and ethyl vinyl ether, using an acidic catalyst. Conventional etherification involving a primary halide was also examined. The monomers thus obtained were successfully polymerised by a free radical mechanism,yielding unbranched linear and soluble polymers with pending sucrose moieties, and some of their physical properties were determined.     

Composite particles of polyethylene @ silica

Polyethylene (PE) and silica are perhaps the simplest and most common organic and inorganic polymers, respectively. We describe, for the first time, a physically interpenetrating nanocomposite between these two elementary polymers. While polymer-silica composites are well known, the nanometric physical blending of PE and silica has remained a challenge. A method for the preparation of such materials, which is based on the entrapment of dissolved PE in a polymerizing tetraethoxysilane (TEOS) system, has been developed. Specifically, the preparation of submicron particles of low-density PE@silica and high-density PE@silica is detailed, which is based on carrying out a silica sol-gel polycondensation process within emulsion droplets of TEOS dissolved PE, at elevated temperatures. The key to the successful preparation of this new composite has been the identification of a surfactant, PE-b-PEG, that is capable of stabilizing the emulsion and promoting the dissolution of the PE. A mechanism for the formation of the particles as well as their inner structure are proposed, based on a large battery of analyses, including transmission electron microscopy (TEM) and scanning electron microscopies (SEM), surface area and porosity analyses, various thermal analyses including thermal gravimetric analysis (TGA/DTA) and differential scanning calorimetry (DSC) measurements, small-angle X-ray scattering (SAXS) measurements and solid-state NMR spectroscopy.