Space-time discontinuous Galerkin method for the solution of fluid-structure interaction

The paper is concerned with the application of the space-time discontinuous Galerkin method (STDGM) to the numerical solution of the interaction of a compressible flow and an elastic structure. The flow is described by the system of compressible Navier-Stokes equations written in the conservative form. They are coupled with the dynamic elasticity system of equations describing the deformation of the elastic body, induced by the aerodynamical force on the interface between the gas and the elastic structure. The domain occupied by the fluid depends on time. It is taken into account in the Navier-Stokes equations rewritten with the aid of the arbitrary Lagrangian-Eulerian (ALE) method. The resulting coupled system is discretized by the STDGM using piecewise polynomial approximations of the sought solution both in space and time. The developed method can be applied to the solution of the compressible flow for a wide range of Mach numbers and Reynolds numbers. For the simulation of elastic deformations two models are used: the linear elasticity model and the nonlinear neo-Hookean model. The main goal is to show the robustness and applicability of the method to the simulation of the air flow in a simplified model of human vocal tract and the flow induced vocal folds vibrations. It will also be shown that in this case the linear elasticity model is not adequate and it is necessary to apply the nonlinear model.     

Parametrically shaped femtosecond pulses in the nonlinear regime obtained by reverse propagation in an optical fiber

We present the experimental realization of a method to generate predetermined, arbitrary pulse shapes after transmission through an optical fiber in the nonlinear regime. The method is based on simulating the reverse propagation of the desired pulse shape in the fiber. First, linear and nonlinear parameters of a single-mode step-index fiber required for the simulation are determined. The calculated pulse shapes are then generated in a pulse shaper.     

Tale of the Breslow intermediate,a central player in N-heterocyclic carbene organocatalysis: then and now

N-Heterocyclic carbenes (NHCs) belong to the popular family of organocatalysts used in a wide range of reactions, including that for the synthesis of complex natural products and biologically active compounds. In their organocatalytic manifestation, NHCs are known to impart umpolung reactivity to aldehydes and ketones, which are then exploited in the generation of homoenolate, acyl anion, and enolate equivalents suitable for a plethora of reactions such as annulation, benzoin, Stetter, Claisen rearrangement, cycloaddition, and C–C and C–H bond functionalization reactions and so on. A common thread that runs through these NHC catalyzed reactions is the proposed involvement of an enaminol, also known as the Breslow intermediate, formed by the nucleophilic addition of an NHC to a carbonyl group of a suitable electrophile. In the emerging years of NHC catalysis, enaminol remained elusive and was largely considered a putative intermediate owing to the difficulties encountered in its isolation and characterization. However, in the last decade, synergistic efforts utilizing an array of computational and experimental techniques have helped in gaining important insights into the formation and characterization of Breslow intermediates. Computational studies have suggested that a direct 1,2-proton transfer within the initial zwitterionic intermediate, generated by the action of an NHC on the carbonyl carbon, is energetically prohibitive and hence the participation of other species capable of promoting an assisted proton transfer is more likely. The proton transfer assisted by additives (such as acids, bases, other species, or even a solvent) was found to ease the kinetics of formation of Breslow intermediates. These important details on the formation, in situ detection, isolation, and characterization of the Breslow intermediate are scattered over a series of reports spanning well over a decade, and we intend to consolidate them in this review and provide a critical assessment of these developments. Given the central role of the Breslow intermediate in organocatalytic reactions, this treatise is expected to serve as a valuable source of knowledge on the same.

Molecular insights on the formation, detection, and even isolation of the Breslow intermediate, which is the most important species in N-heterocyclic carbene (NHC) catalysis, as obtained from experimental and computational studies, are presented.     

Tamarindus indica mucilage and its acrylamide-grafted copolymer as flocculants for removal of dyes

The application of Tamarindus indica seed mucilage (Tam), a food grade polysaccharide, and its acrylamide grafted copolymer as flocculants was assessed for the first time for removal of various types of dyes from model textile wastewater containing azo, basic, and reactive dyes. Acrylamide grafted T. indica mucilage (Tam-g-PAM) was obtained by ceric ion initiated polymerization technique. A series of contact time experiments were conducted to assess the system variables such as concentrations of mucilage and dyes and pH. These flocculants reduce the dye concentration by flocculation and settling. The grafted copolymer, Tam-g-PAM showed better results for dye removal. The optimal flocculant concentration, which was required to effect flocculation, was independent of dye concentration within the range examined. Both the flocculants performed better for removal of azo dyes than for reactive and basic dyes.     

Photopolymers for Rapid Prototyping of Soluble Mold Materials and Molding of Cellular Biomaterials

To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers. These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials. Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials prepared by 3D-photoshaping.     

Scaling law of poly(ethylene oxide) chain permeation through a nanoporous wall

This paper presents a study of the permeation of poly(ethylene oxide) (PEO) chains through the nanoporous wall of hollow polymeric capsules prepared by self-assembly of polyelectrolytes. We employ the method of pulsed field gradient (PFG) NMR diffusion to distinguish chains in different sites, i.e., in the capsule interior and free chains in the dispersion, by their respective diffusion coefficient. From a variation of the observation time, the time scale of the molecular exchange between both sites and thus the permeation rate constant is extracted from a two-site exchange model. Permeation rate constants show two different regimes with a different dependence on chain length. This suggests a transition between two different mechanisms of permeation as the molecular weight is increased. In either regime, the permeation time can be described by a scaling law tau approximately N (b) , with b = (4)/ 3 for short chains and b = (1)/ 3 for long chains. We discuss these exponents, which clearly differ from the theoretical predictions for chain translocation.     

Study of the role of ceramic filler in composite gel electrolytes based on microporous polymer membranes

The presented contribution aims at reconsidering the role of filler in affecting the ionic transport in composite gel electrolytes for Li-ion cells based on microporous polymer membranes. The gels have been prepared by swelling thin PVdF/HFP membranes either with conventional liquid electrolyte or with pure propylene carbonate solvent. The membranes contained dispersed submicron-size modified silica filler added in a wide range of weight ratios. The effect of filler content on the kinetics of liquid phase absorption and evaporation from the composite membranes, as well as on the conductivity of the corresponding gel electrolytes, has been studied and discussed in terms of the “colloidal” and “soggy sand” electrolyte concepts. It has been found that conductivity increase of composite gels is not directly correlated with the liquid electrolyte uptake. On this basis it is concluded that important part of ionic transport in this type of composite gel polymer electrolytes is realized on the filler grain boundaries, through overlapping space charge layers of the silica grains.     

Highly enantioselective organocatalytic direct aldol reaction in an aqueous medium

We have demonstrated that small organic molecules 1 and 2 catalyzed the direct aldol reaction of both acyclic and cyclic ketones with different aldehydes in an excess of water/brine. Excellent enantioselectivities up to >99% and diastereoselectivities up to 99% with very good yields were obtained by using much lower catalyst loadings (0.5 mol %).     

Interaction of the antimicrobial peptide dicynthaurin with membrane phospholipids at the air-liquid interface

This paper reports the first study on the interaction of the antimicrobial peptide dicynthaurin with 1,2-dipalmitoyl-glycerophosphatidyl-glycerol investigated in monolayers at the air-liquid interface. The influence of the peptide on the two-dimensional phase behavior of the negatively charged lipid was elucidated by means of pressure-area isotherm measurements, fluorescence microscopy, and grazing incidence X-ray diffraction measurements. The pure peptide forms a stable monolayer at the air-liquid interface up to 30 mN/m as shown for both the monomeric and the dimeric cynthaurins. The peptide lipid interaction was monitored in isotherm measurements showing a strong adsorption of the peptide and stabilization at the interface promoted by the lipid monolayer. The X-ray diffraction measurements in agreement with fluorescence microscopy studies showed that the peptide destabilizes the condensed chain lattice, leading to a complete fluidization of the condensed lipid phase on physiological buffer. The adsorption of the peptide to the negatively charged lipid monolayer and the fluidization of the condensed chain lattice suggest a direct link to the peptides' ability to expand the bacterial membrane that would be relevant for the in vivo mode of action.     

Synthesis of TiO2 nanoparticles on the Au(111) surface

The growth of titanium oxide nanoparticles on reconstructed Au(111) was investigated by scanning tunneling microscopy and x-ray photoelectron spectroscopy. Ti was deposited by physical-vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. The titanium oxide nanoclusters were synthesized by subsequent exposure to O(2) at 300 K. Two-and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated 110-oriented step-edge morphology suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of the titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO(2) nanocrystals as judged by the Ti(2p) binding energies measured in the x-ray photoelectron data. The nanodispersed TiO(2) on Au(111) is an ideal system to test the various models proposed for the enhanced catalytic reactivity of supported Au nanoparticles.