ALE-FEM for Two-Phase Flows

We present a finite element method for the flow of two immiscible incompressible fluids in two and three dimensions. Thereby the presence of surface active agents (surfactants) on the interface is allowed, which alter the surface tension. The model consists of the incompressible Navier-Stokes equations for velocity and pressure and a convection-diffusion equation on the interface for the distribution of the surfactant. A moving grid technique is applied to track the interface, on that account a Arbitrary-Lagrangian-Eulerian (ALE) formulation of the Navier-Stokes equation is used. The surface tension force is incorporated directly by making use of the Laplace-Beltrami operator technique [5]. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Density Measurements in cholesteryl Myristate

Abstract

The densities of cholesteryl myristate were measured in the smectic, cholesteric, blue and isotropic phase. At the transitions smectic/cholesteric and bluelisotropic within the temperature interval of 0.01 to 0.02°K discontinuities in the density curves occured. which indicate phase transitions of first order. At the transition cholesteric/blue only a change in the expansion coefficients was observed. which points to a phase transition of second order.

Die Dichten von Cholesterylmyristinat wurden in der smektischen, cholesterinischen, blauen und isotropen Phase gemessen. An den Umwandlungen smektisch/cholesterinisch und blau/isotrop treten innerhalb eines Temperdturintervah von 0,O1 bis 0.02°K Diskontinuitäten in den Dichtekurven auf. welche Phasenumwandlungen 1. Ordnung anzeigen. An der Umwandlung cholesterinisch/blau ist nur eine änderung in den Ausdehnungskoeffizienten vorhanden, welche auf eine Phasenumwandlung 2. Ordnung hinweist.     

Time-dependent control of hole-opening degree of porous ZnO hollow microspheres

Well-designed, monodispersed porous ZnO hollow microspheres with controlled hole-opening were successfully synthesized by a facile two-step solution route at low temperature. The hollow microspheres having average diameter of 3-4 μm showed time-dependent hole-opening, i.e. 4-100% for 15-75 min. The hole-opening percentage increases linearly with time until complete opening. The ZnO hollow microspheres also exhibited a high surface area (34 m(2) g(-1)), a large pore volume (0.19 cm(3) g(-1)) and an average pore diameter of 3.8 nm. A plausible growth mechanism for the formation of ZnO hollow microspheres was also proposed.     

Anisotropic organization and microscopic manipulation of self-assembling synthetic porphyrin microrods that mimic chlorosomes: bacterial light-harvesting systems

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems. They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores-which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions-have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces.     

Synthesis and Biological Evaluation of Cremastrine and an Unnatural Analogue

In this Letter, we describe the first total synthesis of cremastrine, a pyrrolizidine alkaloid from Cremastra appendiculata, with anticholinergic activity as well as an unnatural analogue. The streamlined synthesis proceeds in nine steps, seven steps longest linear sequence, in 25.2% overall yield, and features novel methodology to construct the pyrrolizidine core. Biological evaluation of cremastrine and the unnatural analogue indicated that both are pan-mAChR functional antagonists.     

Fourier transform infrared imaging analysis in discrimination studies of squamous cell carcinoma

Oral squamous cell carcinoma (OSCC) of the oral cavity and oropharynx represents more than 95% of all malignant neoplasms in the oral cavity. Histomorphological evaluation of this cancer type is invasive and remains a time consuming and subjective technique. Therefore, novel approaches for histological recognition are necessary to identify malignancy at an early stage. Fourier transform infrared (FTIR) imaging has become an essential tool for the detection and characterization of the molecular components of biological processes, such as those responsible for the dynamic properties of tumor progression. FTIR imaging is a modern analytical technique enabling molecular imaging of a complex biological sample and is based on the absorption of IR radiation by vibrational transitions in covalent bonds. One major advantage of this technique is the acquisition of local molecular expression profiles, while maintaining the topographic integrity of the tissue and avoiding time-consuming extraction, purification, and separation steps. With this imaging technique, it is possible to obtain unique images of the spatial distribution of proteins, lipids, carbohydrates, cholesterols, nucleic acids, phospholipids, and small molecules with high spatial resolution. Analysis and visualization of FTIR imaging datasets are challenging and the use of chemometric tools is crucial in order to take advantage of the full measurement. Therefore, methodologies for this task based on the novel developed algorithm for multivariate image analysis (MIA) are often necessary. In the present study, FTIR imaging and data analysis methods were combined to optimize the tissue measurement mode after deparaffinization and subsequent data evaluation (univariate analysis and MIAs). We demonstrate that it is possible to collect excellent IR spectra from formalin-fixed paraffin-embedded (FFPE) tissue microarrays (TMAs) of OSCC tissue sections employing an optimised analytical protocol. The correlation of FTIR imaging to the morphological tissue features obtained by histological staining of the sections demonstrated that many histomorphological tissue patterns can be visualized in the colour images. The different algorithms used for MIAs of FTIR imaging data dramatically increased the information content of the IR images from squamous cell tissue sections. These findings indicate that intra-operative and surgical specimens of squamous cell carcinoma tissue can be characterized by FTIR imaging.     

Phorone A and Isophorbasone A, Sesterterpenoids Isolated from the Marine Sponge Phorbas sp

A chemical investigation of a Korean marine sponge, Phorbas sp., yielded unprecedented sesterterpenoids phorone A (1) and isophorbasone A (2) along with ansellone B (3) and phorbasone A acetate (4). Their complete structures were elucidated by the combination of spectroscopic data and chemical manipulation. Phorone A (1) and isophorbasone A (2) have the new "phorane"(5) and "isophorbasane"(6) sesterterpenoid carbon skeletons, respectively. Ansellone B (3) and phorbasone A acetate (4) exhibited potent inhibitory activity on nitric oxide production in RAW 264.7 LPS-activated mouse macrophage cells with IC(50) values of 4.5 and 2.8 μM, respectively.     

A hydrogel-based versatile screening platform for specific biomolecular recognition in a well plate format

Precise determination of biomolecular interactions in high throughput crucially depends on a surface coating technique that allows immobilization of a variety of interaction partners in a non-interacting environment. We present a one-step hydrogel coating system based on isocyanate functional six-arm poly(ethylene oxide)-based star polymers for commercially available 96-well microtiter plates that combines a straightforward and robust coating application with versatile bio-functionalization. This system generates resistance to unspecific protein adsorption and cell adhesion, as demonstrated with fluorescently labeled bovine serum albumin and primary human dermal fibroblasts (HDF), and high specificity for the assessment of biomolecular recognition processes when ligands are immobilized on this surface. One particular advantage is the wide range of biomolecules that can be immobilized and convert the per se inert coating into a specifically interacting surface. We here demonstrate the immobilization and quantification of a broad range of biochemically important ligands, such as peptide sequences GRGDS and GRGDSK-biotin, the broadly applicable coupler molecule biocytin, the protein fibronectin, and the carbohydrates N-acetylglucosamine and N-acetyllactosamine. A simplified protocol for an enzyme-linked immunosorbent assay was established for the detection and quantification of ligands on the coating surface. Cell adhesion on the peptide and protein-modified surfaces was assessed using HDF. All coatings were applied using a one-step preparation technique, including bioactivation, which makes the system suitable for high-throughput screening in a format that is compatible with the most routinely used testing systems.     

On factors influencing arc filament plasma actuator performance in control of high speed jets

Localized arc filament plasma actuators (LAFPAs) have been developed and used at The Gas Dynamics and Turbulence Laboratory for the purpose of controlling high-speed and high Reynolds number jets. The ability of LAFPAs for use in both subsonic and supersonic jets has been explored, and experiments to date have shown that these actuators have significant potential for mixing enhancement and noise control applications. While it has been established that the actuators manipulate instabilities of the jet, the exact nature of how the actuation couples to the flow is still unclear. All of the results previously reported have been based on a nozzle extension that has an azimuthal groove of 1 mm width and 0.5 mm depth along the inner surface approximately 1 mm upstream of nozzle extension exit. The ring groove was initially added to shield the plasma arcs from the high-momentum flow. However, the effect of the ring groove on the actuation mechanism is not known. To explore this effect, a new nozzle extension is designed, which relocates the actuators to the nozzle extension face and eliminates the ring groove. Schlieren images, particle image velocimetry and acoustic results of a Mach 0.9 jet of Reynolds number ~6.1 × 10⁵ show similar trends and magnitudes with and without a ring groove. Thus, it is concluded that the ring groove does not play a primary role in the LAFPAs’ control mechanism. Furthermore, the effect of the duty cycle of the actuator input pulse on the LAFPAs’ control authority is investigated. The results show that the minimum duty cycle that provides complete plasma formation has the largest control over the jet.     

Synthesis of complexes bearing NH,NMe-substituted NHCs by oxidative addition of 2-halogenato-N-methylbenzimidazoles to Ni(0)

Reaction of 2-X-N-methylbenzimidazole (X = chloro, iodo) with Ni(0) complexes in the presence of dppe or PEt(3) and an external proton source yielded via an oxidative addition reaction nickel(II) complexes bearing NH,NMe-functionalized NHC ligands.