A chip-based platform for the in vitro generation of tissues in three-dimensional organization

We describe a multi-purpose platform for the three-dimensional cultivation of tissues. The device is composed of polymer chips featuring a microstructured area of 1-2 cm(2). The chip is constructed either as a grid of micro-containers measuring 120-300 x 300 x 300 microm (h x l x w), or as an array of round recesses (300 microm diameter, 300 microm deep). The micro-containers may be separately equipped with addressable 3D-micro-electrodes, which allow for electrical stimulation of excitable cells and on-site measurements of electrochemically accessible parameters. The system is applicable for the cultivation of high cell densities of up to 8 x 10(6) cells and, because of the rectangular grid layout, allows the automated microscopical analysis of cultivated cells. More than 1000 micro-containers enable the parallel analysis of different parameters under superfusion/perfusion conditions. Using different polymer chips in combination with various types of bioreactors we demonstrated the principal suitability of the chip-based bioreactor for tissue culture applications. Primary and established cell lines have been successfully cultivated and analysed for functional properties. When cells were cultured in non-perfused chips, over time a considerable degree of apoptosis could be observed indicating the need for an active perfusion. The system presented here has also been applied for the differentiation analysis of pluripotent embryonic stem cells and may be suitable for the analysis of the stem cell niche.     

Modeling of the dynamics of multi-section waveguide lasers

A dynamic model for the design of multi-section semiconductor lasers is developed based on the Transmission Line Method. The different building blocks of this model are presented and the model is evaluated for a tunable two-section laser device.     

Multistage complexation of fluoride ions by a fluorescent triphenylamine bearing three dimesitylboryl groups: controlling intramolecular charge transfer

A propeller-shaped boron-nitrogen compound (NB(3)) with three binding sites for fluoride anions was synthesized and investigated by optical absorption, luminescence, and ((1)H, (11)B, (13)C, (19)F) NMR spectroscopy. Binding of fluoride in dichloromethane solution occurs in three clearly identifiable steps and leads to stepwise blocking of the three initially present nitrogen-to-boron charge transfer pathways. As a consequence, the initially bright blue charge transfer emission is red-shifted and decreases in intensity, until it is quenched completely in presence of large fluoride excess. Fluoride binding constants were determined from global fits to optical absorption and luminescence titration data and were found to be K(a1) = 4 × 10(7) M(-1), K(a2) = 2.5 × 10(6) M(-1), and K(a3) = 3.2 × 10(4) M(-1) in room temperature dichloromethane solution. Complexation of fluoride to a given dimesitylboryl site increases the electron density at the central nitrogen atom of NB(3), and this leads to red shifts of the remaining nitrogen-to-boron charge transfer transitions involving yet unfluorinated dimesitylboryl groups.     

Rearrangements in cobaltic fluoride fluorinations of cycloalkanes with seven or more ring carbons

Cyclo-heptane, -octane, -decane, -dodecane and -octadecane have been fluorinated in the vapour phase with cobaltic fluoride. The perfluorocarbons obtained revealed varying degrees of skeletal rearrangements. Thus, cycloheptane gave perfluoro-cycloheptane and -methylcyclohexane; cyclooctane gave at least eight fluorocarbons including-bicyclo(3,3,0)octane and -cyclooctane; cyclodecane gave a complex mixture from which were isolated perfluoro cis- and trans-bicyclo(4,4,0)decanes but no perfluorocyclodecane; cyclododecane and cyclooctadecane gave complex fluorocarbon mixtures in which none of the fluorocarbons with the original cycloalkene skeleton could be detected.Tetradecafluorobicyclo(3,3,0)octane gave dodecafluorobicyclo (3,3,0)oct-1(5)-ene and decafluorobicyclo(3,3,0)octa-di-1(5), 2-ene when pyrolysed over iron gauze.The fluorination of cyclooctane also afforded 1$\text{H}$-pentadecafluorocyclooctane which was dehydrofluorinated to tetradecafluorocyclooctene. This was converted to a range of derivatives including dodecafluorosuberic acid, 1,2-dichlorotetradecafluorocyclooctane, 1-methoxy tridecafluorocyclooctene and tetradecafluorocyclooctanone.     

Direct calculation of interconversion barriers in dynamic chromatography and electrophoresis: Isomerization of captopril

Dynamic capillary electrophoresis (DCE) and direct calculation of the rate constants of isomerization has been applied to determine the cis-trans isomerization barriers of the angiotensin-converting enzyme inhibitor captopril. The separation of the rotational cis-trans isomeric drug has been performed in an aqueous 50 mM borate buffer at pH 9.3. Interconversion profiles featuring plateau formation, peak-broadening, and peak coalescence were observed. To determine the rate constants of the forward and backward reaction (k(cis-->trans) and k(trans-->cis)) of the isomerization process in dynamic capillary electrophoresis, a novel straightforward calculation method using the experimental parameters plateau height, h(plateau), peak width at half height w(h), the total migration times of the cis-trans isomers t(R) and the electroosmotic break-through time t(0) as well as the peak ratio of the cis-trans isomers is presented for the first time. From temperature dependent measurements the rate constants k(cis-->trans) and k(trans-->cis) and the kinetic activation parameters DeltaG( not equal), DeltaH( not equal), and DeltaS( not equal) of the cis-trans isomerization of captopril were obtained. From the activation parameters the isomerization barriers of captopril at 37 degrees C under basic conditions were calculated to be DeltaG( not equal) (cis-->trans) = 90.3 kJ.mol(-1)and DeltaG( not equal) (trans-->cis) = 90.0 kJ.mol(-1*).     

Thermal Analysis of Adsorbed Poly(methyl methacrylate) on Silica

Modulated differential scanning calorimetry has been used to quantify the glass transitions of small adsorbed amounts of poly(methyl methacrylate) (PMMA) on silica. While a relatively narrow, single glass transition was found for bulk PMMA, broader two-component transitions were found for the adsorbed polymer. A two-state model based on loosely bound polymer (glass transition similar to bulk) and more tightly bound polymer (glass transition centered around 156 degrees C) was used to interpret the thermograms. On the basis of this model, the amount of tightly bound polymer was found to be approximately 1.3 mg/m2, corresponding to a 1.1 nm thick layer. The change in heat capacity for the tightly bound polymer at the glass transition temperature was estimated to be about 16% of that of the bulk polymer.     

Cellular logic with orthogonal ribosomes

The creation and use of unnatural molecules to control cellular function is a long standing goal of the chemical community, but in general, these efforts have been directed at finding molecules to inhibit or activate a particular molecular target or function, or to elicit a particular phenotype. Here we show that multiple unnatural molecules (orthogonal ribosomes) can be used combinatorially, in a single cell, to program Boolean logic functions. These experiments show how attention to the molecular specificity of noncovalent interactions between unnatural macromolecules allows the synthesis of complex function from the "bottom-up" in living matter.     

Surface segregation of dissolved salt ions

Surface segregation of iodide, but not of fluoride or cesium ions, is observed by a combination of metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS(HeI)) of amorphous solid water exposed to CsI or CsF vapor. The same surface ionic behavior is also derived from molecular dynamics (MD) simulations of the corresponding aqueous salt solutions. The MIES results show the propensity of iodide, but not fluoride, for the surface of the amorphous solid water film, providing thus strong evidence for the suggested presence of heavier halides (iodide, bromide, and to a lesser extent chloride) at the topmost layer of aqueous surfaces. In contrast, no appreciable surface segregation of ions is observed in methanol, neither in the experiment nor in the simulation. Furthermore, the present results indicate that, as far as the thermodynamic aspects of solvation of alkali halides are concerned, amorphous solid water and methanol surfaces behave similarly as surfaces of the corresponding liquids.