Synthesis and Cytotoxicity of 1,4‐Dihydropyridines and an Unexpected 1,3‐Oxazin‐6‐one

Eight heterocycles have been prepared in a one‐pot reaction manner based on the Hantzsch dihydropyridine synthesis. The synthesis afforded seven dihydropyridines (DHP) and one unexpected 1,3‐oxazin‐6‐one. Their structures were confirmed based on NMR spectroscopy and mass spectrometry. The obtained products have been evaluated for their cytotoxicity against eight cancer cell lines and one normal cell line. Two halogenated DHPs ( 7 and 8 ) displayed cytotoxicity toward all the nine tested cancer cell lines with IC₅₀ values from 4.10 to 58.90 μm, while others showed selective activities. DHPs ( 7 and 8 ) bearing a Me group at C(2) and C(6) as well as a halogenated substituent at C(4′) were more antiproliferative than the others.     

Micro-structural Impact of Different Strut Shapes and Porosity on Hydraulic Properties of Kelvin-Like Metal Foams

Various ideal periodic isotropic structures of foams (tetrakaidecahedron) with constant ligament cross section are studied. Different strut shapes namely circular, square, diamond, hexagon, star, and their various orientations are modeled using CAD. We performed direct numerical simulations at pore scale, solving Navier–Stokes equation in the fluid space to obtain various flow properties namely permeability and inertia coefficient for all shapes in the porosity range, \(0.60<\varepsilon <0.95\) for wide range of Reynolds numbers, \(10^{-6} . We proposed an analytical model to obtain pressure drop in metallic foams in order to correlate the resulting macroscopic pressure and velocity gradients with the Ergun-like approach. The analytical results are fully compared with the available numerical data, and an excellent agreement is observed.     

On the selectivity in some Rh(III) catalyzed CH activation cross-couplings

In the last few years, Rh(III)-catalyzed CH functionalizations have made tremendous progress and, consequently, have recently received increasing attention. These CH activation reactions, generally involving a chelate assisting directing group, have been utilized to form valuable heterocycles and to run useful coupling reactions. In this paper, three different transformations are presented and discussed. In order to unequivocally determine the stereochemistry of some of these transformations, crystal structural analysis data are provided.     

An operando DRIFTS investigation into the resistance against CO2 poisoning of a Rh/alumina catalyst during toluene hydrogenation

CO(2) is a major contaminant of renewable H(2) derived from biomass fermentation. The effect of the presence of CO(2) on the activity of alumina-supported Pt and Rh catalysts used for the hydrogenation of toluene at 348 K was investigated. The use of operando diffuse reflectance spectroscopy (DRIFTS) was crucial in unravelling the changes in the nature and abundance of species adsorbed at the sample surface and relating those to the changes of catalytic activity. Rhodium supported on alumina was only partly deactivated by the introduction of CO(2) during the hydrogenation of toluene, contrary to the case of Pt/alumina. Rh was only partially covered by carbonyl species derived from CO(2) and it was shown that toluene could successfully compete with some of the linearly adsorbed carbonyls for adsorption. The alumina support stored many CO(2)-derived adsorbates (carbonates, hydrogenocarbonates, carboxylates) that could spill over to the metal and form carbonyl species even after the removal of CO(2) from the feed.     

Through-bond versus through-space coupling in mixed-valence molecules: observation of electron localization at the single-molecule scale

Scanning tunneling microscopy (STM) is used to study two dinuclear organometallic molecules, meta-Fe2 and para-Fe2, which have identical molecular formulas but differ in the geometry in which the metal centers are linked through a central phenyl ring. Both molecules show symmetric electron density when imaged with STM under ultrahigh-vacuum conditions at 77 K. Chemical oxidation of these molecules results in mixed-valence species, and STM images of mixed-valence meta-Fe2 show pronounced asymmetry in electronic state density, despite the structural symmetry of the molecule. In contrast, images of mixed-valence para-Fe2 show that the electronic state density remains symmetric. Images are compared to constrained density functional (CDFT) calculations and are consistent with full localization of charge for meta-Fe2 on to a single metal center, as compared with charge delocalization over both metal centers for para-Fe2. The conclusion is that electronic coupling between the two metal centers occurs through the bonds of the organic linker, and through-space coupling is less important. In addition, the observation that mixed-valence para-Fe2 is delocalized shows that electron localization in meta-Fe2 is not determined by interactions with the Au(111) substrate or the position of neighboring solvent molecules or counterion species.     

Adamantyl‐endcapped polyynes

Polyynes spanning from a diyne to a dodecayne with adamantyl endgroups have been synthesized using the Fritsch–Buttenberg–Wiechell rearrangement as a key step to construct the acetylenic framework. Molecular properties as a function of polyyne length have been analyzed by UV–Vis spectroscopy, cyclic voltammetry, differential scanning calorimetry, and X‐ray crystallography. Copyright © 2011 John Wiley & Sons, Ltd.     

Suppression of parasitic lasing in high energy, high repetition rate Ti:sapphire laser amplifiers

Transverse parasitic lasing is well known for limiting the signal gain and the pulse energy that can be extracted from Ti:sapphire petawatt amplifiers. We have developed a technique for suppressing these parasitic lasing modes based on perfect refractive index-matching liquid doped with a broad-bandwidth absorber to suppress the transverse lasing while ensuring proper heat removal from the Ti:sapphire crystal. The 800 nm laser output with a bandwidth of 41 nm (FWHM) and peak energy of 22.7 J at a repetition rate of 1 Hz is demonstrated.     

95 GHz millimeter wave signal generation using an arrayed waveguide grating dual wavelength semiconductor laser

We report the generation of a 95?GHz carrier frequency by optical heterodyning of two wavelengths from adjacent channels from an arrayed waveguide grating-based multiwavelength laser. The extended cavity structure of the device provides low phase noise and narrow optical linewidth, further enhanced by the intracavity filter effect of the arrayed waveguide grating. We demonstrate that the generated RF beat note, at 95?GHz, has a -3 dB linewidth of 250?kHz. To the best of our knowledge, this is the narrowest RF linewidth generated from a free-running dual-wavelength semiconductor laser. The device is realized as a photonic integrated circuit using active-passive integration technology, and fabricated on a multiproject wafer run, constituting a novel approach for a compact, low-cost dual-wavelength heterodyne source.     

Direct loading of polymer matrices in plastic microchips for rapid DNA analysis: A comparative study

We report the design and performance validation of microfluidic separation technologies for human identification using a disposable plastic device suitable for integration into an automated rapid DNA analysis system. A fabrication process for a 15-cm long hot-embossed plastic microfluidic devices with a smooth semielliptical cross section out of cyclic olefin copolymer is presented. We propose a mixed polymer solution of 95% w/v hydroxyethylcellulose and 5% w/v polyvinylpyrrolidone for a final polymer concentration of 2.5 or 3.0% to be used as coating and sieving matrix for DNA separation. This formulation allows preparing the microchip without pretreatment in a single-loading step and provides high-resolution separation (≈1.2 bp for fragments <200 bp), which is superior to existing commercial matrices under the same conditions. The hot-embossed device performance is characterized and compared to injection-molded devices made out of cyclic olefin copolymer based on their respective injector geometry, channel shape, and surface charges. Each device design is assessed by fluorescence videomicroscopy to evaluate the formation of injection plugs, then by comparing electropherograms for the separation of a DNA size standard relevant to human identification.     

Design and FPGA-realization of a self-synchronizing chaotic decoder in the presence of noise

This paper describes requirement for wireless transmission of Chaotic Code Division Multiplexed Access (Chaotic CDMA) and it focuses on real-time synchronization algorithm embedded into electronic programmable device. CDMA with quasi-orthogonal codes is used to allow multi-users to transmit simultaneously in the same channel. Since the channel is shared between all users, the receiver system has to cope with channel noise and overall with interference from other users. As a result, one of the main problems of communication with quasi-orthogonal chaotic codes is to implement a real time decoder in presence of noise. Even if set-membership algorithm are efficient in real time synchronization of chaotic discrete generators in the presence of noise, these algorithms require a large memory resource. In this paper, we propose an evolution of set-membership algorithm toward genetic algorithm to be implemented into electronic programmable device. The advantage of genetic algorithm compared with set-membership algorithm is that they require a fixed size of memory.