New regiocontrolled synthesis of functionalized pyrroles from 2-azetidinone-tethered allenols

A new one-pot approach to synthesize densely substituted racemic and enantiopure pyrroles from beta-lactams has been developed. The approach relies on the regiocontrolled cyclization of beta-allenamine intermediates derived from the ring opening of 2-azetidinone-tethered allenols. In this approach four points of diversity are introduced, one of which is the position of the allene moiety on the beta-lactam ring.     

Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Structure and bonding in third-row main group dicarbides C2X (X=K-Br)

The molecular structures of third-row main group dicarbides C(2)X (X=K-Br) have been studied by theoretical methods. It is found that K, Ca, and Ga favor C(2v)-symmetric (T-shape) ground states, whereas As, Se, and Br have linear or quasilinear ground states. In the case of germanium. a very flat potential energy surface is found and an L-shape structure seems to be the ground state. Dissociation energies into X+C(2) are relatively high. The main features of these compounds, in particular, the preference for linear or cyclic structures, have been rationalized in terms of the most relevant interactions between the third-row atom and dicarbon with the help of an energy decomposition analysis.     

Quality evaluation of microscopy and scanned histological images for diagnostic purposes

In this work we present a study for assessing and comparing the fidelity of biopsy and cytology images captured with two different devices, that is optical microscopes and scanners, at 40× magnification in bright field. The devices use different ways to magnify images. Microscopes use a set of lenses while scanners capture light through arrays of micro-photoreceptors. The objective is to carry out a quantitative evaluation to discern which of the two devices provides better image quality in terms of contrast, colour and stain. Since there is no unanimous consensus on quality metrics, we will make use of both an objective metric based on perceptual features, together with a subjective psychophysical test as the International Telecommunications Union (ITU) recommends in ITU-R BT.500 for such type of tests. Both techniques indicate a slight preference for the scanner over the microscope in terms of better image quality, considering defocus as the main problem followed by colour distortions. However, the image quality of both devices is suitable for clinical, educational and research purposes.     

Probing the mechanical unzipping of DNA

A study of the micromechanical unzipping of DNA in the framework of the Peyrard-Bishop-Dauxois model is presented. We introduce a Monte Carlo technique that allows accurate determination of the dependence of the unzipping forces on unzipping speed and temperature. Our findings agree quantitatively with experimental results for homogeneous DNA, and for lamda-phage DNA we reproduce the recently obtained experimental force-temperature phase diagram. Finally, we argue that there may be fundamental differences between in vivo and in vitro DNA unzipping.