Catalyzed Asymmetric Arylation Reactions

Addition and substitution reactions with carbon nucleophiles are fundamental processes in organic synthesis, and the development of general catalytic asymmetric variants thereof is still a major challenge today. In contrast to enantioselective alkyl transfer reactions, the corresponding arylations have not yet reached a high level of maturity. The existing protocols are either of no general applicability or are limited in terms of selectivity. This article summarizes established routes for catalytic asymmetric aryl transfer together with the latest developments in this area. The scope and limitations of this reaction are discussed.     

Molecular and conformational properties of comb-like polymers with ionically bound side chains studied in organic solvent

Conformational and dynamo-optical properties of a homologous series of poly(cetyltrimethylammonium 2-acrylamido-2-methylpropane sulfonates) with molecular masses ranging from 80 to 700?kDa were studied in chloroform solutions by viscometry, dynamic light scattering, sedimentation, and flow birefringence. The Mark–Kuhn–Houwink Equations for this polymer in chloroform were obtained; the values of hydrodynamic diameter and the Kuhn segment length as well as the value of intrinsic anisotropy of polarizability of the monomer unit were defined.     

Magnesium Hexafluoridozirconates MgZrF6·5H2O,MgZrF6·2H2O,and MgZrF6: Structures,Phase Transitions,and Internal Mobility of Water Molecules

The MgZrF₆ · n H₂O (n = 5, 2 and 0) compounds were studied by the methods of X‐ray diffraction and ¹⁹F, MAS ¹⁹F, and ¹H NMR spectroscopy. At room temperature, the compound MgZrF₆ · 5H₂O has a monoclinic C‐centered unit cell and is composed of isolated chains of edge‐sharing ZrF₈ dodecahedra reinforced with MgF₂(H₂O)₄ octahedra and uncoordinated H₂O molecules and characterized by a disordered system of hydrogen bonds. In the temperature range 259 to 255 K, a reversible monoclinic ? two‐domain triclinic phase transition is observed. The phase transition is accompanied with ordering of hydrogen atoms positions and the system of hydrogen bonds. The structure of MgZrF₆ · 2H₂O comprises a three‐dimensional framework consisting of chains of edge‐sharing ZrF₈ dodecahedra linked to each other through MgF₄(H₂O)₂ octahedra. The compound MgZrF₆ belongs to the NaSbF₆ type and is built from regular ZrF₆ and MgF₆ octahedra linked into a three‐dimensional framework through linear Zr–F–Mg bridges. The peaks in ¹⁹F MAS spectra were attributed to the fluorine structural positions. The motions of structural water molecules were studied by variable‐temperature ¹H NMR spectroscopy.     

Unfolding Features of Bovine Testicular Hyaluronidase Studied by Fluorescence Spectroscopy and Fourier Transformed Infrared Spectroscopy

Chemical unfolding of bovine testicular hyaluronidase (HAase) has been studied by fluorescence spectroscopy and Fourier transformed infrared spectroscopy (FTIR). Thermodynamic parameters were determined for unfolding HAase from changes in the intrinsic fluorescence emission intensity and the formations of several possible unfolding intermediates have been identified. This was further confirmed by representation of fluorescence data in terms of ‘phase diagram’. The secondary structures of HAase have been assigned and semiquantitatively estimated from the FTIR. The occurrence of conformational change during chemical unfolding as judged by fluorescence and FTIR spectroscopy indicated that the unfolding of HAase may not follow the typical two-state model.     

Coaxially gated in-wire thin-film transistors made by template assembly

Nanowire field effect transistors were prepared by a wet chemical template replication method using anodic aluminum oxide membranes. The membrane pores were first lined with a thin SiO2 layer by the surface sol-gel method. Au, CdS (or CdSe), and Au wire segments were then sequentially electrodeposited within the pores, and the resulting nanowires were released by dissolution of the membrane. Electrofluidic alignment of these nanowires between source and drain leads and evaporation of gold over the central CdS (CdSe) stripe affords a "wrap-around gate" structure. At VDS = -2 V, the Au/CdS/Au devices had an ON/OFF current ratio of 103, a threshold voltage of 2.4 V, and a subthreshold slope of 2.2 V/decade. A 3-fold decrease in the subthreshold slope relative to that of planar nanocrystalline CdSe devices can be attributed to coaxial gating. The control of dimensions afforded by template synthesis should make it possible to reduce the gate dielectric thickness, channel length, and diameter of the semiconductor segment to sublithographic dimensions while retaining the simplicity of the wet chemical synthetic method.     

Global Solutions of an Obstacle-Problem-Like Equation with Two Phases

Concerning the obstacle-problem-like equation , where ₊ > 0 and _– > 0, we give a complete characterization of all global two-phase solutions with quadratic growth both at 0 and infinity.     

Symmetry and electronic structure of noble-metal nanoparticles and the role of relativity

We present high resolution UV-photoelectron spectra of cold mass selected Cun-, Agn-, and Aun- with n=53-58. The observed electron density of states is not the expected simple electron shell structure, but is strongly influenced by electron-lattice interactions. Only Cu55- and Ag55- exhibit highly degenerate states. This is a direct consequence of their icosahedral symmetry, as is confirmed by density functional theory calculations. Neighboring sizes exhibit perturbed electronic structures, as they are formed by removal or addition of atoms to the icosahedron and therefore have lower symmetries. Gold clusters in the same size range show completely different spectra with almost no degeneracy, which indicates that they have structures of much lower symmetry. This behavior is related to strong relativistic bonding effects in gold, as demonstrated by ab initio calculations for Au55-.     

Using path sampling to build better Markovian state models: predicting the folding rate and mechanism of a tryptophan zipper beta hairpin

We propose an efficient method for the prediction of protein folding rate constants and mechanisms. We use molecular dynamics simulation data to build Markovian state models (MSMs), discrete representations of the pathways sampled. Using these MSMs, we can quickly calculate the folding probability (P(fold)) and mean first passage time of all the sampled points. In addition, we provide techniques for evaluating these values under perturbed conditions without expensive recomputations. To demonstrate this method on a challenging system, we apply these techniques to a two-dimensional model energy landscape and the folding of a tryptophan zipper beta hairpin.     

Optical waveguide sensor for on-line monitoring of bacteria

A grating-coupled planar optical waveguide sensor is presented for sensing of bacteria by evanescent waves. The waveguide design results in increased depth of penetration into the sample volume, which makes it suitable for detecting micrometer-sized biological objects. We tested the sensor's performance by monitoring the adhesion of Escherichia coli K12 cells to the sensor surface.