Synthetische Juvenilhormone 3. Mitteilung. p-Substituierte 4-Phenyl-buten(1)-carbonsäurederivate

The syntheses of p-substituted 2-methyl-4-phenylbuten(1)-carboxylic acid derivatives are described, using Blanc's chloromethylation reaction, the Friedel-Crafts alkylation of unsaturated ketones or the Meerwein arylation; the formed intermediates react in subsequent steps to the title compounds.     

The Peierls transition of Perylene radical cation salts with 2:1 stoichiometry containing tetrahydrofuran

Crystal structure, microwave conductivity and static magnetic susceptibility were analyzed for the conducting perylene (PE) radical cation salts of nominal composition (PE)₂(PF₆)_1–x (AsF₆) _x ·2/3 THF for 0x1. Crystallographic phase transitions in the high-temperature metal phase were also characterized by differential scanning calorimetry and electron spin resonance. The Peierls transition occuring at 100–120 K (depending onx) and the opening of the energy gap in the semiconductor phase were determined from the magnetic data. The dependence of these properties on the size of the complex anions and the packing of the PE molecules is discussed.     

Receptor-bound conformation of an alpha(5)beta(1) integrin antagonist by (15)N-edited 2D transferred nuclear overhauser effects

We report the results of (15)N-edited 2D transferred NOE experiments of the partially (15)N-labeled alpha(5)beta(1) antagonist c[Mpa(15)N-Arg-(15)N-Gly-(15)N-Asp-(15)N-Asp-(15)N-Val-Cys]-NH(2) (Mpa denotes mercaptopropionic acid) in the presence of the native alpha(5)beta(1) receptor. The alpha(5)beta(1) integrin receptor is believed to be involved in tumor metastasis and the rational design of alpha(5)beta(1) integrin antagonist is therefore of considerable interest. Our experiments provide insight into the alpha(5)beta(1) receptor-bound conformation of the antagonist c[MpaRGDDVC]-NH2 and will be important for the design of novel antagonists.     

Beiträge zur Chemie der Halogensilan-Addukte. XXII. Wasserstoffbrückenbindung und Ionisierung Pentakoordinierter SiCl-Verbindungen. Darstellung,Eigenschaften, Kristall- und Molekülstruktur von 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridiniumchlorid-Chloroform(1/1),

Contributions to the Chemistry of Halosilane Adducts. XXII. Hydrogen Bonding and Ionization of Pentacoordinated Si-Compounds. Preparation, Properties, Crystal and Molecular Structure of 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridinium-chloride-Chloroform(1/1), The title compound ( 1 ) is obtained by the reaction of 2-trimethylsilylaminopyridine and Me₂CH₂ClSiCl in CHCl₃. The SiCl bond is ionic (X-ray structure determination). 1 crystallizes monoclinic space group P2₁/c (Z = 8). The asymmetric unit contains two symmetrically nonequivalent molecular cations of 1 , two Cl anions and two CHCl₃. Silicon is tetracoordinate with Si? N-bond distances of 1.766 Å and 1.777 Å. The shortest SiCl distances (3.908 and 4.110 Å) correspond to ionic interactions. Both Cl anions are hydrogen bonded to CHC1₃. Additionally one C1_? is hydrogen bonded to the NH groups of two neighbouring cations. Structural comparison with related compounds suggests these interactions to be responsible for the transition from pentacoordination to tetracoordination at Si (ionization of the Sic1 bond). ¹H- and ²⁹Si-NMR investigations of 1 show this transition to be dependent on the combined effect of NH…?C1^? and C1₃CH…?C1_? interactions. 1 is completely ionized in CDCl₃ in the temperature range ?80° to +80°C while in the weaker acceptor solvent benzonitrile a temperature dependent shift from the ionic tetracoordinate to the pentacoordinate structure is observed with increasing pentacoordination with increase of temperature.     

Single-beam and enhanced two-beam second-harmonic generation from silicon nanocrystals by use of spatially inhomogeneous femtosecond pulses

Optical second-harmonic generation (SHG) is used as a noninvasive probe of the interfaces of Si nanocrystals (NCs) embedded uniformly in an SiO2 matrix. Measurements of the generated SH mode verify that the second-harmonic polarization has a nonlocal dipole form proportional to (E x Delta inverted) E that depends on inhomogeneities in the incident field E, as proposed in recent models based on a locally noncentrosymmetric dipolar response averaged over the spherical NC interfaces. A two-beam SHG geometry is found to enhance this polarization greatly compared to single-beam SHG, yielding strong signals useful for scanning, spectroscopy, and real-time monitoring. This configuration provides a general strategy for enhancing the second-order nonlinear response of centrosymmetric samples, as demonstrated here for both Si nanocomposites and their glass substrates.     

X-Ray diffraction at high temperatures

Experimental equipment for X-ray diffraction at high temperatures is introduced and the possibility to directly observe the evolution of the atomic (geometric) structure as a function of temperature is discussed. Recent results on crystallization investigations of amorphous iron-based alloys and on the structural development in thin molybdenum sulphide films are given. The kinetics of the process was followed by means of time resolved experiments in both cases.     

Background-free cars studies of carbon monoxide in a flame

Background-free coherent anti-Stokes Raman spectra (CARS) of carbon monoxide have been obtained in a rich methane-air flat flame. Use of this background rejection method, requiring only two laser frequencies, results in an increase in signal-to-noise of over 200 in the |x⁽³⁾|² spectrum in comparison with normal CARS. In addition, this technique provides a means for determining the symmetry of observed Raman transitions. The principles of background-free CARS are derived, and the capabilities are demonstrated with experimental data.     

Spectroscopy and rectification of three donor-sigma-acceptor compounds, consisting of a one-electron donor (pyrene or ferrocene), a one-electron acceptor (perylenebisimide), and a C19 swallowtail

We report spectroscopic characterization and unimolecular rectification (asymmetric electrical conduction) measurements of three donor-sigma-acceptor (D-sigma-A) compounds N-(10-nonadecyl)-N-(1-pyrenylmethyl)perylene-3,4,9,10-bis(dicarboximide) (1), N-(10-nonadecyl)-N-(4-[1-pyrenyl]butyl)perylene-3,4,9,10-bis(dicarboximide) (2), and N-(10-nonadecyl)-N-(2-ferrocenylethyl)perylene-3,4,9,10-bis(dicarboximide) (3). These molecules were arranged as one-molecule thick Langmuir-Blodgett monolayers between Au electrodes. In such an "Au | D-sigma-A | Au" sandwich, molecule 1 is a unimolecular rectifier, with rather small rectification ratios (between 2 and 3 at +/-1 V) that decrease upon cycling. Molecule 2 does not rectify. Molecule 3 rectifies, with a rectification ratio of between 14 and 28 at +/-1 V; the through-film rectification and currents persist, even with scans of +/-2 V, for up to 40 cycles of measurement. Qualitative arguments, based on a two-level rectification mechanism, are consistent with the current asymmetries observed in the monolayers of 1 and 3.     

Highly Efficient Implementation of ANS/ EAS ‘Solid-Shell’ Finite Elements for Explicit Time Integration

In an explicit time integration algorithm, the most time-consuming part of an analysis is the computation of the internal nodal force vector. An implementation concept for element routines for volumetric shell ­ so-called Solid-Shell - elements based on the application of the symbolic programming tool ACEGEN, a plug-in for the computer algebra software MATHEMATICA is presented. Symbolic implementation means that vector and matrix operations and differentiations can be performed symbolically in order to generate program code, which supports the implementation, reduces programming effort and helps to avoid programming errors almost completely. The program code is generated in FORTRAN and simultaneously optimized automatically, which leads to very efficient routines compared to manually implemented code. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)