Darstellung,Eigenschaften und Molekülstrukturen von Dimethylaminomethylferrocenyl‐Verbindungen ausgewählter Elemente der Gruppen 13 und 14

Preparation, Properties, and Molecular Structures of Dimethylaminomethyl Ferrocenyl Compounds of selected Elements of Group 13 and 14 Dimethylmetalchlorides of gallium and indium react with dimethylaminomethylferrocenyllithium (FcNLi) to give the corresponding dimethylmetaldimethylaminomethylferrocenes 1 and 2 [Me₂MFcN; M=Ga, In]. In a similar manner dialkylmetaldichlorides of germanium and tin yield the expected chlordialkylmetaldimethylaminomethylferrocenes 3 – 5 [R₂(Cl)MFcN; M=Ge; R = Me ( 3 ), M=Sn; R=Me ( 4 ), Ph ( 5 )]. In a reaction of Me₃Al and Me₂AlCl with dimethylaminomethylferrocene the formation of the 1 : 1 adducts 7 and 8 could be observed. All compounds were characterised by ¹H and ¹³C nmr spectroscopy. The molecular structures of 1 , 3 , 4 and 7 were determined. 3 and 4 build in contrast to 1 monomeric molecules with chelat rings as a result of the M–N coordination. Compound 7 consist of monomeric molecules with 4 coordinated Al atoms.     

Anisotropic unstructured mesh adaption for flow simulations

Three new ideas for anisotropic adaption of unstructured triangular grids are presented, with particular emphasis on fluid flow computations. © 1997 John Wiley & Sons, Ltd.     

Anisotropic agarose gels

Agarose hydrogels deswell reversibly over a wide range of concentration. Two types of deswelling measurements are considered here, isotropic and uniaxial. We describe some of the properties of the gels observed in the deswollen state. In both the isotropic and uniaxial geometry, the swelling pressure varies approximately as the square of the concentration.     

A photoprogrammable electronic nose with switchable selectivity for VOCs using MOF films

Advanced analytical applications require smart materials and sensor systems that are able to adapt or be configured to specific tasks. Based on reversible photochemistry in nanoporous materials, we present a sensor array with a selectivity that is reversibly controlled by light irradiation. The active material of the sensor array, or electronic nose (e-nose), is based on metal–organic frameworks (MOFs) with photoresponsive fluorinated azobenzene groups that can be optically switched between their trans and cis state. By irradiation with light of different wavelengths, the trans–cis ratio can be modulated. Here we use four trans–cis values as defined states and employ a four-channel quartz-crystal microbalance for gravimetrically monitoring the molecular uptake by the MOF films. We apply the photoprogrammable e-nose to the sensing of different volatile organic compounds (VOCs) and analyze the sensor array data with simple machine-learning algorithms. When the sensor array is in a state with all sensors either in the same trans- or cis-rich state, cross-sensitivity between the analytes occurs and the classification accuracy is not ideal. Remarkably, the VOC molecules between which the sensor array shows cross-sensitivity vary by switching the entire sensor array from trans to cis. By selectively programming the e-nose with light of different colors, each sensor exhibits a different isomer ratio and thus a different VOC affinity, based on the polarity difference between the trans- and cis-azobenzenes. In such photoprogrammed state, the cross-sensitivity is reduced and the selectivity is enhanced, so that the e-nose can perfectly identify the tested VOCs. This work demonstrates for the first time the potential of photoswitchable and thus optically configurable materials as active sensing material in an e-nose for intelligent molecular sensing. The concept is not limited to QCM-based azobenzene-MOF sensors and can also be applied to diverse sensing materials and photoswitches.

A sensor array with four identical photoresponsive azobenzene-containing metal–organic framework films is selectively irradiated. By photoprogamming the array, the sensor selectivity is switched and optimized.     

ortho‐Fluoroazobenzenes: Visible Light Switches with Very Long‐Lived Z Isomers

Improving the photochemical properties of molecular photoswitches is crucial for the development of light‐responsive systems in materials and life sciences. ortho‐Fluoroazobenzenes are a new class of rationally designed photochromic azo compounds with optimized properties, such as the ability to isomerize with visible light only, high photoconversions, and unprecedented robust bistable character. Introducing σ‐electron‐withdrawing F atoms ortho to the N?N unit leads to both an effective separation of the n→π* bands of the E and Z isomers, thus offering the possibility of using these two transitions for selectively inducing E/Z isomerizations, and greatly enhanced thermal stability of the Z isomers. Additional para‐electron‐withdrawing groups (EWGs) work in concert with ortho‐F atoms, giving rise to enhanced separation of the n→π* transitions. A comprehensive study of the effect of substitution on the key photochemical properties of ortho‐fluoroazobenzenes is reported herein. In particular, the position, number, and nature of the EWGs have been varied, and the visible light photoconversions, quantum yields of isomerization, and thermal stabilities have been measured and rationalized by DFT calculations.     

The materials science X‐ray beamline BL8 at the DELTA storage ring

The hard X‐ray beamline BL8 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA is described. This beamline is dedicated to X‐ray studies in the spectral range from ～1 keV to ～25 keV photon energy. The monochromator as well as the other optical components of the beamline are optimized accordingly. The endstation comprises a six‐axis diffractometer that is capable of carrying heavy loads related to non‐ambient sample environments such as, for example, ultrahigh‐vacuum systems, high‐pressure cells or liquid‐helium cryostats. X‐ray absorption spectra from several reference compounds illustrate the performance. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments have been performed. The results show that high‐quality EXAFS data can be obtained in the quick‐scanning EXAFS mode within a few seconds of acquisition time, enabling time‐resolved in situ experiments using standard beamline equipment that is permanently available. The performance of the new beamline, especially in terms of the photon flux and energy resolution, is competitive with other insertion‐device beamlines worldwide, and several sophisticated experiments including surface‐sensitive EXAFS experiments are feasible.     

Anodic silver (II) oxides investigated by combined electrochemistry,ex situ XPS and in situ X‐ray absorption spectroscopy

Silver (II) oxide layers (AgO) were prepared by anodic oxidation of pre‐oxidized, Ag₂O‐covered silver electrodes in 1 M NaOH (pH 13.8). The oxidized electrodes were investigated using a combination of electrochemical techniques, ex situ X‐ray photoelectron spectroscopy (XPS) and in situ surface‐sensitive grazing incidence X‐ray absorption spectroscopy (EXAFS) under full potential control. The application of these different techniques leads to a detailed, consistent picture of the anodic silver (II) oxide layer formation. The experiments have shown that the chemical composition of the AgO layer varies significantly with oxidation potential, revealing a decreasing oxygen deficiency with increasing anodization potential and oxidation time. XPS as well as EXAFS experiments support the interpretation of the oxide as a mixed valence Ag ⁺ Ag^{3 +} O₂ with different contributions of Ag ⁺ and Ag^{3 +} species, depending on potential and anodization time. Copyright © 2009 John Wiley & Sons, Ltd.     

Towards photocontrol over the helix-coil transition in foldamers: synthesis and photoresponsive behavior of azobenzene-core amphiphilic oligo(meta-phenylene ethynylene)s

Introduction of photochromic azobenzene units into amphiphilic oligo(meta-phenylene ethynylene)s allowed photocontrol over the helix-coil transition in this important class of foldamers. Two design principles were followed in efforts to accommodate cis- and trans-azobenzene moieties within the helical structure to selectively turn the helical state on and off, respectively. Several oligomer series with varying connectivities to the central azobenzene chromophore were synthesized and these photochromic oligomers were investigated with regard to their folding behavior in both dark and irradiated states. Both the foldamers' chain lengths and the electronic structures of the azobenzene moieties had to be optimized to ensure folding differences and selective excitation of the photochrome. The design of such stimuli-responsive macromolecules, displaying large structural changes upon irradiation, should guide the design of future materials in, for example, "smart" delivery applications.     

Anomalous small angle x-ray scattering determination of ion distribution around a polyelectrolyte biopolymer in salt solution

The distribution of counterions in solutions of high molecular mass hyaluronic acid, in near-physiological conditions where mono- and divalent ions are simultaneously present, is studied by small angle neutron scattering and anomalous small angle x-ray scattering. The solutions contain either sodium or rubidium chloride together with varying concentrations of calcium or strontium chloride. The effects of monovalent-divalent ion exchange dominate the amplitude and the form of the counterion cloud. In the absence of divalent ions, the shape of the anomalous scattering signal from the monovalent ions is consistent with the distribution calculated from the Poisson-Boltzmann equation, as found by other workers. In mixtures of monovalent and divalent ions, however, as the divalent ion concentration increases, both the diameter and the amplitude of the monovalent ion cloud decrease. The divalent counterions always occupy the immediate neighborhood of the charged polyanion. Above a given concentration their anomalous scattering signal saturates. Even in a large excess of divalent ions, ion exchange is incomplete.