Cobalt(II) Complexes of Nitrile‐Functionalized Ionic Liquids

A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C₁C_1CNPyr)₂(Tf₂N)₄] and [Co(C₁C_2CNPyr)₆][Tf₂N]₈, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids.     

Redox-induced ligand reorganization and helicity inversion in copper complexes of N,N-dialkylmethionine derivatives

N,N'-Dipicolyl, bis(stilbylvinylpyridylmethyl), and diquinaldyl methionine derivatives form stable Cu(II) complexes with metal ligation by three nitrogen atoms and the carboxylate. One-electron reduction results in the exchange of carboxylate for sulfide in the complexes. This ligand reorganization is accompanied by inversion of the helical orientation of the two arms containing nitrogen heterocycles, resulting in nearly mirror image circular dichroism spectra. This paper provides details for the synthesis of these complexes and the evidence for the remarkable stereochemical interconversion that accompanies the reduction reaction. Detailed analysis of the electronic spectra of the ligands and metal complexes is provided along with X-ray crystallographic structures of Cu(II) and Zn(II) complexes of the N,N'-dipicolylmethionine complexes.     

Chemical effects during formation of the electronic surface structure of III–V semiconductors in a sulfide solution

The electronic properties of the (100) surface of n-GaAs, p-GaAs, and n-InP semiconductors treated with various sulfide solutions have been studied. Sulfide treatment was shown to increase the photoluminescence intensity, decrease the depth of the near-surface depleted region in the semiconductor, and shift the surface Fermi level toward the conduction band. These effects are the stronger, the higher the sulfur chemical activity in the solution. Fiz. Tverd. Tela (St. Petersburg) 41, 875–878 (May 1999)     

Redox inversion of helicity in propeller-shaped molecules derived from s-methyl cysteine and methioninol

One-electron reduction inverts the helicity of copper complexes formed from derivatives of S-methylcysteine and methioninol. The change in conformation of the organic ligand is followed in the exciton-coupled circular dichroism (ECCD) spectra of the complexes.     

Zum Reaktionsmechanismus von Glutaraldehyd mit Proteinen

The interaction of glutaraldehyde with model aliphatic amines was studied in order to understand the crosslinking reaction of glutaraldehyde with proteins. The reaction in organic solvents gave N-alkyl-1,4-dihydropyridines and N,N-dialkyl-1,5-diiminopentanes. The isolated products are new or were previously described by us for the first time¹. Hydration of the reaction products led to stable N-alkylpiperidines and N,N-dialkyl-1,5-diaminopentanes. In aqueous solution the reaction depends on thepH: at apH above 7, N-alkyl-1,4-dihydropyridines and at apH below 7, polymers were obtained. For the crosslinking reaction of proteins with glutaraldehyde the following mechanism is proposed: Monomeric glutaraldehyde reacts with the protein to give intermediate N-alkyl-2,6-dihydroxypiperidines. Intramolecular dehydration leads to the corresponding N-alkyl-1,4-dihydropyridines. Condensation of the cyclic monohydrate of glutaraldehyde and N-alkyl-2,6-dihydroxypiperidines gives linear polymeric crosslinks containing -oxo-N-alkylpiperidine units.

Lubig R., Dissertation, RWTH Aachen, 1974.     

Optical spectroscopy for in situ characterisation of semiconductor interfaces and layers

The potential of optical techniques for semiconductor interfaces and growing layers is demonstrated using in particular the example of Raman spectroscopy in combination with molecular beam epitaxial (MBE) growth. Recent developments allow this method to be applied not only in situ but while growth progresses. This application critically depends on the resonant excitation which provides the required sensitivity for layers in the nanometre range. Here the heteroepitaxy of II–VI compound semiconductors on III–V substrates serves as an example to illustrate the wealth of information, e.g. on layer composition, crystallinity, growth rate, and interfacial reactivity. Very recent results on gallium nitride growth clearly reveal that such experiments can be performed even at temperatures as high as 685?°C.     

Identification of ultra-thin layers by cross-sectional Raman spectroscopy

 Micro-Raman spectroscopy measurements in a cross-sectional sample geometry were performed for three heterosystems (3C-SiC/Si(100), diamond/Si(100), and ZnS_xSe_1-x/GaAs(100)). Using an automated xy-stage with a minimum step width of 100 nm one-dimensional scans across the interface were taken. It is demonstrated that sufficient sensitivity for the detection of ultra-thin layers with thicknesses in the nanometer range can be achieved. Thus surface and interface layers not accessible in a plane-view geometry can be identified. In addition, the depth-resolved variation of sample properties like interfacial reactions, stress, and stoichiometry will be discussed. Received: 24 June 1996/Revised: 9 December 1996/Accepted: 13 December 1996     

Über die Molekulargewichtsverteilung von Desoxyribonucleinsäure in der Ultrazentrifuge

Zusammenfassung Das Molekulargewicht der aus der Forellenmilch gewonnenen Desoxyribonucleins?ure wurde mit Hilfe der Ultrazentrifuge untersucht. Wegen der hohen Viskosit?t mu?te man eine sehr verdünnte L?sung von 0,002% DNS inMcIlvaine- Puffer (p_H 4,97) anwenden. Die experimentellen Konzentrationskurven wurden mit UV-Absorptionsoptik aufgenommen, und danach lie?en sich auch die theoretischen Gradientenkurven ableiten. Es hat sich gezeigt, da? DNS mehrere polydisperse Fraktionen enth?lt, die erne mehrgipfelige charakteristische Verteilung darstellen mit einer mittleren Sedimentationskonstante von 19,35 sved. Auf Grund dieser Konstante sowie auch aus den Viskosit?tsmessungen, die die „intrinsic viscosity“ 〈[π]Φ=0〉=6541 liefern, wurde der Mittelwert für das Achsenverh?ltnis 〈p〉= 380 und für das Molekulargewicht 〈M〉=6100000 festgestellt. Die mittlere Dicke der DNS-Moleküle ist 25 ? und die L?nge 1,178μ. Die Bestimmung der Molekulargewichtsverteilung kann nach dieser Methode sowie auch nach der neuen Momentenmethode bzw. nach der „Dreipunktmethode“ unmittelbar aus der experimentellen Gradientenkurve abgeleitet werden. Mit Unterstützung der Deutschen Forschungsgemeinschaft. Frl. Dr.L. Hübner aus dem Paul-Ehrlich-Institut, Frankfurt a. M., und HerrnG. Zwarg aus dem Beckman-Werk in München danken wir für die Hilfe und die Mitarbeit bei der Durchführung der Sedimentationsversuche.