Molecular vibrations in a gradient extremal path

Summary The calculation of vibrational states using a gradient extremal path is discussed. Gradient extremal paths are defined by local criteria, which lead to stable solutions. This has certain advantages in comparison with a steepest-descent path, which is often difficult to determine accurately. For cases where a reaction path formalism is applicable, a path based on the gradient extremal concept gives results in close agreement with those obtained using traditional steepest-descent methods. We present algorithms for carrying out such calculations and also give some numerical results.     

Complex study of nickel skeleton catalysts: V. Study of novel non-pyrophoric nickel skeleton catalysts by derivatograph

The structure and properties of non-pyrophoric skeleton catalysts prepared from NiSi, NiAlSi, NiMg and NiZn alloys have been studied—apart from other thermal methods—by means of the derivatograph.Our experimental results have contributed to the explanation of the non-pyrophoric behaviour of these catalysts. We demonstrated that the desorption of the hydrogen content in our catalysts is not accompanied by the oxidation of active nickel. This oxidation takes place only at higher temperatures, above 200°C, at a rate proportional to the amount of active nickel.Other constituents of the catalysts (adsorbed water, hydroxide content) were also determined from the experimental data. The outstandingly high Mg(OH)₂ content of the NiMg catalyst indicates that its structure is dissimilar: Mg(OH)₂ also acts as support for the catalyst.     

Stereoselective formation of glycosyl sulfoxides and their subsequent equilibration: ring inversion of an alpha-xylopyranosyl sulfoxide dependent on the configuration at sulfur

A series of four S-allyl D-thiopyranosides, alpha- and beta-manno and xylo, were oxidized with MCPBA at low temperature to give seven of the eight possible sulfoxides, whose configuration at sulfur was determined either directly by X-ray crystallography or by correlation with closely related structures. For the axial thioglycosides oxidation leads very predominantly to the (R)(S)-diastereomer in the xylo series and exclusively so in the manno series; the configuration at C2 is of little importance in determining the stereoselectivity of oxidation of axial thioglycopyranosides. In the equatorial series the configuration at C2 has a significant effect on the outcome of the reaction as, although both series favored the (S)(S)-sulfoxide, selectivity was significantly higher in the case of the beta-mannoside than of the beta-xyloside. The two alpha-xylo sulfoxides have different conformations of the pyranoside ring with the (R)(S)-isomer adopting the (1)C(4) chair and the (S)(S)-diastereomer the (4)C(1). Each pair of diastereomeric sulfoxides was thermally equilibrated in C(6)D(6) and in CD(3)OD. In the mannose series the kinetic isomers are also thermodynamically preferred. In the xylose series, on the other hand, the nature of the thermodynamic isomer in both the alpha- and beta-anomers is a function of solvent with a switch observed on going from C(6)D(6) to CD(3)OD. The results are rationalized in terms of the exo-anomeric effect, steric shielding provided by H3 and H5 in the axial series, the interaction of the C2-O2 and sulfoxide dipoles, and increased steric interactions on hydrogen bonding of the sulfoxides to CD(3)OD.     

ICP-MS determination of heavy metals in submerged cultures of wood-rotting fungi

Accumulation of five heavy metal ions by five species of wood-rotting basidiomycetes during a 9-day cultivation was studied. Contents of Cd, Cu, Pb, and Zn were measured using ICP-MS; the amount of mercury was determined directly in solid samples using the Advanced Mercury Analyser. A standard operation procedure for the sample preparation and determination of metal content was developed and validated. Presence of Cd, Cu, Hg, and Pb decreased the accumulation of zinc by the fungi. The basidiomycete Pycnoporus cinnabarinus exhibited the highest metal binding capacity of all fungi tested.     

Polarography in solution of some problems in organic chemistry: recent applications

Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques.     

Synthesis of 2,2-Dimethyl-1,2-Dihydro-3H-pyrrol-3-one Preliminary Communication

The title compound 3g is obtained via two different routes, either in a multistep synthesis starting from 2-amino-2-methylpropionic acid (methylalanine) or by light-induced, oxidative dealkylation of the corresponding N-isopropyl derivative 3c .     

Labeling vibrations by light: ultrafast transient 2D-IR spectroscopy tracks vibrational modes during photoinduced charge transfer

We report on a novel ultrafast two-dimensional infrared laser experiment that correlates vibrational bands of reactant and product of a photoreaction. The possibilities of this technique are demonstrated for the metal-to-ligand charge transfer (MLCT) in [Re(CO)3Cl(dmbpy)] (dmbpy = 4,4'-dimethyl-2,2'bipyridine) where we correlated the CO vibrational modes of the ground state and the MLCT state. A distinct vibrational mode is excited in the electronic ground state by an infrared laser pulse. This vibrational label survives the subsequent electronic excitation and can be followed in the excited electronic state. It is shown that the order of the vibrational energy levels is not preserved when exciting the molecule as was commonly assumed in the literature.     

High-energy collision-induced dissociation of oxosteroids derivatised to Girard hydrazones

Neutral oxosteroids have been derivatised with Girard T and P hydrazine reagents to give the corresponding Girard hydrazone quaternary ammonium salts. Both Girard T (GT) and Girard P (GP) hydrazones of oxosteroids give very intense [M](+) ion signals in electrospray (ES) mass spectra and fragment within the ES interface and collision cell to give characteristic fragment ions. GT and GP derivatives give informative high-energy collision-induced dissociation spectra, from which the structure of the precursor oxosteroid can be determined. Both charge-remote and charge-mediated mechanisms are responsible for the formation of the fragment ions at high collision-energy.     

Two parameter donor-acceptor approach to solvent effects on the electrode kinetics of cations

A two parameter approach to solvent variations in the electroreduction rate constants of cobalt complexes and europium cations is presented and discussed in terms of solvent—solute and solvent—solvent interactions.

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Ein Zwei-Parameter Donor-Acceptor-Ansatz für Lösungsmitteleffekte bei der Elektrodenkinetik von Kationen (Kurze Mitteilung)

Zusammenfassung Es wird eine Zwei-Parameter-Annäherung der Lösungsmitteleinflüsse auf die Geschwindigkeitskonstanten der Elektroreduktion von Kobalt-Komplexen und Europium-Kationen präsentiert und auf der Basis von Lösungsmittel—gelöster Stoff- und Lösungsmittel—Lösungsmittel-Wechselwirkung diskutiert.