Identification of an aliphatic epoxide and the corresponding dihydrodiol as novel congeners of zearalenone in cultures of Fusarium graminearum.

The mycotoxin zearalenone (ZEN) is produced by various Fusarium fungi and frequently found as a contaminant in food and feed. There are reports in the literature that several closely related analogues of ZEN are also formed in cultures of Fusarium species. We have therefore analyzed the organic extract from a 40 day culture of Fusarium graminearum by LC-DAD-MS and detected 15 compounds, which could be congeners of ZEN because of their ultraviolet, mass spectroscopy, and tandem mass spectroscopy spectra. In addition to confirming the previously reported α- and ß-stereoisomers of 5-hydroxy-ZEN and 10-hydroxy-ZEN, we identified seven ZEN congeners for the first time. One of the major novel congeners was shown by nuclear magnetic resonance spectroscopy and chemical synthesis to have the structure of an aliphatic ZEN epoxide, whereas two minor products proved to be the corresponding dihydrodiols. In addition, three stereoisomers of a cyclization product of the dihydrodiols, carrying a spiro-acetal group, were identified as fungal products for the first time. The latter may be artifacts, because the ZEN epoxide and dihydrodiol are unstable under acidic conditions and rearrange easily to the spiro-acetal compounds.

Nanoparticulate functional materials.

Nanoparticulate functional materials offer manifold perspectives for the increasing miniaturization and complexity of technical developments. Nanoparticles also make a major contribution to utilization of materials that is sparing of natural resources. Besides these obvious aspects, however, the importance of nanoparticles is due to their fundamentally novel properties and functions. These include photonic crystals and efficient luminophors, single particles and thin films for electronic storage media and switching elements, magnetic fluids and highly selective catalysts, a wide variety of possibilities for surface treatments, novel materials and concepts for energy conversion and storage, contrast agents for molecular biology and medical diagnosis, and fundamentally novel forms and structures of materials, such as nanocontainers and supercrystals. Creating high-quality nanoparticles requires that numerous parameters, involving the particle core and surface, colloidal properties, and particle deposition, are taken into consideration during synthesis of the material. An appropriate characterization and evaluation of the properties requires the incorporation of a wide range of expertise from widely differing areas. These circumstances are what challenges and appeals to the nanoscientist.

Stereoelectronic effects in cyclic sulfoxides, sulfones, and sulfilimines: application of the Perlin effect to conformational analysis.

The 1JC--H coupling constants in conformationally constrained sulfoxides, bissulfoxides, sulfoxide-sulfones, and sulfilimines derived from 2-benzylidene-1,3-dithiane and 2-(2,2-dimethylpropylidene)-1,3-dithiolane were measured by means of HMQC and HSQC NMR experiments and the Perlin effects were calculated. The type and the relative configuration of S==X groups (X= O, NTos) in these compounds have a strong influence on the magnitude of coupling constants for axial and equatorial C--H bonds, respectively. Axial S==O bonds give rise to a stereoelectronic effect on antiperiplanar axial C--H bonds. The resultant weakening of the respective C--H bonds leads to a smaller coupling constant than for a respective equatorial C--H bond. Equatorial S==O groups have an influence on beta-C--H bonds through a homoanomeric effect. Here, the axial C--H bond is weakened and a smaller coupling constant is measured. Sulfilimine groups show similar effects to sulfoxide groups.

4-[(3-chlorophenyl)diazenyl]-2-([tris(hydroxymethyl)methyl]aminomethylene)cyclohexa-3,5-dien-1(2H)-one.

The title compound, C(17)H(18)ClN(3)O(4), adopts the keto-amine tautomeric form and displays an intramolecular N-H...O hydrogen bond [N...O = 2.639 (2) A]. The configuration around the azo N=N double bond is trans, and the dihedral angle between the planes of the two aromatic rings is 20.5 (2) degrees. The molecules are linked by O-H...O hydrogen bonds to form a three-dimensional network.

A Novel Method for the Demetalation of Tricarbonyliron-Diene Complexes by a Photolytically Induced Ligand Exchange Reaction with Acetonitrile.

The photochemical exchange of all three carbonyl ligands with acetonitrile converts tricarbonyliron-diene complexes into the very labile triacetonitrile-iron-diene complexes. These easily demetalate in high yields to the corresponding free ligands on injection of air at -30°C [Eq. (1)]. The novel demetalation procedure is applied to the tricarbonyliron complexes of cyclopentadienones, cyclohexa-1,3-dienes, and buta-1,3-dienes.

Demetalation of Tricarbonyl(cyclopentadienone)iron Complexes Initiated by a Ligand Exchange Reaction with NaOH-X-Ray Analysis of a Complex with Nearly Square-Planar Coordinated Sodium.

A sequential exchange of one carbonyl ligand by a hydrido ligand with NaOH, and then by an iodo ligand with iodopentane and finally treatment with acid transforms tricarbonyl(η4-cyclopentadienone)iron complexes into dicarbonyl(η5-hydroxycyclopentadienyl)iodoiron complexes. These iodo complexes demetalate with high selectivity to the corresponding free ligands on contact with air in daylight. Under basic reaction conditions at the stage of the iodo complex an anionic dicarbonyl(η4-cyclopentadienone)iodoiron complex is generated, which is dimeric in the solid state and has an almost square-planar arrangement of the ligands at the sodium counterion.