Fumonisin mycotoxins which are hazardous to humans and animals were produced in a Fusarium verticillioides-infected solid rice culture. To decrease the possibility of the formation of artifacts, the fumonisins were analysed by reversed-phase high-performance liquid chromatography/electrospray ionization time-of-flight (RP-HPLC/ESI-TOFMS) and ion trap mass spectrometry (RP-HPLC/ESI-ITMS) immediately after the extraction of the culture material, without any further sample clean-up. The fumonisin isomers were separated by using a flat gradient on a special, high-coverage C(18), narrow-bore HPLC column (YMC-Pack J'sphere ODS H80) suggested for the separation of structural isomers by the manufacturer. Exact mass measurements (TOFMS) of the protonated molecules and extraction of the ion chromatogram corresponding to the empirical formula (C(34)H(59)NO(15)) of FB(1) toxins led to the identification of 29 peaks and shoulders, including those of FB(1). The FB(1) toxin and 28 of its isomers were also detected by ITMS after separation with RP-HPLC. The characteristic m/z values of the product ions, including the backbones obtained by ITMS(2), undoubtedly indicated the structures of the FB(1) isomers for 28 peaks and shoulders. In the MS(2) spectra of the protonated molecules of the FB(1) isomers, with some exceptions, 15 characteristic product ions including the hydrocarbon backbone at m/z 299 were observed. The abundance ratio of the cation at m/z 299 ranged up to 5.8%. The relative quantities of the isomers found in the sample extract were expressed as percentages of the FB(1) content (0.001-0.579%). The total amount of the 28 FB(1) isomers was 2.803% of the quantity of FB(1) that is important from the aspect of food and feed safety.
Inherently chiral dinuclear rhodium complexes have been synthesized from the well-known dirhodium(II)-acetate and chiral/achiral amino acids. These complexes have a twisted paddlewheel structure due to axial chirality. Chiral induction could be observed when the ligands were chiral, opposite to the case of achiral ligands, where a racemic mixture was formed. The racemic mixture was separated by chiral HPLC-ECD. The stereochemical properties of these complexes were determined by VCD spectroscopy supported by theoretical calculations at the DFT level. We present a simple route to determine the absolute configuration by an exciton chirality method using VCD spectroscopy.
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