Identification of clusters from reactions of ruthenium arene anticancer complex with glutathione using nanoscale liquid chromatography fourier transform ion cyclotron mass spectrometry combined with <Superscript>18</Superscript>O-labeling

Reactions of the anticancer complex [(eta(6)-bip)Ru(en)Cl](+) (where bip is biphenyl and en is ethylenediamine) with the tripeptide glutathione (gamma-L-Glu-L-Cys-Gly; GSH), the abundant intracellular thiol, in aqueous solution give rise to two ruthenium cluster complexes, which could not be identified by electrospray mass spectrometry (ESI-MS) using a quadrupole mass analyzer. Here we use Fourier transform ion cyclotron mass spectrometry (nanoLC-FT-ICR MS) to identify the clusters separated by nanoscale liquid chromatography as the tetranuclear complex [{(eta(6)-bip)Ru(GSO(2))}(4)](2-) (2) and dinuclear complex [{(eta(6)-bip)Ru(GSO(2))(2)}(2)](8-) (3) containing glutathione sulfinate (GSO(2)) ligands. Use of (18)OH(2) showed that oxygen from water can readily be incorporated into the oxidized glutathione ligands. These data illustrate the power of high-resolution MS for identifying highly charged multinuclear complexes and elucidating novel reaction pathways for metallodrugs, including ligand-based redox reactions.     

Studies on the Reactivity of 4-Acetoxy-3-acylamino-2-azetidinones: Stereospecific trans Carbon-Carbon Bond Formation

The recent publication of Reuschling and co-workers2 on the synthesis of a carbapenem utilizing, as the key step in the sequence, the stereospecific C-C coupling of 3-substituted-acetoxy-2-azetidinones with cuprates, prompts us to report our related work in this area.     

Focus on H/D exchange of proteins in solution

Editorial

Focus on H/D exchange of proteins in solution     

Inert site in a protein zinc cluster: isotope exchange by high resolution mass spectrometry

Using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, we show that one Zn2+ ion in the Zn4 cluster of cyanobacterial metallothionein is inert to exchange with 67Zn2+. We suggest that this is zinc in site A, which together with the surrounding alpha and beta secondary structure forms a zinc-finger fold.     

Monitoring and fast detection of mycotoxin-producing fungi based on headspace solid-phase microextraction and headspace sorptive extraction of the volatile metabolites

Solid phase microextraction in combination with capillary GC-MS was used as monitoring technique for the collection and detection of the fungal volatile metabolite (+)-aristolochene by sporulated surface cultures of Penicillium roqueforti. A comparison was made between different toxigenic and nontoxigenic strains of P. roqueforti. Different growth conditions and media, such as malt extract agar, potato dextrose agar and sabouraud dextrose agar were compared. Whereas toxigenic strains produced large amounts of (+)-aristolochene, beta-elemene, valencene and germacrene A, nontoxigenic P. roqueforti strains showed a remarkably different headspace profile, in which ethyl-2-hexenoate, E-beta-caryophyllene, aromadendrene and beta-patchoulene were the predominant volatiles, apart from other sesquiterpene hydrocarbons present at lower concentrations. Stir bar sorptive extraction, was also applied in the headspace sampling mode, i.e. headspace sorptive extraction (HSSE) for the enrichment of fungal volatiles from sporulated surface cultures to differentiate between toxigenic and nontoxigenic fungi. Hence, it can be concluded that headspace analysis of volatile fungal metabolites by SPME and HSSE in combination with capillary GC-MS is a suitable monitoring technique for the fast detection of mycotoxin producing fungi.