Fingerprinting of chlorinated paraffins and their transformation products in plastic consumer products.

Chlorinated paraffins (CPs) can be classified according to their length as short-chain (SC, C10-C13), medium-chain (MC, C14-C17) and long-chain (LC, C ≥ 18) CPs. Technical CP-mixtures can contain a wide range of carbon- (C-, nC = 10-30) and chlorine- (Cl-, nCl = 3-19) homologues. CPs are high-production volume chemicals (>106 t/y). They are used as flame-retardants, plasticizers and coolant fluids. Due to the persistence, bioaccumulation, long-range environmental transport potential and adverse effects, SCCPs are regulated as persistent organic pollutants (POPs) by the Stockholm Convention. Transformation of CPs can lead to the formation of unsaturated compounds such as chlorinated mono- (CO), di- (CdiO) and tri-olefins (CtriO). Such transformation reactions can occur at different stages of CP manipulation providing characteristic C-/Cl-homologue distributions. All this results in unique patterns that collectively create a fingerprint, which can be distinguished from CP-containing samples. Therefore, CP-fingerprinting can develop into a promising tool for future source apportionment studies and with it, the reduction of environmental burden of CPs and hazards to humans. Herein, CP-containing plastics were studied to establish fingerprints and develop this method. We analyzed four household items by reverse-phase liquid-chromatography coupled with a mass spectrometer with an atmospheric pressure chemical ionization source and an Orbitrap mass analyzer (RP-LC-APCI-Orbitrap-MS) operated at a resolution of 120000 (FWHM at m/z 200). MS-data of different CP-, CO-, CdiO- and CtriO-homologues were efficiently processed with an R-based automatic mass spectra evaluation routine (RASER). From the 16720 ions searched for, up to 4300 ions per sample were assigned to 340 C-/Cl-homologues of CPs and their transformation products. Specific fingerprints were deduced from the C-/Cl-homologues distributions, the carbon- (nC) and chlorine- (nCl) numbers and saturation degree. These fingerprints were compared with the ones obtained by a GC-ECNI-Orbitrap-MS method.

Characterization of ageing products of ester-based synthetic lubricants by liquid chromatography with electrospray ionization mass spectrometry and by electrospray ionization (tandem) mass spectrometry.

Ageing products of a commercial jet engine oil based on pentaerythritol tetraesters which were formed upon operation in an aviation turbine were detected by electrospray ionization mass spectrometry (ESI-MS) and characterized by LC-ESI-MS. The fatty acid composition of these ageing products was investigated by ESI-MS-MS analysis. The ammonium adducts of the newly formed pentaerythritol tetraester degradation products were found to be suitable parent ions for further structure elucidation work. ESI-MS, LC-ESI-MS and ESI-MS-MS proved to be versatile tools to study the chemical composition (distribution of homologues) as well as the mechanism of ageing of ester based lubricants on a molecular level. Due to its high sensitivity, ESI-MS can also be used to characterize and identify trace levels of ester-based lubricants.

Stabilization of beta-ribbon structures in peptides using disulfide bonds.

The effect of a disulfide crosslink between two peptide chains on the stability of beta-ribbon secondary structures formed by these peptides has been investigated. Based on structural principles, we hypothesized that introduction of an unstrained disulfide crosslink at appropriate locations on two peptide chains should have a stabilizing effect on the beta-ribbon structure formed by these two peptide chains. To test this hypothesis, we designed and synthesized two sets of 9-residue peptides incorporating cysteine in one and (S)-alpha-amino-epsilon-mercaptohexanoic acid in the other. Comparison of the CD data clearly show that the dimer containing a disulfide bond between the longer sidechains of (S)-alpha-amino-epsilon-mercaptohexanoic acid shows dramatically higher beta-ribbon character as compared to the dimer with cystine disulfide bond, thus validating our structural hypothesis.