Signal suppression/enhancement in high-performance liquid chromatography tandem mass spectrometry

The review discusses the pitfalls of the matrix effect in mass spectrometry detection hyphenated to liquid chromatography separation. Matrix effect heavily influences both qualitative and quantitative analyses, giving rise to suppression or enhancement of the signal. As generally recognised, the predominant cause is the presence of undesired components that co-elute in the chromatographic separation and alter the ionisation process. The interfering species can be components of the sample, compounds released during the pre-treatment/extraction process or reagents added to the mobile phase to improve chromatographic resolution. The different mechanisms proposed in literature to explain the suppression or the enhancement of the signal both in electrospray and atmospheric pressure chemical ionisations are presented and the results observed in the different experimental conditions are compared and discussed. All data together lead to conclude that the chemical properties of the target analyte, the kind of matrix, the matrix to analyte concentration ratio, the extraction process, the chromatographic conditions as well as the kind of the mass spectrometry instrumentation and the ionisation conditions can play a role. Likely all these potential causes act in a synergic way and the final effect observed is hardly due to only one of them. Depending on an unpredictable combination of conditions, signal suppression or enhancement can be observed. The review discusses the matrix effects observed in HPLC–MS and HPLC–MS/MS analysis proposes hypotheses to explain the observed behaviours and proposes methods and strategies to overcome the matrix effects.     

The generating graph of some monolithic groups

For a finite group G let Γ(G) denote the graph defined on the non-identity elements of G in such a way that two distinct vertices are connected by an edge if and only if they generate G. We look for conditions on the positive integer m that ensure that Γ(G) contains a Hamiltonian cycle when G=S?Cm is the wreath product of a finite simple group S and a cyclic group of order m.     

Enhancing the Peroxygenase Activity of a Cofactor-Independent Peroxyzyme by Directed Evolution Enabling Gram-Scale Epoxide Synthesis

Peroxygenases selectively incorporate oxygen into organic molecules making use of the environmentally friendly oxidant H₂O₂ with water being the sole by-product. These biocatalysts can provide ‘green’ routes for the synthesis of enantioenriched epoxides, which are fundamental intermediates in the production of pharmaceuticals. The peroxyzyme 4-oxalocrotonate tautomerase (4-OT), catalysing the epoxidation of a variety of α,β-unsaturated aldehydes with H₂O₂, is outstanding because of its independence from any cost-intensive cofactor. However, its low-level peroxygenase activity and the decrease in the enantiomeric excess of the corresponding α,β-epoxy-aldehydes under preparative-scale conditions is limiting the potential of 4-OT. Herein we report the directed evolution of a tandem-fused 4-OT variant, which showed an ∼150-fold enhanced peroxygenase activity compared to 4-OT wild type, enabling the synthesis of α,β-epoxy-aldehydes in milligram- and gram-scale with high enantiopurity (up to 98 % ee) and excellent conversions. This engineered cofactor-independent peroxyzyme can provide new opportunities for the eco-friendly and practical synthesis of enantioenriched epoxides at large scale.     

Synthesis and characterization of high-molecular-weight syndiotactic amorphous polypropylene

Heterocycle-fused titanium indenyl silylamido dimethyl complexes produce very high molecular weight polypropylene having a prevailingly syndiotactic microstructure with syndiotactic pentad contents rrrr up to 40-55% (sam-PP). The samples are basically amorphous and may slowly develop a low level of crystallinity (16-20%) at room temperature. A structural characterization has shown that sam-PP samples crystallize in disordered modifications of the helical form I of syndiotactic polypropylene (s-PP). The stretching of compression-molded films of sam-PP samples produce oriented crystalline fibers in the trans-planar mesomorphic form of s-PP. The low stereoregularity prevents the formation of the ordered trans-planar form III of s-PP, which instead is obtained in stretched fibers of the highly stereoregular and crystalline s-PP. The trans-planar mesomorphic form, obtained in stretched fibers, in turn transforms into the helical form I upon releasing the tension. The analysis of the mechanical properties has shown that sam-PP samples show good elastic behavior in a large range of deformation with remarkable strength, due to the presence of crystallinity. A comparison with the mechanical properties of less syndiotactic and fully amorphous samples is reported. These fully amorphous samples present lower strength and experience rapid viscous flow of the chains at high deformations and/or by application of stresses for long times. The higher strength in the semicrystalline sam-PP samples makes these materials interesting thermoplastic elastomers showing high toughness and ductility.