High resolution orbitrap mass spectrometry in comparison with tandem mass spectrometry for confirmation of anabolic steroids in meat

A prominent trend which has been observed in recent years in the analysis of veterinary drugs and growth-promoting agents is the shift from target-oriented procedures, mainly based on liquid chromatography coupled to triple-quadrupole mass spectrometry (LC-QqQ-MS), towards accurate mass full scan MS (such as time of flight (ToF) and Fourier Transform (FT) Orbitrap MS). In this study the applicability of high resolution single-stage-Orbitrap-MS for confirmatory analysis of growth-promoting agents in meat was compared to that of a QqQ-MS. Validation according to CD 2002/657/EC demonstrated that steroid analysis based on Orbitrap MS, operating at a resolution of 50,000 FWHM, is indeed capable to compete with QqQ-MS in terms of selectivity/specificity, while providing excellent linearity (for most compounds >0.99) but somewhat inferior sensitivity. Indeed, CC_αs reached from 0.04–0.88 μg kg⁻¹ for the 34 anabolic steroids upon MS/MS detection, while upon Orbitrap MS detection a range of 0.07–2.50 μg kg⁻¹ was observed. Using QqQ-MS adequate precision was obtained since relative standard deviations, associated with the repeatability and intra-laboratory reproducibility, were below 20%. In the case of Orbitrap MS, for some compounds (i.e. some estrogens) this threshold was exceeded and thus poor precision was observed, which is possibly caused by the lack in sensitivity. Overall, it may be concluded that Orbitrap-MS offers an adequate performance in terms of linearity and precision but lacks in sensitivity for some of the compounds.     

Surfactant Hydrogels for the Dispersion of Carbon‐Nanotube‐Based Catalysts

Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru₄POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media.     

Panchromatic ruthenium sensitizer based on electron-rich heteroarylvinylene π-conjugated quaterpyridine for dye-sensitized solar cells

The first example of a heteroarylvinylene π-conjugated quaterpyridine Ru(II) sensitizer (N1044) was synthesized and used in dye-sensitized solar cells; the dye has an effective panchromatic absorption band, covering the entire visible spectrum up to the NIR region, and superior electrochemical characteristics (HOMO/LUMO and bandgap energies) with respect to previous representative Ru(II) bi- and quaterpyridine sensitizers. A record IPCE curve ranging from 360 to 920 nm has been measured with a maximum of 65% at 646 nm and still 33% efficiency at 800 nm; this leads to substantially increased photocurrent (19.2 mA cm(-2)) when compared to the prototype N719 Ru(II) sensitizer.     

Liquid crystal orientation in elliptic droplets in nematic emulsions

Elliptic droplets of nematic liquid crystal dispersed in a fluid organic monomer were obtained by phase separation from an isotropic mixture consisting of an organic monomer and a nematic liquid crystal contained in a poly(ethylene terephthalate) cell with inner surfaces treated with rubbed polyimide. The elliptic shape is a consequence of the constraint upon droplet growth along the direction perpendicular to the cell surfaces owing to the small thickness. Then, the resulting droplets will have a contact area with the inner surfaces of the cell treated with polyimide, which will impart a planar orientation on the liquid crystal in the droplet. By means of an optical microscope, using a simple pin hole of 5 μ m, we have selected single droplets for a series of samples having different contact areas. By polarized infrared spectroscopy we have also studied the liquid crystal orientation in selected areas of the droplets. We then report the dependence of the order parameter of the liquid crystal on different contact areas with the alignment surface of the cell. The good degree of planar alignment of the liquid crystal in the elliptic droplets allows the use of such a technique for realizing electro-optical films operating in the reverse mode. We report the electro-optical transmission of reverse mode films with different sizes of elliptic droplet.     

The electro‐optical properties of ‘charged’ PDLCs

The application of high intensity electric fields to polymer dispersed liquid crystal (PDLC) films can induce changes in their electro‐optical properties and morphology. In particular, a quasilinear electro‐optical response to an external electric field can be achieved if an internal built‐in d.c. field is induced. In this work, we show how the liquid crystal/polymer weight ratio influences the electro‐optical response of ‘charged’ PDLCs, i.e. of PDLC films after the application of a high intensity electric field. We observed that a quasilinear electro‐optical response can be achieved in a well determined range of composition. Larger liquid crystal concentrations are unable to maintain the built‐in field, while PDLCs with lower liquid crystal loadings do not allow the onset of a built‐in d.c. field.     

New Chemistry of α-Silyl Vinylsulfides

α-Silyl Vinylsulfides, obtained in a stereoselective manner through enethiolizable silyl thioketones, can be used for the synthesis of vinylsulfides and vinylsilane with a specific geometry, and for the preraration of bicyclic and open chain thiofunzionalized enones.