Determination of Benzo[a]pyrene in smoking-flavour agents (water-soluble liquid smoke) by second derivative constant-wavelength synchronous spectrofluorimetry

We have developed a simple, rapid, inexpensive method for the determination of benzo[a]pyrene (BP, a known carcinogen) in smoking-flavour agents (water-soluble liquid smoke; WSLS). After purification of the WSLS by a single passage through a Sep Pak C18 Plus cartridge, BP in the hexane eluate was determined by second derivative constant-wavelength synchronous spectrofluorimetry. Method precision (RSD < 6%) and recovery ( approximately 92%) were satisfactory, and the detection and quantification limits (1.05 and 2.28 mug kg(-1) respectively) indicated that the current maximum permissible concentration of BP in smoke flavourings (10 mug kg(-1)) can be monitored by this method.     

Extraction based on the flow-injection principle : Part 6. Film formation and dispersion in liquid—liquid segmented flow extraction systems

The dispersion mechanism in flow-injection extraction systems has been investigated. The phase with the highest affinity for the tubing material forms a thin film on the wall (e.g., 0.055 mm in a 0.7-mm i.d. PTFE tube with pentanol/water at a flow velocity of 11 cm s^?1). The film thickness increases linearly with increasing flow velocity and can be related to the viscosity/interfacial tension ratio in such a way that a low ratio indicates a thin film. The analyte is extracted into the film and into the adjacent segments. The film is stationary relative to the moving segments and this results in a backward transport of analyte molecules giving rise to dispersion. The thicker the film, the larger the dispersion. By decreasing the tube diameter and the flow velocity, lower dispersion results. Minimum dispersion is obtained for systems in which the phase carrying the analyte does not form the film.     

Chemoselective hydrosilylation of hydroxyketones

A chemoselective method for the hydrosilylation of ketones has been developed, using the combination of triphenylsilane and a catalyst prepared from Ni(COD)₂ and the simple N-heterocyclic carbene IMes. The most notable feature of this method is that free hydroxyls are largely unaffected, thus providing a simple one-step procedure for the conversion of hydroxyketones to mono-protected diols, wherein the protecting group is exclusively installed on the ketone-derived hydroxyl. The process is typically high yielding with both simple ketones and more complex hydroxyketone substrates.     

Local Hartree–Fock orbitals using a three‐level optimization strategy for the energy

Using the three‐level energy optimization procedure combined with a refined version of the least‐change strategy for the orbitals—where an explicit localization is performed at the valence basis level—it is shown how to more efficiently determine a set of local Hartree–Fock orbitals. Further, a core–valence separation of the least‐change occupied orbital space is introduced. Numerical results comparing valence basis localized orbitals and canonical molecular orbitals as starting guesses for the full basis localization are presented. The results show that the localization of the occupied orbitals may be performed at a small computational cost if valence basis localized orbitals are used as a starting guess. For the unoccupied space, about half the number of iterations are required if valence localized orbitals are used as a starting guess compared to a canonical set of unoccupied Hartree–Fock orbitals. Different local minima may be obtained when different starting guesses are used. However, the different minima all correspond to orbitals with approximately the same locality. © 2013 Wiley Periodicals, Inc.     

Crystal Engineering of Supramolecular 1,4-Benzene Bisamides by Side-Chain Modification – Towards Tuneable Anisotropic Morphologies and Surfaces

Benzene bisamides are promising building blocks for supramolecular nano-objects. Their functionality depends on morphology and surface properties. However, a direct link between surface properties and molecular structure itself is missing for this material class. Here, we investigate this interplay for two series of 1,4-benzene bisamides with symmetric and asymmetric peripheral substitution. We elucidated the crystal structures, determined the nano-object morphologies and derived the wetting behaviour of the preferentially exposed surfaces. The crystal structures were solved by combining single-crystal and powder X-ray diffraction, solid-state NMR spectroscopy and computational modelling. Bulky side groups, here t-butyl groups, serve as a structure-directing motif into a packing pattern, which favours the formation of thin platelets. The use of slim peripheral groups on both sides, in our case linear perfluorinated, alkyl chains, self-assemble the benzene bisamides into a second packing pattern which leads to ribbon-like nano-objects. For both packing types, the preferentially exposed surfaces consist of the ends of the peripheral groups. Asymmetric substitution with bulky and slim groups leads to an ordered alternating arrangement of the groups exposed to the surface. This allows the hydrophobicity of the surfaces to be gradually altered. We thus identified two leitmotifs for molecular packings of benzene bisamides providing the missing link between the molecular structure, the anisotropic morphologies and adjustable surface properties of the supramolecular nano-objects.     

Analysis of the Lipidome of Xenografts Using MALDI-IMS and UHPLC-ESI-QTOF

Human tumor xenografts in immunodeficient mice are a very popular model to study the development of cancer and to test new drug candidates. Among the parameters analyzed are the variations in the lipid composition, as they are good indicators of changes in the cellular metabolism. Here, we present a study on the distribution of lipids in xenografts of NCI-H1975 human lung cancer cells, using MALDI imaging mass spectrometry and UHPLC-ESI-QTOF. The identification of lipids directly from the tissue by MALDI was aided by the comparison with identification using ESI ionization in lipid extracts from the same xenografts. Lipids belonging to PCs, PIs, SMs, DAG, TAG, PS, PA, and PG classes were identified and their distribution over the xenograft was determined. Three areas were identified in the xenograft, corresponding to cells in different metabolic stages and to a layer of adipose tissue that covers the xenograft.

Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers

A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C₆₀ moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C₆₀. Electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C₆₀ moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C₆₀ and C₆₀–BPTTF‐C₆₀ dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C₆₀.