Determination of eleven coccidiostats in animal feed by liquid chromatography-tandem mass spectrometry at cross contamination levels

A confirmatory multi-residue method has been developed to allow for the detection, confirmation and quantification of eleven coccidiostats in animal feed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method can be used to determine halofuginone, robenidine, nicarbazin, diclazuril, decoquinate, semduramicin, lasalocid, monensin, salinomycin, narasin, maduramicin at levels relating to unavoidable carry over as stated in Regulation 2009/8/EC. Feed samples are extracted with water and acetonitrile with the addition of anhydrous magnesium sulphate and sodium chloride. The extract then undergoes a freezing out step before being diluted and injected onto the LC-MS/MS system. The LC-MS/MS system is run in MRM mode with both positive and negative electrospray ionisation and can confirm all eleven analytes in a run time of 19 min. The sensitivity of the method allows quantification and confirmation for all coccidiostats at a 0.5% carry over level. The method was validated over three days in accordance with of European legislation; Commission Decision 2002/657/EC. Validation criteria of accuracy, precision, decision limit (CCα), and detection capability (CCβ) along with measurement uncertainty are calculated for all analytes. The method was then successfully used to analyse a number of feed samples that contained various coccidiostat substances.     

Evaluation of ‘east-to-west’ ether-forming strategies for the total synthesis of maoecrystal V

Model systems that evaluated different approaches to construct the central ether ring of maoecrystal V are described. Our first model systems attempted the ether formation using C–H functionalization reactions, which led to interesting rearrangements but none of the desired ether product. An intramolecular conjugate addition strategy was then explored that successfully formed the targeted C–O bond but resulted in the undesired stereochemistry.     

Monte-Carlo based background reduction and shielding optimisation for a large hyper-pure germanium detector

The performance of a radiation shielding system for a hyper-pure germanium detector has been characterised for Terrestrial radiation sources, Cosmic muons, X-ray fluorescence and the Compton scattering of source photons. Several methods to reduce the background seen are quantified, including increasing the inner radius of the Pb cave, and increasing the thickness of the shielding. Substantial improvements in the reduction of fluorescence X-rays are found to be achievable by modifying the liner thicknesses used. Increasing the Sn liner from 1.5 to 2.5 mm will increase the shielding of Pb X-rays from 95 to 99.5 %. Reducing the Cu liner from 1.0 to 0.5 mm maintains a 99.5 % level of shielding for Sn/Cd X-rays, however it greatly reduces the amount of Compton scattering of source photons into the detector (a process that is shown to cause an order of magnitude more events in the background than X-ray fluorescence). Cosmic muons were found to increase the amount of background radiation seen, both through direct interaction and the production of secondary radiation. The Cosmic muon contribution, however, was found to produce a much smaller effect than that caused by Terrestrial radiation and Compton scattered photons/fluorescence from the source. The total level of background radiation entering the detector chamber was found to decrease up to the full 200 mm of Pb shielding simulated.     

Study of interference in a double-slit without walls by plasmon tomography techniques

We investigate the free propagation of two parallel surface plasmon polaritons (SPP) beams using plasmon tomography. In the Fourier-plane images, we observed interference features that are not in correspondence with the images of SPPs on the sample's surface. We clearly observed that the interference maxima and minima are distributed over an arc of a circle. We explain the characteristics of the observed interference patterns assuming that each SPP beam can be considered as a “slit without walls”. We discuss important implications of this work for SPP tomography and interferometric plasmonic sensors.     

Spin and the honeycomb lattice: lessons from graphene

A model of electrons hopping from atom to atom in graphene's honeycomb lattice gives low-energy electronic excitations that obey a relation formally identical to a 2+1 dimensional Dirac equation. Graphene's spin equivalent, "pseudospin," arises from the degeneracy introduced by the honeycomb lattice's two inequivalent atomic sites per unit cell. Previously it has been thought that the usual electron spin and the pseudospin indexing the graphene sublattice state are merely analogues. Here we show that the pseudospin is also a real angular momentum. This identification explains the suppression of electron backscattering in carbon nanotubes and the angular dependence of light absorption by graphene. Furthermore, it demonstrates that half-integer spin like that carried by the quarks and leptons can derive from hidden substructure, not of the particles themselves, but rather of the space in which these particles live.     

Can amorphous nuclei grow crystalline clathrates? The size and crystallinity of critical clathrate nuclei

Recent studies reveal that amorphous intermediates are involved in the formation of clathrate hydrates under conditions of high driving force, raising two questions: first, how could amorphous nuclei grow into crystalline clathrates and, second, whether amorphous nuclei are intermediates in the formation of clathrate crystals for temperatures close to equilibrium. In this work, we address these two questions through large-scale molecular simulations. We investigate the stability and growth of amorphous and crystalline clathrate nuclei and assess the thermodynamics and kinetic factors that affect the crystallization pathway of clathrates. Our calculations show that the dissociation temperature of amorphous clathrates is just 10% lower than for the crystals, facilitating the formation of metastable amorphous intermediates. We find that, at any temperatures, the critical crystalline nuclei are smaller than critical amorphous nuclei. The temperature dependence of the critical nucleus size is well described by the Gibbs-Thomson relation, from which we extract a liquid-crystal surface tension in excellent agreement with experiments. Our analysis suggests that at high driving force the amorphous nuclei may be kinetically favored over crystalline nuclei because of lower free energy barriers of formation. We investigated the role of the initial structure and size of the nucleus on the subsequent growth of the clathrates, and found that both amorphous and sI crystalline nuclei yield crystalline clathrates. Interestingly, growth of the metastable sII crystal polymorph is always favored over the most stable sI crystal, revealing kinetic control of the growth and indicating that a further step of ripening from sII to sI is needed to reach the stable crystal phase. The latter results are in agreement with the observed metastable formation of sII CO(2) and CH(4) clathrate hydrates and their slow conversion to sI under experimental conditions.     

Atomic-scale characterization of graphene grown on copper (100) single crystals

Growth of graphene on copper (100) single crystals by chemical vapor deposition has been accomplished. The atomic structure of the graphene overlayer was studied using scanning tunneling microscopy. A detailed analysis of moire? superstructures present in the graphene topography reveals that growth occurs in a variety of orientations over the square atomic lattice of the copper surface. Transmission electron microscopy was used to elucidate the crystallinity of the grown graphene. Pristine, defect-free graphene was observed over copper steps, corners, and screw dislocations. Distinct protrusions, known as "flower" structures, were observed on flat terraces, which are attributed to carbon structures that depart from the characteristic honeycomb lattice. Continuous graphene growth also occurs over copper adatoms and atomic vacancies present at the single-crystal surface. The copper atom mobility within vacancy islands covered with suspended graphene sheets reveals a weak graphene-substrate interaction. The observed continuity and room-temperature vacancy motion indicates that copper mobility likely plays a significant role in the mechanism of sheet extension on copper substrates. Lastly, these results suggest that the quality of graphene grown on copper substrates is ultimately limited by nucleation at the surface of the metal catalyst.     

Molecular orientation and optical luminescence properties of soluble star shaped oligothiophene molecules for organic electronic applications

Angle resolved near-edge absorption fine structure measurements of the C 1s edge of a film of the star-shaped molecule 4(HPBT) show a high degree of order, with the molecules maintaining a largely planar geometry in an upright configuration. X-ray excited optical luminescence measurements showed a dependence of the luminescence spectrum on the excitation energy, with (0–0), (0–1), and (0–2) vibrational modes being clearly visible when exciting off-resonance; the appearance of these features under off-resonance is attributed to a scattering process that is quenched when the excitation approaches a core absorption resonance. The HOMO–LUMO gap is estimated from the luminescence measurements (2.28 eV), and this value is confirmed by the comparison of the C 1s absorption and C Kα emission spectra.     

Stereocontrolled Syntheses of Tetralone‐ and Naphthyl‐Type Lignans by a One‐Pot Oxidative [3,3] Rearrangement/Friedel–Crafts Arylation

The development of a stereoselective one‐pot oxidative [3,3] sigmatropic rearrangement/Friedel–Crafts arylation that provides enantioenriched benzhydryl compounds is reported. The utility of this new transformation is demonstrated by the concise synthesis of several tetralone‐ and naphthyl‐type lignan natural products, many of which display anti‐malarial activity.