Characterisation of nicotine and related compounds using electrospray ionisation with ion trap mass spectrometry and with quadrupole time-of-flight mass spectrometry and their detection by liquid chromatography/electrospray ionisation mass spectrometry

Electrospray ionisation ion trap mass spectrometry (ESI-MS(n)) has been used to study the fragmentation patterns of nicotine and nine of its related compounds. From this study certain characteristic fragmentations are apparent with generally the pyrrolidine or piperidine ring being subject to chemical modifications. The structures of the product ions proposed for the ESI-MS(n) study have been supported by results from electrospray ionisation quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS). Compounds with pyrrolidine and piperidine rings that possess an unsubstituted N atom have been shown to lose NH(3) at the MS(2) stage. Those compounds with N-methyl groups lose CH(3)NH(2) at the MS(2) stage. The loss of NH(3) or CH(3)NH(2) leaves the corresponding rings opened and this is followed by ring closure at the pyridine-2 carbon atom. Mono-N-oxides fragment in a similar way but the di-N-oxide can also fragment by cleavage of the bond between the pyridine and pyrrolidine rings. Cotinine also can undergo cleavage of this bond between the rings.This data therefore provides useful information on how substituents and the nature of the non-pyridine ring can affect the fragmentation patterns of nicotine and its related compounds. This information can be used in the characterisation of these compounds by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) which results in the separation of nicotine and its related compounds with limits of detection (LODs) ranging from 15 to 105 ng/mL. The use of LC/ESI-MS to study nicotine-containing samples resulted in the simultaneous and unambiguous identification of seven of the compounds discussed in this paper: cotinine identified at retention time 12.5 min (with its [M+H](+) ion at m/z 177), nornicotine 16.0 min (m/z 149), anatabine 18.0 min (m/z 161), myosmine 18.5 min (m/z 147), anabasine 20.4 min (m/z 163), nicotine 22.2 min (m/z 163), and nicotyrine 31.4 min (m/z 159). For quality control of nicotine replacement therapy products, these nicotine impurities can be readily identified and determined at levels up to 0.3% for single impurities and up to 1.0% for total impurities.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.     

Tools for micropatterning epithelial cells into microcolonies on transwell filter substrates

Despite the importance of epithelial tissue in most major organs there have been limited attempts to tissue engineer artificial epithelium. A key feature of mature epithelium is the presence of an apical-basal polarization, which develops over 7-20 days in culture. Currently, the most widely used 2D system to generate polarized epithelium in vitro involves the filter insert culture system, however this system is expensive, laborious and requires large numbers of cells per sample. We have developed a set of micropatterning techniques to spatially control the organization of epithelial cells into microsheets on filter inserts under the culture conditions necessary to induce epithelial cell polarization. Micropatterning improves cell uniformity within each microsheet, allows multiple sheet analysis on one filter insert, and reduced cell number requirements. We describe an agarose patterning method that allows maintenance of cell patterns for over 15 days, the time necessary to induce apical-basal polarization. We also describe a Parafilm? patterning method that allows patterning for 5 to 15 days depending on cell type and only allows the generation of stripes and circular microsheets. The parafilm? method however is extremely straightforward and could be easily adopted by any laboratory without the need of access to specialized microfabrication equipment. We also demonstrate that micropatterning epithelial cells does not alter the localization of the apical-basal marker ZO-1 or the formation of cilia, a marker of epithelium maturation. Our methods provide a novel tool for studying epithelial biology in polarized epithelium microsheets of controlled size.     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.     

The simultaneous analysis of proteins, lipids, and diterpenoid resins found in cultural objects

We report a GC-MS method for the simultaneous analysis of proteins oil, and diterpenoid resins found in cultural objects. The method was initially designed for protein analysis of protenaceous paints and adhesives and involves acid hydrolysis as the first step. The amino acids in the protein hydrolysates, thus obtained, are treated with propan-l-ol/ hydrogen chloride and then pentafluoropropionic anhydride. The procedure was found also to yield the propyl esters of fatty acids derived from lipids and diterpenoid acids derived from natural resins, and thus allows the choice of a single method for the analysis of artists media which contain either oil s or proteins or mixtures of both proteins and oils or even resins. Thus natural mixtures such as egg yolk and also mixtures made by the artist such as animal glue/seed oil emulsions can be analysed. Coupled with FTIR analysis of paints and the staining of cross sections, to indicate layer structure the method can help to elucidate the paints and adhesives used by artists.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

Linear augmented Slater-type orbital method for free standing clusters

We have developed a Scalable Linear Augmented Slater-Type Orbital (LASTO) method for electronic-structure calculations on free-standing atomic clusters. As with other linear methods we solve the Schr?dinger equation using a mixed basis set consisting of numerical functions inside atom-centered spheres and matched onto tail functions outside. The tail functions are Slater-type orbitals, which are localized, exponentially decaying functions. To solve the Poisson equation between spheres, we use a finite difference method replacing the rapidly varying charge density inside the spheres with a smoothed density with the same multipole moments. We use multigrid techniques on the mesh, which yields the Coulomb potential on the spheres and in turn defines the potential inside via a Dirichlet problem. To solve the linear eigen-problem, we use ScaLAPACK, a well-developed package to solve large eigensystems with dense matrices. We have tested the method on small clusters of palladium.