Product systems over right-angled Artin semigroups

We build upon Mac Lane's definition of a tensor category to introduce the concept of a product system that takes values in a tensor groupoid . We show that the existing notions of product systems fit into our categorical framework, as do the -graphs of Kumjian and Pask. We then specialize to product systems over right-angled Artin semigroups; these are semigroups that interpolate between free semigroups and free abelian semigroups. For such a semigroup we characterize all product systems which take values in a given tensor groupoid . In particular, we obtain necessary and sufficient conditions under which a collection of -graphs form the coordinate graphs of a -graph.     

Synthesis and studies of a tetradecanuclear manganese(II)/(III) cage

A novel Mn14 cluster is reported; this is a new nuclearity for manganese cages and highly unusual in that the ligands are not exclusively oxygen donors.     

Thiol–ene polymerizations using imide‐based monomers

New diene and dithiol monomers, based on aromatic imides such as benzophenone‐3,3′,4,4′‐tetracarboxylic diimide were synthesized and used in thiol‐ene polymerizations which yield poly(imide‐co‐thioether)s. These linear polymers exhibit limited solubility in various organic solvents. The molecular weights of the polymers were found to decrease with increasing imide content. The glass transition temperature (T_g) of these polymers is dependent on imide content, with T_g values ranging from ?55 °C (with no imide) up to 13 °C (with 70% imide). These thermal property improvements are due to the H‐bonding and rigidity of the aromatic imide moieties. Thermal degradation, as studied by thermogravimetric analysis, was not significantly different to the nonimide containing thiol‐ene polymers made using trimethyloylpropane diallyl ether and 3,5‐dioxa‐1,8‐dithiooctane. It is expected that such monomers may lead to increased glass transition temperatures in other thiol‐ene polymer systems as these normally exhibit low glass transition temperatures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4637–4642     

Liquid flow patterns about barbotage bubbles

This paper summarizes the results of a flow visualization study on the liquid motion around barbotage bubbles during growth and departure. Flow patterns, as well as for the first time, instantaneous velocities, are reported as a function of time and location about the bubbles. The experiments, employing the hydrogen-bubble technique and high-speed cine photography, were with: water as the liquid, air as the bubbled gas, orifice diameters of 0.116 and 0.252 cm, and different air flow rates; the two limiting cases of constant supply pressure and constant volumetric flow rate were covered. It was found that the liquid around a barbotage bubble assumes two velocity maxima, the first an outward maximum during bubble growth and the second in the opposite direction approximately at the time of bubble departure; further, liquid velocities were found to be higher close to the bubbling site. Certain differences in liquid velocities between the constant pressure and constant flow cases are explained in terms of available theoretical solutions to the bubble growth rate. Qualitative comparisons of the barbotage liquid flow patterns and those recently reported for boiling flow patterns are also presented.     

Two-phase flow in a horizontal equal-sided impacting tee junction

Pressure-drop and phase-distribution data were generated for air–water flows in a horizontal impacting tee junction. All three sides of the junction (37.8-mm i.d.) were oriented horizontally. The data correspond to a junction pressure of 1.5 bar (abs), ambient temperature, inlet flow regimes of wavy, stratified, and annular, and a wide range of mass splits at the junction. Most of the range for the phase-distribution data corresponds to conditions that were untested in previous investigations. In general, it was found that the phases did not distribute themselves evenly between the two outlets unless the mass split is equal. There is a serious lack of data in the literature on the two-phase pressure drop in impacting tee junctions and therefore, the present data add substantially to the existing data. A mechanistic model capable of predicting the phase distribution and pressure drop was developed and shown to be in general good agreement with the present data and others from the literature.     

Correlation of p16(INK4A) expression and HPV copy number with cellular FTIR spectroscopic signatures of cervical cancer cells

Cervical cancer, a potentially preventable disease, has its main aetiology in infection by high risk human papillomavirus (HR-HPV). Approaches to improving cervical cancer screening and diagnostic methodologies include molecular biological analysis, targeting of biomarker proteins, but also exploration and implementation of new techniques such as vibrational spectroscopy. This study correlates the biomarker protein p16(INK4A) expression levels dependent on HPV copy number with the infrared absorption spectral signatures of the cervical cancer cell lines, HPV negative C33A, HPV-16 positive SiHa and CaSki and HPV-18 positive HeLa. Confocal fluorescence microscopy demonstrated that p16(INK4A) is expressed in all investigated cell lines in both nuclear and cytoplasmic regions, although predominantly in the cytoplasm. Flow cytometry was used to quantify the p16(INK4A) expression levels and demonstrated a correlation, albeit nonlinear, between the reported number of integrated HPV copies and p16(INK4A) expression levels. CaSki cells were found to have the highest level of expression, HeLa intermediate levels, and SiHa and C33A the lowest levels. FTIR spectra revealed differences in nucleic acid, lipid and protein signatures between the cell lines with varying HPV copy number. Peak intensities exhibited increasing tendency in nucleic acid levels and decreasing tendency in lipid levels with increasing HPV copy number, and although they were found to be nonlinearly correlated with the HPV copy number, their dependence on p16(INK4A) levels was found to be close to linear. Principal Component Analysis (PCA) of the infrared absorption spectra revealed differences between nuclear and cytoplasmic spectroscopic signatures for all cell lines, and furthermore clearly differentiated the groups of spectra representing each cell line. Finally, Partial Least Squares (PLS) analysis was employed to construct a model which can predict the p16(INK4A) expression level based on a spectral fingerprint of a cell line, demonstrating the diagnostic potential of spectroscopic techniques.     

Nachweis und Bestimmung des Eisens, sowie seine Trennung von anderen Elementen

Ohne Zusammenfassung     

Synthesis of pallescensin-E : Use of crown ether in the Wadsworth procedure for olefin formation

The furanosesquiterpene, pallescensin-E has been prepared by a route involving reaction of a dimethyl 3-furylmethyl phosphonate anion with 2,3-dimethylbenzaldehyde in the presence of 15-crown-5; this reaction has been shown to have general applicability.     

Marine natural products—XV : Polyhalogenated cyclic monoterpenes from the red alga plocamium cartilagineum of antarctica

Examination of the red alga Plocamium cartilagineum (L.) Dixon collected along the Antarctic Peninsula yielded several new cyclic halogenated monoterpenes. The structures of a 2,4-dichloro-trans-1-chloro-vinyl-1-methyl-5-methylene-cyclohexane, a 2-chloro-4-bromo-trans-1-chlorovinyl-1-methyl-5-methylene-cyclohexane, a 2-chloro-trans-1-chlorovinyl-1-methyl-5-chloromethyl-4-cyclohexene, and a 2,5-dichloro-4-bromo-trans-1-chlorovinyl-1-methyl-5-bromomethyl-cyclohexane are described. The structures were determined by spectroscopic methods and chemically related to the halogenated monoterpene violacene.     

Copper thioether chemistry: The synthesis and single crystal X-ray structures of [Cu2([18]aneS6)(NCMe)2](ClO4)2 and [Cu([9]aneS3)(AsPPh3)](ClO4)

Reaction of [18]aneS₆ with two molar equivalents of [Cu(NCMe)₄](ClO₄) in CH₂Cl₂-MeCN affords the binuclear copper(I) complex [Cu₂([18]aneS₆)(NCMe)₂](ClO₄)₂. The single crystal X-ray structure of the complex shows a centrosymmetric cation with two tetrahedral copper(I) centres each coordinated to three thioether S-donors of [18]aneS₆,Cu---S(1) = 2.3200(15), Cu---S(4) = 2.3415(16), Cu---S(7) = 2.3250(15) Å, and to one MeCN molecule, Cu---N(1) = 1.939(5) Å, to give an overall NS₃-donation at the metal centres. Additionally, S(7′) shows a long-range interaction, Cu …S(7′) = 3.318(2) Å thus distorting the coordination geometry of the metal ion towards trigonal bipyramidal. The metal-metal separation of 4.428(2) Å suggests that there is no significant interaction between the copper centres of the dimer. Reaction of [9]aneS₃ with one molar equivalent of [Cu(NCMe)₄](ClO₄) in refluxing MeCN in the presence of ligands, L, affords the adducts [Cu([9]aneS₃)L]⁺ (L = PPh₃, AsPh₃). The single crystal X-ray structure of the complex [Cu([9]aneS₃)(AsPh₃)](ClO₄) shows tetrahedral AsS₃ coordination at copper(I) with [9]aneS₃ bound facially to the metal centre, Cu---S = 2.303(6), Cu---As = 2.322(4) Å.