Humidity dependence of carbon dioxide generation during photodegradation of biaxially oriented polypropylene in oxygen

UV generation of CO₂ gas from a range of biaxially oriented polypropylene (BOPP) films exposed in oxygen gas has been measured by in situ infrared spectrometry and compared with the development of absorption at 1713 cm⁻¹ due to carbonyl formation in the same films. As in studies of other polyalkene films, the CO₂ measurements, which take only 3 h, correlate well with carbonyl development measurements that require hundreds of hours.Upon UV irradiation of BOPP in dry oxygen an induction time of ∼60 min preceded a linear increase of photogenerated CO₂. In wet oxygen, no noticeable induction time preceded the linear increase of CO₂. The rate of CO₂ increase was greater when the oxygen was humidified. This pattern was observed for four different types of film and for films of different thickness. The increase in the rate of CO₂ photogeneration with increased humidity was greater for thicker films. The correlation between the amount of CO₂ generated and the strength of the carbonyl absorption developed under standard conditions was better for BOPP oxidation in dry than in humidified oxygen. The inclusion of recycled polymer caused an increase in the rate of photodegradation.Although measurements on each subset of films demonstrated a clear increase in the photogeneration of CO₂ at high humidity, the mechanism by which the CO₂ generation from BOPP is enhanced remains unclear and further work is necessary to resolve this puzzle.     

Controlled thermo-catalytic modification of regenerated cellulosic fibres using magnesium chloride Lewis acid

The Lewis-acid catalytic reactions of magnesium chloride with regenerated cellulosic fibres under baking conditions can be interpreted using existing semi-crystalline morphological models. Reaction at 180 °C is associated with chain scission, which takes place randomly within the accessible regions of the fibre structure. This causes a rapid reduction in the cellulose degree of polymerization, which stabilizes at a limiting value, analogous to that observed with wet-state mineral acid catalysed hydrolysis. A slower scission-reaction is also observed, believed to be due to the liberation of single glucan units from crystallite ends, again analogous to wet-state mineral acid hydrolysis. Dry-state catalysis is promoted by thermal molecular motion, allowing migration of catalyst ions and also conformational flexing of the cellulose polymer, which also induces a small amount of recrystallisation at crystallite lateral surfaces. Differences in the dry-state reaction have been observed for lyocell, viscose and modal regenerated fibres, which can be related to differences in crystallinity and resulting accessibility of the magnesium chloride catalyst. For lyocell the accessibility towards magnesium chloride is lower than found with mineral acids, which may be significant in the development of treatments to promote mechanical fibrillation, without sacrificing fibre tensile properties.     

Selective on-line serum peptide extraction and multidimensional separation by coupling a restricted-access material-based capillary trap column with nanoliquid chromatography–tandem mass spectrometry

As the serum peptidome gets increasing attention for biomarker discovery, one of the important issues is how to efficiently extract the peptides from highly complex human serum for peptidome analysis. Here we developed a fully automated platform for direct injection, on-line extraction, multidimensional separation and MS detection of peptides present in human serum. A capillary SPE column packed with a novel mix mode restricted access material (RAM) exhibiting strong cation exchange and size exclusion chromatography (SCX/SEC) properties were coupled with a nanoliquid chromatography–mass spectrometry (nanoLC-MS) system. The capillary SPE column excludes the high abundant serum proteins such as HSA by size exclusion chromatography and simultaneously extracts the low molecular weight peptides by binding to sulfonic acid residues. Subsequently, the trapped peptides are eluted to a capillary LC column packed with a RP-C18 stationary phase. After injection of only 2 μL human serum to the one-dimensional nanoLC-MS system around 400 peptides could be identified. When conducting a multidimensional separation, the described SCX/SEC/RP-MS platform allows the separation and identification of 1286 peptides present in human serum by the injection and on-line processing of 20 μL human serum sample.     

Reversible Storage of Lithium in a Rambutan‐Like Tin–Carbon Electrode

Fruity electrodes : A simple bottom‐up self‐assembly method was used to fabricate rambutan‐like tin–carbon (Sn@C) nanoarchitecture (see scheme, green Sn) to improve the reversible storage of lithium in tin. The mechanism of the growth of the pear‐like hairs is explored.

     

Clifford Product and Lorentzian Plane Displacements In 3-Dimensional Lorentzian Space

In this paper, by defining Clifford algebra product in 3-dimensional Lorentz space, L ³, it is shown that even Clifford algebra of L ³ corresponds to split quaternion algebra. Then, by using Lorentzian matrix multiplication, pole point of planar displacement in Lorentz plane L ² is obtained. In addition, by defining degenerate Lorentz scalar product for L ³ and by using the components of pole points of Lorentz plane displacement in particular split hypercomplex numbers, it is shown that the Lorentzian planar displacements can be represented as a special split quaternion which we call it Lorentzian planar split quaternion.      

Thermal effects in orthotropic porous elastic beams

This paper is concerned with the linear theory of anisotropic porous elastic bodies. The extension and bending of orthotropic porous elastic cylinders subjected to a plane temperature field is investigated. The work is motivated by the recent interest in the using of the orthotropic porous elastic solid as model for bones and various engineering materials. First, the thermoelastic deformation of inhomogeneous beams whose constitutive coefficients are independent of the axial coordinate is studied. Then, the extension and bending effects in orthotropic cylinders reinforced by longitudinal rods are investigated. The three-dimensional problem is reduced to the study of two-dimensional problems. The method is used to solve the problem of an orthotropic porous circular cylinder with a special kind of inhomogeneity.      

On graphs determining links with maximal number of components via medial construction

Let G be a connected plane graph, D(G) be the corresponding link diagram via medial construction, and μ(D(G)) be the number of components of the link diagram D(G). In this paper, we first provide an elementary proof that μ(D(G))≤n(G)+1, where n(G) is the nullity of G. Then we lay emphasis on the extremal graphs, i.e. the graphs with μ(D(G))=n(G)+1. An algorithm is given firstly to judge whether a graph is extremal or not, then we prove that all extremal graphs can be obtained from K₁ by applying two graph operations repeatedly. We also present a dual characterization of extremal graphs and finally we provide a simple criterion on structures of bridgeless extremal graphs.     

Invertible and nilpotent matrices over antirings

In this paper, we characterize invertible matrices over an arbitrary commutative antiring S with 1 and find the structure of GL_n(S). We find the number of nilpotent matrices over an entire commutative finite antiring. We prove that every nilpotent n×n matrix over an entire antiring can be written as a sum of ⌈log₂n⌉ square-zero matrices and also find the necessary number of square-zero summands for an arbitrary trace-zero matrix to be expressible as their sum.     

The heat of formation of chlorine-isocyanate and the relative stability of isoelectronic molecules: an experimental and theoretical study

Accurate thermochemical data of small molecules are invaluable to the progress of every aspect of chemistry, especially in the atmosphere, combustion and industry. In this work, photofragmentation translational spectroscopy and 1st principles electronic structure theory reveal the literature value of the heat of formation of chlorine-isocyanate to be in error by more than 40 kcalmol. We report a revised experimental value for D0(Cl-NCO) = 51+/-3 kcal/mol which leads to a Delta Hf (ClNCO) = 8.5+/-3 kcal/mol. High level ab initio (CCSD(T)) electronic structure calculations extrapolated to the complete basis set limit give D0(Cl-NCO) = 6.3 kcal/mol, in good agreement with experiment. In light of the present results, the destabilization of azides relative to isoelectronic isocyanates has been evaluated empirically for three pairs of related molecules. It is found to be 90-110 kcal/mol, and has been attributed mainly to the weakening of the N-NN bond relative to the N-CO bond. Electronic structure calculations employing decomposition analysis suggest that, compared to homopolar N2, the (+delta)CO(-delta) pi polarity provides better orbital interaction (charge transfer) and electrostatic attraction and results in a closer encounter and larger stabilization between the fragments and that this is the origin of isoelectronic destabilization of azides relative to the isocyanates.