Oxygen Sorption and Desorption Properties of Selected Lanthanum Manganites and Lanthanum Ferrite Manganites

Temperature‐programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid‐oxide fuel cell (SOFC) cathode materials (La_0.85Sr_0.15)_0.95MnO_3+δ (LSM) and La_0.60Sr_0.40Fe_0.80Mn_0.20O_3‐δ (LSFM). The powders were characterized by X‐ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second‐order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate‐determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re‐adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order.     

Integral relations for the heat and mass transfer resistivities of the liquid–vapor interface

We derived integral relations for the heat and mass transfer resistivities of the liquid–vapor interface in a one-component system. These relations were obtained assuming the validity of the standard expression for the local entropy production rate as the product of the measurable heat flux times the gradient of the inverse temperature through the surface. The integral relations will be useful to interpret results from nonequilibrium molecular dynamics simulations. We verified in this paper that earlier results obtained using the nonequilibrium van der Waals square gradient model are reproduced. For this case, we calculated the Kapitza length along the coexistence curve.     

Optimal flux patterns in cellular metabolic networks

The availability of whole-cell-level metabolic networks of high quality has made it possible to develop a predictive understanding of bacterial metabolism. Using the optimization framework of flux balance analysis, I investigate the metabolic response and activity patterns to variations in the availability of nutrient and chemical factors such as oxygen and ammonia by simulating 30,000 random cellular environments. The distribution of reaction fluxes is heavy tailed for the bacteria H. pylori and E. coli, and the eukaryote S. cerevisiae. While the majority of flux balance investigations has relied on implementations of the simplex method, it is necessary to use interior-point optimization algorithms to adequately characterize the full range of activity patterns on metabolic networks. The interior-point activity pattern is bimodal for E. coli and S. cerevisiae, suggesting that most metabolic reactions are either in frequent use or are rarely active. The trimodal activity pattern of H. pylori indicates that a group of its metabolic reactions (20%) are active in approximately half of the simulated environments. Constructing the high-flux backbone of the network for every environment, there is a clear trend that the more frequently a reaction is active, the more likely it is a part of the backbone. Finally, I briefly discuss the predicted activity patterns of the central carbon metabolic pathways for the sample of random environments.     

Mapping Enzyme Activity on Tissue by Functional Mass Spectrometry Imaging

Enzymes are central components of most physiological processes, and are consequently implicated in various pathologies. High‐resolution maps of enzyme activity within tissues therefore represent powerful tools for elucidating enzymatic functions in health and disease. Here, we present a novel mass spectrometry imaging (MSI) method for assaying the spatial distribution of enzymatic activity directly from tissue. MSI analysis of tissue sections exposed to phospholipid substrates produced high‐resolution maps of phospholipase activity and specificity, which could subsequently be compared to histological images of the same section. Functional MSI thus represents a new and generalisable method for imaging biological activity in situ.     

Parallel nanoliter detection of cancer markers using polymer microchips

A general multipurpose microchip technology platform for point-of-care diagnostics has been developed. Real-time nucleic acid sequence-based amplification (NASBA) for detection of artificial human papilloma virus (HPV) 16 sequences and SiHa cell line samples was successfully performed in cyclic olefin copolymer (COC) microchips, incorporating supply channels and parallel reaction channels. Samples were distributed into 10 parallel reaction channels, and signals were simultaneously detected in 80 nl volumes. With a custom-made optical detection unit, the system reached a sensitivity limit of 10(-6) microM for artificial HPV 16 sequences, and 20 cells microl(-1) for the SiHa cell line. This is comparable to the detection limit of conventional readers, and clinical testing of biological samples in polymer microchips using NASBA is therefore possible.     

3-Halotetrahydropyran-4-one Derivatives from Homopropargyl Acetal

A gold(I)-catalyzed regioselective method for the preparation of 3-bromo/iodo-tetrahydropyran-4-one derivatives from homopropargyl acetal is reported. A one-pot procedure based on a gold(I)-catalyzed Petasis–Ferrier rearrangement/cyclization and subsequent electrophilic halogenation was developed. Corresponding hemiacetals were not suitable substrates for the formation of the 3-halo-pyran derivatives. The present transformation is a useful method to readily afford highly substituted 3-halo-tetrahydropyran-4-ones, which are suitable substrates in a variety of reactions in further synthesis.     

Crosslinking and alkyl substitution in nano-structured grafted fluoropolymer for use as proton-exchange membranes in fuel cells

In order to develop cheaper and better fuel-cell electrolyte membranes than the polyperfluorosulfonic acids, an effort has been made to improve the fuel-cell relevant properties of sulfonated styrene/divinylbenzene-grafted poly(ethylene-alt-tetrafluoroethylene) membranes. Thus the influence of the crosslinking agent divinylbenzene has been investigated and its amount optimized. Substitution of styrene by methylstyrene and t-butylstyrene has been performed with the purpose of improving the chemical stability of the membranes. Grafting with a fraction of divinylbenzene in the order of 1–2 vol-% of the total monomers has been found to be the best compromise between high grafting yield, good chemical stability, and high proton conductivity of the final membrane. The use of methylstyrene and t-butylstyrene as grafting monomers instead of styrene results in substantially increased chemical stability, with reasonable proton conductivity still being possible to obtain.     

Simplices rarely contain their circumcenter in high dimensions

Acute triangles are defined by having all angles less than π/2, and are characterized as the triangles containing their circumcenter in the interior. For simplices of dimension n ≥ 3, acuteness is defined by demanding that all dihedral angles between (n?1)-dimensional faces are smaller than π/2. However, there are, in a practical sense, too few acute simplices in general. This is unfortunate, since the acuteness property provides good qualitative features for finite element methods. The property of acuteness is logically independent of the property of containing the circumcenter when the dimension is greater than two. In this article, we show that the latter property is also quite rare in higher dimensions. In a natural probability measure on the set of n-dimensional simplices, we show that the probability that a uniformly random n-simplex contains its circumcenter is 1/2 ⁿ .