Cathode materials for solid oxide fuel cells: a review

The composition and microstructure of cathode materials has a large impact on the performance of solid oxide fuel cells (SOFCs). Rational design of materials composition through controlled oxygen nonstoichiometry and defect aspects can enhance the ionic and electronic conductivities as well as the catalytic properties for oxygen reduction in the cathode. Cell performance can be further improved through microstructure optimization to extend the triple-phase boundaries. A major degradation mechanism in SOFCs is poisoning of the cathode by chromium species when chromium-containing alloys are used as the interconnect material. This article reviews recent developments in SOFC cathodes with a principal emphasis on the choice of materials. In addition, the reaction mechanism of oxygen reduction is also addressed. The development of Cr-tolerant cathodes for intermediate temperature solid oxide fuel cells, and a possible mechanism of Cr deposition at cathodes are briefly reviewed as well. Finally, this review will be concluded with some perspectives on the future of research directions in this area.     

Performance of a sheathless porous tip sprayer for capillary electrophoresis-electrospray ionization-mass spectrometry of intact proteins

The performance of a prototype porous tip sprayer for sheathless capillary electrophoresis-mass spectrometry (CE-MS) of intact proteins was studied. Capillaries with a porous tip were inserted in a stainless steel needle filled with static conductive liquid and installed in a conventional electrospray ionization (ESI) source. Using a BGE of 100 mM acetic acid (pH 3.1) and a positively charged capillary coating, a highly reproducible and efficient separation of four model proteins (insulin, carbonic anhydrase II, ribonuclease A and lysozyme) was obtained. The protein mass spectra were of good quality allowing reliable mass determination of the proteins and some of their impurities. Sheath-liquid CE-MS using the same porous tip capillary and an isopropanol-water-acetic acid sheath liquid showed slightly lower to similar analyte responses. However, as noise levels increased with sheath-liquid CE-MS, detection limits were improved by a factor 6.5-20 with sheathless CE-MS. The analyte response in sheathless CE-MS could be enhanced using a nanoESI source and adding 5% isopropanol to the BGE, leading to improved detection limits by 50-fold to 140-fold as compared to sheath liquid interfacing using the same capillary - equivalent to sub-nM detection limits for three out of four proteins. Clearly, the sheathless porous tip sprayer provides high sensitivity CE-MS of intact proteins.     

Diffusion of Active Ingredients in Textiles

Most practical textile models are based on a two scale approach: a one-dimensional fiber model and a fabric model, see Fan et al. (Commun Comput Phys 4(4):929–948, 2008). No meso-level is used in between, i.e. the yarn scale is neglected in this setup. For dense textile substrates this seems appropriate as the yarns connect everywhere, but for loose fabrics or scrims this approach cannot be kept. Specifically when one is interested in tracking an active component released by the fibers, the yarn level plays an important role. This is because the saturation vapor pressure will influence the release rate from the fibers, and its value will vary over the yarn cross-section. Therefore, in this work we present a three step multiscale model: the active component is tracked in the fiber, the yarn, and finally at the fabric level. At the fiber level a one-dimensional reduction to a non-linear diffusion equation is performed, and solved on an as needed basis. At the yarn level both a two-dimensional or a one-dimensional model can be applied, and finally the yarn result is upscaled to the fabric level.     

Asteropine A, a sialidase-inhibiting conotoxin-like peptide from the marine sponge Asteropus simplex

Marine sponges contain structurally intriguing and biologically active peptides of nonribosomal peptide synthase origin, often containing amino acids with novel structures. Here we report the discovery of asteropine A (APA), a cystine knot to be isolated from marine sponges. The solution structure of APA as determined by NMR belongs to the four-loop class of cystine knots similar to those of some conotoxins and spider toxins. However, the highly negatively charged surface of APA is uncommon among other cystine knots. APA competitively inhibits bacterial sialidases, but not a viral sialidase. APA was inactive against all other enzymes tested and did not have any apparent antitumor activity. Our data suggest that APA and other knotting peptides may be important leads for antibacterial and even antiviral drug development.     

Control of the electrical conductivity of composites of antimony doped tin oxide (ATO) nanoparticles and acrylate by grafting of 3-methacryloxypropyltrimethoxysilane (MPS)

The effect of the addition of antimony doped tin oxide (ATO) nanoparticles on the electrical conductivity of acrylate films is described. To enable dispersing of ATO in acrylate matrices, 3-methacryloxypropyltrimethoxysilane (MPS) was grafted on the surface of the filler. The amount of MPS used for this surface modification was found to strongly affect the electrical conductivity. Surface modification with a large amount of MPS resulted in colloidally stable dispersions of ATO, leading to a homogeneous distribution. Surface modification with small amounts of MPS led to instable ATO dispersions and aggregation of ATO into a fractal type network, which gives a much higher conductivity especially at low-volume fractions. For composites with a fractal type ATO network a second effect was found. Decreasing the amount of on ATO grafted MPS resulted in an increase of the electrical conduction between the ATO particles.     

Wavelets with patchwise cancellation properties

We construct wavelets on general -dimensional domains or manifolds via a domain decomposition technique, resulting in so-called composite wavelets. With this construction, wavelets with supports that extend to more than one patch are only continuous over the patch interfaces. Normally, this limited smoothness restricts the possibility for matrix compression, and with that the application of these wavelets in (adaptive) methods for solving operator equations. By modifying the scaling functions on the interval, and with that on the -cube that serves as parameter domain, we obtain composite wavelets that have patchwise cancellation properties of any required order, meaning that the restriction of any wavelet to each patch is again a wavelet. This is also true when the wavelets are required to satisfy zeroth order homogeneous Dirichlet boundary conditions on (part of) the boundary. As a result, compression estimates now depend only on the patchwise smoothness of the wavelets that one may choose. Also taking stability into account, our composite wavelets have all the properties for the application to the (adaptive) solution of well-posed operator equations of orders for .

     

Whitney towers and gropes in 4-manifolds

Many open problems and important theorems in low-dimensional topology have been formulated as statements about certain 2-complexes called gropes. This paper describes a precise correspondence between embedded gropes in 4-manifolds and the failure of the Whitney move in terms of iterated `towers' of Whitney disks. The `flexibility' of these Whitney towers is used to demonstrate some geometric consequences for knot and link concordance connected to -solvability, -cobordism and grope concordance. The key observation is that the essential structure of gropes and Whitney towers can be described by embedded unitrivalent trees which can be controlled during surgeries and Whitney moves. It is shown that a Whitney move in a Whitney tower induces an IHX (Jacobi) relation on the embedded trees.

     

Regiochemistry of the Condensation of 2-Aroyl-cyclohexanones and 2-Cyanoacetamide: (13)C-Labeling Studies and Semiempirical MO Calculations

Hydroxy-aryl-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles represent interesting chemical scaffolds, but synthetic access to these compounds is limited. The reaction of 2-aroyl-cyclohexanones with 2-cyanoacetamide and base in ethanol has been reported to lead to the formation of the tetrahydroisoquinoline isomer. We show that depending on the electronic nature of the para-substituent on the aryl ring, formation of the regioisomeric tetrahydroquinoline isomer can significantly compete. The electron-donating or -withdrawing properties of the para-substituent of the aryl ring determines the ratio of product isomers. A series of 2-aroyl-cyclohexanones, with para-substituents ranging from electron-donating to electron-withdrawing, were reacted with [2-(13)C]-cyanoacetamide. The product ratio and absolute regiochemistry were directly determined by quantitative (13)C, HMBC, and NOESY NMR spectroscopy on the reaction mixtures. A clear relationship between the regioisomeric product ratio and the Hammett sigma values of the substituents is demonstrated. This is explained by the separate in situ yields, which reveal that the pathway leading to the tetrahydroquinoline regioisomer is significantly more sensitive toward the electronic nature of the para-substituent than the pathway leading to the tetrahydroisoquinoline. Semiempirical AM1 molecular orbital calculations on the starting electrophile 2-aroyl-cyclohexanone support a correlation between the energy of the LUMOs and the regioisomeric product ratio. Our results facilitate synthetic access to a range of these interesting synthetic intermediates.     

Duality properties of indicatrices of knots

The bridge index and superbridge index of a knot are important invariants in knot theory. We define the bridge map of a knot conformation, which is closely related to these two invariants, and interpret it in terms of the tangent indicatrix of the knot conformation. Using the concepts of dual and derivative curves of spherical curves as introduced by Arnold, we show that the graph of the bridge map is the union of the binormal indicatrix, its antipodal curve, and some number of great circles. Similarly, we define the inflection map of a knot conformation, interpret it in terms of the binormal indicatrix, and express its graph in terms of the tangent indicatrix. This duality relationship is also studied for another dual pair of curves, the normal and Darboux indicatrices of a knot conformation. The analogous concepts are defined and results are derived for stick knots.