Current dependence of grain boundary magnetoresistance in La_0.67Ca_0.33MnO_3 films

We prepared epitaxial ferromagnetic manganite films on bicrystal substrates by pulsed laser ablation. Their low- and high-field magnetoresistance (MR) was measured as a function of magnetic field, temperature and current. At low temperatures hysteretic changes in resistivity up to 70% due to switching of magnetic domains at the coercitive field are observed. The strongly non-ohmic behavior of the current-voltage leads to a complete suppression of the MR effect at high bias currents with the identical current dependence at low and high magnetic fields. We discuss the data in view of tunneling and mesoscale magnetic transport models and propose an explicit dependence of the spin polarization on the applied current in the grain boundary region.Comment: 5 pages, to appear in J. Appl. Phy

Chemical Transformation Motifs - Modelling Pathways as Integer Hyperflows

We present an elaborate framework for formally modelling pathways in chemical reaction networks on a mechanistic level. Networks are modelled mathematically as directed multi-hypergraphs, with vertices corresponding to molecules and hyperedges to reactions. Pathways are modelled as integer hyperflows and we expand the network model by detailed routing constraints. In contrast to the more traditional approaches like Flux Balance Analysis or Elementary Mode analysis we insist on integer-valued flows. While this choice makes it necessary to solve possibly hard integer linear programs, it has the advantage that more detailed mechanistic questions can be formulated. It is thus possible to query networks for general transformation motifs, and to automatically enumerate optimal and near-optimal pathways. Similarities and differences between our work and traditional approaches in metabolic network analysis are discussed in detail. To demonstrate the applicability of the mathematical framework to real-life problems we first explore the design space of possible non-oxidative glycolysis pathways and show that recent manually designed pathways can be further optimised. We then use a model of sugar chemistry to investigate pathways in the autocatalytic formose process. A graph transformation-based approach is used to automatically generate the reaction networks of interest

Inferring Chemical Reaction Patterns Using Rule Composition in Graph Grammars

Modeling molecules as undirected graphs and chemical reactions as graph rewriting operations is a natural and convenient approach tom odeling chemistry. Graph grammar rules are most naturally employed to model elementary reactions like merging, splitting, and isomerisation of molecules. It is often convenient, in particular in the analysis of larger systems, to summarize several subsequent reactions into a single composite chemical reaction. We use a generic approach for composing graph grammar rules to define a chemically useful rule compositions. We iteratively apply these rule compositions to elementary transformations in order to automatically infer complex transformation patterns. This is useful for instance to understand the net effect of complex catalytic cycles such as the Formose reaction. The automatically inferred graph grammar rule is a generic representative that also covers the overall reaction pattern of the Formose cycle, namely two carbonyl groups that can react with a bound glycolaldehyde to a second glycolaldehyde. Rule composition also can be used to study polymerization reactions as well as more complicated iterative reaction schemes. Terpenes and the polyketides, for instance, form two naturally occurring classes of compounds of utmost pharmaceutical interest that can be understood as "generalized polymers" consisting of five-carbon (isoprene) and two-carbon units, respectively

Generic Strategies for Chemical Space Exploration

Computational approaches to exploring "chemical universes", i.e., very large sets, potentially infinite sets of compounds that can be constructed by a prescribed collection of reaction mechanisms, in practice suffer from a combinatorial explosion. It quickly becomes impossible to test, for all pairs of compounds in a rapidly growing network, whether they can react with each other. More sophisticated and efficient strategies are therefore required to construct very large chemical reaction networks. Undirected labeled graphs and graph rewriting are natural models of chemical compounds and chemical reactions. Borrowing the idea of partial evaluation from functional programming, we introduce partial applications of rewrite rules. Binding substrate to rules increases the number of rules but drastically prunes the substrate sets to which it might match, resulting in dramatically reduced resource requirements. At the same time, exploration strategies can be guided, e.g. based on restrictions on the product molecules to avoid the explicit enumeration of very unlikely compounds. To this end we introduce here a generic framework for the specification of exploration strategies in graph-rewriting systems. Using key examples of complex chemical networks from sugar chemistry and the realm of metabolic networks we demonstrate the feasibility of a high-level strategy framework. The ideas presented here can not only be used for a strategy-based chemical space exploration that has close correspondence of experimental results, but are much more general. In particular, the framework can be used to emulate higher-level transformation models such as illustrated in a small puzzle game

Ferroelectricity and structure of BaTiO3 grown on YBa2Cu3O7-d thin films

We have investigated the crystal structure and the ferroelectric properties of BaTiO3 thin films with YBa2Cu3O7-d as the bottom and Au as the top electrode. Epitaxial heterostructures of YBa2Cu3O7-d and BaTiO3 were prepared by dc and rf sputtering, respectively. The crystal structure of the films was characterised by x-ray diffraction. The ferroelectric behaviour of the BaTiO3 films was confirmed by hysteresis loop measurements using a Sawyer Tower circuit. We obtain a coercive field of 30 kV/cm and a remanent polarisation of 1.25 \muC/cm. At sub-switching fields the capacitance of the films obeys a relation analogous to the Rayleigh law. This behaviour indicates an interaction of domain walls with randomly distributed pinning centres. At a field of 5 MV/m we calculate 3% contribution of irreversible domain wall motion to the total dielectric constant.Comment: 12 pages and 9 figure