Graph-theoretic formalization of hybridization in DNA sticker complexes

Sticker complexes are a formal graph-based data model for a restricted class of DNA complexes, motivated by potential applications to databases. This data model allows for a purely declarative definition of hybridization. We introduce the notion of terminating hybridization, which intuitively means that only a finite number of different products can be generated. We characterize this notion in purely graph-theoretic terms. Under a finite alphabet, each product is shown to be of polynomial size. Yet, terminating hybridization can still produce results of exponential size, in that there may be exponentially many different (nonisomorphic) finished products. We indicate a class of complexes where hybridization is guaranteed to be polynomially bounded.     

Inverse modelling of an aneurysm’s stiffness using surrogate-based optimization and fluid-structure interaction simulations

Characterization of the mechanical properties of arterial tissues is highly relevant. In this work, we apply an inverse modelling approach to a model accounting for an aneurysm and the distal part of the circulation which can be modified using two independent stiffness parameters. For given values of these parameters, the position of the arterial wall as a function of time is calculated using a forward simulation which takes the fluid-structure interaction (FSI) into account. Using this forward simulation, the correct values of the stiffness parameters are obtained by minimizing a cost function, which is defined as the difference between the forward simulation and a measurement. The minimization is performed by means of surrogate-based optimization using a Kriging model combined with the expected improvement infill criterion. The results show that the stiffness parameters converge to the correct values, both for a zero-dimensional and for a three-dimensional model of the aneurysm.     

Stress-assisted crystallisation in anodic titania

The relationship between the microstructural and internal stress evolution during Ti anodising is discussed. Samples anodised galvanostatically to 12 V and 40 V, corresponding to different stages of the internal stress evolution, were examined by in-plane and cross-section transmission electron microscopy. Electron diffraction patterns have been complemented with stoichiometry data obtained from energy loss near edge structure spectra. The sample anodised to 40 V was observed to consist of two regions, with a crystallised inner region adjacent to the metal/oxide interface. Crystallisation of this region is associated with the presence of large compressive internal stresses which build up during anodising up to 12 V.     

A systematic methodology for kinetic modeling of chemical reactions applied to n‐hexane hydroisomerization

Kinetic modeling provides chemical engineers with a unique opportunity to better understand reaction kinetics in general and the underlying chemistry in particular. How to systematically approach a modeling assignment in chemical reaction kinetics is typically less clear, especially for novices in the field. The proposed modeling methodology pursues an adequate compromise between statistical significance and physical meaning of the kinetic model and the corresponding parameters and typically results in models of an appropriate complexity. It comprises the following activities: (1) data analysis, aiming at qualitative information on the reaction mechanism and corresponding rate equations, (2) model regression to quantify this information via optimal parameter values, and (3) validation of the statistical significance and physical meaning of the parameter estimates. This methodology is successfully applied to n‐hexane hydroisomerization on a bifunctional catalyst. © 2014 American Institute of Chemical Engineers AIChE J, 61: 880–892, 2015     

Thiol Redox and pKa Properties of Mycothiol,the Predominant Low‐Molecular‐Weight Thiol Cofactor in the Actinomycetes

The thiol pK_a and standard redox potential of mycothiol, the major low‐molecular‐weight thiol cofactor in the actinomycetes, are reported. The measured standard redox potential reveals substantial discrepancies in one or more of the other previously measured intracellular parameters that are relevant to mycothiol redox biochemistry.     

A Novel Technology for Natural Gas Conversion by Means of Integrated Oxidative Coupling and Dry Reforming of Methane

A novel process concept for the oxidative coupling of methane followed by the oligomerization to liquids has been developed within the frame of the EU integrated project OCMOL. This technology is based on process intensification principles via cutting‐edge structured microreactor technology. It is also a fully integrated industrial process through the re‐use and the recycling of by‐products, in particular CO₂, at every process stage. The focus of this contribution is on the reaction engineering aspects of the core steps, i.e., catalysts, kinetics and reactor design for the methane coupling and reforming.     

Chemical Stability of α‐Tocopherol in Colloidal Lipid Particles with Various Morphologies

Colloidal lipid particles (CLPs) are promising encapsulation systems for lipophilic bioactives, such as oil‐soluble antioxidants that are applied in food and pharmaceutical formulations. Currently, there is no clear consensus regarding the relation between particle structure and the chemical stability of such bioactives. Using α‐tocopherol as a model antioxidant, it is shown that emulsifier type (Tween 20 or 40, or sodium caseinate) and lipid composition (tripalmitin, tricaprylin, or combinations thereof) modulated particle morphology and antioxidant stability. The emulsifier affects particle shape, with the polysorbates facilitating tripalmitin crystallization into highly ordered lath‐like particles, and sodium caseinate resulting in less ordered spherical particles. The fastest degradation of α‐tocopherol is observed in tripalmitin‐based CLPs, which may be attributed to its expulsion to the particle surface induced by lipid crystallization. This effect is stronger in CLPs stabilized by Tween 40, which may act as a template for crystallization. This work not only shows how the architecture of CLPs can be controlled through the type of lipid and emulsifier used, but also gives evidence that lipid crystallization does not necessarily protect entrapped lipophilic bioactives, which is an important clue for encapsulation system design. Practical Applications: Interest in enriching food and pharmaceutical products with lipophilic bioactives such as antioxidants through encapsulation in lipid particles is growing rapidly. This research suggests that for efficient encapsulation, the particle architecture plays an important role; to tailor this, the contribution of both the lipid carrier and the emulsifier needs to be considered.     

Microbially mediated phosphine emission

There is still a lot of controversy in literature concerning the question whether a biochemical system exists enabling micro-organisms to reduce phosphate to phosphine gas. The search for so-called 'de novo synthesised' phosphine is complicated by the fact that soils, slurries, sludges, etc., which are often used as inocula, usually contain matrix bound phosphine (MBP). Matrix bound phosphine is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. A study was carried out to compare the different digestion methods, used to transform matrix bound phosphine into phosphine gas. It was demonstrated that caustic and acidic digestion methods should be used to measure the matrix bound phosphine of the inoculum prior to inoculation to avoid false positive results concerning de novo synthesis. This is especially true if anthropogenically influenced inocula possibly containing minute steel or aluminium particles are used. The comparative study on different digestion methods also revealed that the fraction of phosphorus in mild steel, converted to phosphine during acid corrosion depended on the temperature. Following these preliminary studies, anaerobic growth experiments were set up using different inocula and media to study the emission of phosphine gas. Phosphine was detected in the headspace gases and its quantity and timeframe of emission depended on the medium composition, suggesting microbially mediated formation of the gas. The amount of phosphine emitted during the growth experiments never exceeded the bound phosphine present in inocula, prior to inoculation. Hence, de novo synthesis of phosphine from phosphate could not be demonstrated. Yet, microbially mediated conversion to phosphine of hitherto unknown reduced phosphorus compounds in the inoculum was evidenced.     

Investigation on germanium oxide-based glasses for infrared optical fibre development

We demonstrate the suitability of GeO₂ for fibre engineering by compositional modifications of core and cladding glasses using the rod-in-tube technique, which have been matched for fibre drawing. The methods adopted for identifying the core–clad combination (56GeO₂–31PbO–9Na₂O–4Ga₂O₃ and 55GeO₂–30PbO–11Na₂O–4Ga₂O₃) are explained, based on the thermal, viscosity, and optical properties. We specially point out to the relatively high transformation temperature range (T_g > 380 °C) of the glass, which is suitable for chemical sensing and metrological applications in the 150–200 °C. The total intrinsic loss is compared with the measured loss in multi- and single-mode fibres from 0.532 to 2.02 μm, with loss less than 2.5 dB m⁻¹ in the 1000–1600 nm range. The origin of larger loss outside this region is explained.