Mathematical Model and Numerical Simulation of Conductometric Biosensor of Urea

In this article, a mathematical model was developed to describe and optimize the configuration of the urea biosensor. The biosensor is based on interdigitated gold microelectrodes modified with a urease enzyme membrane. The model presented here focuses on the enzymatic reaction and/or diffusion phenomena that occur in the enzyme membrane and in the diffusion layer. Numerical resolution of differential equations was performed using the finite difference technique. The mathematical model was validated using experimental biosensor data. The responses of the biosensor to various conditions were simulated to guide experiments, improve analytical performance, and reduce development costs.     

Local Structure Analysis and Modelling of Lignin-Based Carbon Composites through the Hierarchical Decomposition of the Radial Distribution Function

Carbonized lignin has been proposed as a sustainable and domestic source of activated, amorphous, graphitic, and nanostructured carbon for many industrial applications as the structure can be tuned through processing conditions. However, the inherent variability of lignin and its complex physicochemical structure resulting from feedstock and pulping selection make the Process-Structure-Property-Performance (PSPP) relationships hard to define. In this work, radial distribution functions (RDFs) from synchrotron X-ray and neutron scattering of lignin-based carbon composites (LBCCs) are investigated using the Hierarchical Decomposition of the Radial Distribution Function (HDRDF) modelling method to characterize the local atomic environment and develop quantitative PSPP relationships. PSPP relationships for LBCCs defined by this work include crystallite size dependence on lignin feedstock as well as increasing crystalline volume fraction, nanoscale composite density, and crystallite size with increasing reduction temperature.     

A multiscale gradient-dependent plasticity model for size effects

The mechanical behaviour of polycrystalline material is closely correlated to grain size. In this study, we investigate the size-dependent phenomenon in multi-phase steels using a continuum dislocation dynamic model coupled with viscoplastic self-consistent model. We developed a dislocation-based strain gradient plasticity model and a stress gradient plasticity model, as well as a combined model, resulting in a theory that can predict size effect over a wide range of length scales. Results show that strain gradient plasticity and stress gradient plasticity are complementary rather than competing theories. The stress gradient model is dominant at the initial strain stage, and is much more effective for predicting yield strength than the strain gradient model. For larger deformations, the strain gradient model is dominant and more effective for predicting size-dependent hardening. The numerical results are compared with experimental data and it is found that they have the same trend for the yield stress. Furthermore, the effect of dislocation density at different strain stages is investigated, and the findings show that the Hall–Petch relation holds for the initial strain stage and breaks down for higher strain levels. Finally, a power law to describe the size effect and the transition zone between the strain gradient and stress gradient dominated regions is developed.     

An intercausal cancellation model for Bayesian-network engineering

When constructing Bayesian networks with domain experts, network engineers often use the noisy-OR model, and causal interaction models more generally, to alleviate the burden of probability elicitation: the use of such a model serves to reduce the number of probabilities to be elicited on the one hand, and on the other hand forestalls experts having to give assessments for probabilities with compound conditions which they feel are hard to envision. Recently, we have shown that ill-considered use of the noisy-OR model specifically can substantially decrease a network's performance, especially in domains in which causal mechanisms include cancellation effects. Motivated by this observation, we designed a new causal interaction model, with the same engineering advantages as the noisy-OR model, to describe such effects. We detail properties of our intercausal cancellation model, and compare it against existing causal interaction models. We further illustrate the application of our model in the real-world domain of pharmacology.     

A generalised model of hydrogen diffusion in metals with multiple trap types

Continuum modelling of hydrogen diffusion in metals, which accounts for both trapping and an imposed force field, is revisited. A generalised model of hydrogen diffusion and trapping is developed as a continuous interpretation of the discrete random-walk theory. A system of nonlinear equations describing the phenomenon of diffusion with multiple types of traps is derived without the assumption of a local equilibrium among hydrogen populations in dissimilar positions. Lattice-trap interchange kinetics can degenerate into local equilibrium as a limit case. Moreover, certain terms in general equations may be negligible in specific situations. By removing these terms, known particularised models of hydrogen diffusion and trapping are recovered. Determining the terms, which are disregarded in reduced models, enables a straightforward assessment of the applicability of these models. The advantages and limitations of particularised models applied to hydrogen embrittlement analyses are discussed.     

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.     

A refined numerical model for determining inflation-burst behavior of composite membrane structures

The airship structures made of multi-layer composite fabrics or membranes can offer the platform for earth observations, wireless communications and space research due to light weight and good mechanical performance. The structural safety and serviceability strongly depend on material properties and working conditions. Available studies are limited within service stress limits or are lack of suitable biaxial tensile constitutive models for understanding structural behavior. This paper thus focuses on a refined numerical model for determining inflation-burst behavior of composite airship structures considering new biaxial constitutive equations, novel failure criteria and manufacture factors.The differences between ideal and real forms of airship structures, e.g. volume difference, demonstrate the necessity for incorporating cutting-pattern effects in the initial numerical model. For structural analysis, stress distributions on real structural forms are different from those on ideal forms because of welding parts that can enhance local stiffness. The ultimate pressures are 56.7 kPa and 59.5 kPa for ideal and real structural forms. Structural breaking initiated at the maximum diameter of ideal structural forms propagates fast while welding parts can prevent breaking propagation for real structural forms. Therefore, the refined numerical model can reveal basic structural behavior and safety performance of airship structures in the inflation-burst processes.     

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.