Feedstock flexibility in sustainable chemistry: Bridging sectors still not sufficiently familiar with each other – Showcases of ongoing and emerging initiatives

The replacement of the fossil resources historically employed for chemicals' production is of major scientific interest the last decades, as a result of the environmental issues arisen and the price versatility of petroleum. Biotechnological routes present promising alternatives for the production of various platform chemicals such as succinic, lactic and muconic acids among others. The utilisation of agricultural and agro-industrial waste and by-product streams would not only reduce the overall production cost but also it would assist towards the direction of the bio-economy era. This review presents some important chemicals produced from renewable feedstocks, aiming to bridge the waste suppliers to the chemical production industries.     

Symmetry and the golden ratio in the analysis of a regular pentagon

The regular pentagon had a symbolic meaning in the Pythagorean and Platonic philosophies and a subsequent important role in Western thought, appearing also in arts and architecture. A property of regular pentagons, which was probably discovered by the Pythagoreans, is that the ratio between the diagonal and the side of these pentagons is equal to the golden ratio. Here, we will study some relations existing between a regular pentagon and this ratio. First, we will focus on the group of fivefold rotational symmetry, to find the position in the complex plane of the vertices of this geometric figure. Then, we will propose an analytic method to solve the same problem based on the Cartesian coordinates, a method where we find the golden ratio without any specific geometric consideration. This study shows a comparison of the use of complex numbers, symmetries and analytic methods, applied to a subject which can be interesting for general education in mathematics. In fact, the proposed approach can convey and link several concepts, requiring only a general pre-college education, showing at the same time the richness that mathematics can offer in solving geometric problems.     

Mathematical modelling and the learning trajectory: tools to support the teaching of linear algebra

In this article we present a didactic proposal for teaching linear algebra based on two compatible theoretical models: emergent models and mathematical modelling. This proposal begins with a problematic situation related to the creation and use of secure passwords, which leads students toward the construction of the concepts of spanning set and span. The objective is to evaluate this didactic proposal by determining the level of match between the hypothetical learning trajectory (HLT) designed in this study with the actual learning trajectory in the second experimental cycle of an investigation design-based research more extensive. The results show a high level of match between the trajectories in more than half of the conjectures, which gives evidence that the HLT has supported, in many cases, the achievement of the learning objective, and that additionally mathematical modelling contributes to the construction of these linear algebra concepts.     

Coupled SPH and Phase Field method for hydraulic fracturing

Simulation of fracture initiation and propagation using classical mesh-based methods involves computationally expensive operations for pre-processing and (adaptive) remeshing of complex geometries. To overcome the difficulties we propose to use a Smoothed Particle Hydrodynamics (SPH) method to model hydraulic fracturing. SPH is a meshless Lagrangian method highly suitable for large deformations [1]. The present contribution discusses a numerical approach to model fractures initiation and propagation, by coupling SPH with the Phase Field method [2]. The proposed hybrid method overcomes the instability problems that can present SPH due to kernel incompleteness. We first validate the proposed model with a stationary elastic fracture and compare the results with the classical SPH to the SPH-Phase Field approach. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanocomposite Polymer Electrolytes of Sodium Alginate and Montmorillonite Clay

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na⁺)- or lithium (SCa-3-Li⁺)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na⁺ and SCa-3-Li⁺ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na⁺ clay presented the highest conductivity of 1.96 × 10⁻² S/cm², and Alg with 10 wt% of SCa-3-Li⁺ showed conductivity of 1.30 × 10⁻² S/cm², both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.     

One-Pot and Two-Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D-Labeled Derivatives

Acetylene surrogates are efficient tools in modern organic chemistry with largely unexplored potential in the construction of heterocyclic cores. Two novel synthetic paths to 3,6-disubstituted pyridazines were proposed using readily available acetylene surrogates through flexible C₂ unit installation procedures in a common reaction space mode (one-pot) and distributed reaction space mode (two-chamber): (1) an interaction of 1,2,4,5-tetrazine and its acceptor-functionalized derivatives with a CaC₂−H₂O mixture performed in a two-chamber reactor led to the corresponding pyridazines in quantitative yields; (2) [4+2] cycloaddition of 1,2,4,5-tetrazines to benzyl vinyl ether can be considered a universal synthetic path to a wide range of pyridazines. Replacing water with D₂O and vinyl ether with its trideuterated analog in the developed procedures, a range of 4,5-dideuteropyridazines of 95–99% deuteration degree was synthesized for the first time. Quantum chemical modeling allowed to quantify the substituent effect in both synthetic pathways.     

Walk of a Line Defect in Quasicrystals

Quasicrystalline alloys are quasiperiodic aggregates in which local atomic changes (phason activity) influence prominently the gross deformative behavior. The effects of these rearrangements on a line defect are analyzed here. Balances of standard and phason interactions are derived along the line together with the balance of actions driving eventually it the former are found to be covariant while the latter follows from a requirement of invariance with respect to the action of the group of isochoric diffeomorphisms. The results can be applied to the analysis of dislocations in quasicrystals.     

Force–displacement relationship in micro-metric pantographs: Experiments and numerical simulations

In this paper, we reveal that the mathematical discrete model of Hencky type, introduced in [1], is appropriate for describing the mechanical behavior of micro-metric pantographic elementary modules. This behavior does not differ remarkably from what has been observed for milli-metric modules, as we prove with suitably designed experiments. Therefore, we conclude that the concept of pantographic microstructure seems feasible for micro-metrically architected microstructured (meta)materials as well. These results are particularly indicative of the possibility of fabricating materials that can have an underlying pantographic microstructure at micrometric scale, so that its unique behavior can be exploited in a larger range of technological applications.     

Weighted Cumulative Past Extropy and Its Inference

This paper introduces and studies a new generalization of cumulative past extropy called weighted cumulative past extropy (WCPJ) for continuous random variables. We explore the following: if the WCPJs of the last order statistic are equal for two distributions, then these two distributions will be equal. We examine some properties of the WCPJ, and a number of inequalities involving bounds for WCPJ are obtained. Studies related to reliability theory are discussed. Finally, the empirical version of the WCPJ is considered, and a test statistic is proposed. The critical cutoff points of the test statistic are computed numerically. Then, the power of this test is compared to a number of alternative approaches. In some situations, its power is superior to the rest, and in some other settings, it is somewhat weaker than the others. The simulation study shows that the use of this test statistic can be satisfactory with due attention to its simple form and the rich information content behind it.