Evaluation of the degree of rate control via automatic differentiation

The degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate-limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady-state and transient kinetics. Furthermore, we illustrate a hybrid local-global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high-quality results efficiently.     

Design of Trehalose-Based Amide/Sulfonamide C-type Lectin Receptor Signaling Compounds

Mincle agonists have been shown to induce inflammatory cytokine production, such as tumor necrosis factor-alpha (TNF) and promote the development of a Th1/Th17 immune response that might be crucial to development of effective vaccination against pathogens such as Mycobacterium tuberculosis. As an expansion of our previous work, a library of 6,6′-amide and sulfonamide α,α-d -trehalose compounds with various substituents on the aromatic ring was synthesized efficiently in good to excellent yields. These compounds were evaluated for their ability to activate the human C-type lectin receptor Mincle by the induction of cytokines from human peripheral blood mononuclear cells. A preliminary structure–activity relationship (SAR) of these novel trehalose diamides and sulfonamides revealed that aryl amide-linked trehalose compounds demonstrated improved activity and relatively high potency cytokine production compared to the Mincle ligand trehalose dibehenate adjuvant (TDB) and the natural ligand trehalose dimycolate (TDM) inducing dose-dependent and human-Mincle-specific stimulation in a HEK reporter cell line.     

Biofortification with selenium and lithium improves nutraceutical properties of major winery grapes in the Midwestern United States

Enriching the micronutrients, selenium (Se) and lithium (Li), in grapes to improve their nutraceutical properties were implemented by foliar application of organic fertiliser rich in Se and Li onto five grape cultivars. The effects of this biofortification on vine vigour, fruit quality, overall micronutrients and phenolic compounds also were investigated. Agronomic biofortification was found greatly increased the Se and Li content in the whole grape by multiple times, meanwhile it did not significantly affect the vine vigour and fruit quality of grapes. However, the biofortification did impact the Ionome (including all the mineral nutrients and trace elements) and phenolic compounds in grapes and this varied among cultivars. This study demonstrated foliar spray of organic Se/Li fertiliser was a very effective strategy to biofortify these micronutrients in grape berries, particularly in the skin, and therefore might be a promising strategy to increase the consumption and awareness of these grapes.     

Short-Term Creep of St3 Steel Under Low-Frequency Cyclic Loading

Strength of Materials - Creep constitutive equations have been derived for the materials that exhibit the properties of orthotropy (transversal isotropy) and transient creep under cyclic loading. A...     

Mixture ratio modeling of dynamic systems

Any knowledge extraction relies (possibly implicitly) on a hypothesis about the modelled-data dependence. The extracted knowledge ultimately serves to a decision-making (DM). DM always faces uncertainty and this makes probabilistic modelling adequate. The inspected black-box modeling deals with “universal” approximators of the relevant probabilistic model. Finite mixtures with components in the exponential family are often exploited. Their attractiveness stems from their flexibility, the cluster interpretability of components and the existence of algorithms for processing high-dimensional data streams. They are even used in dynamic cases with mutually dependent data records while regression and auto-regression mixture components serve to the dependence modeling. These dynamic models, however, mostly assume data-independent component weights, that is, memoryless transitions between dynamic mixture components. Such mixtures are not universal approximators of dynamic probabilistic models. Formally, this follows from the fact that the set of finite probabilistic mixtures is not closed with respect to the conditioning, which is the key estimation and predictive operation. The paper overcomes this drawback by using ratios of finite mixtures as universally approximating dynamic parametric models. The paper motivates them, elaborates their approximate Bayesian recursive estimation and reveals their application potential.     

Experimental investigation of Co and Fe-Doped CuO nanostructured electrode material for remarkable electrochemical performance

The current research work presents a facile and cost–effective co-precipitation method to prepare doped (Co & Fe) CuO and undoped CuO nanostructures without usage of any type of surfactant or capping agents. The structural analysis reveals monoclinic crystal structure of synthesized pure CuO and doped-CuO nanostructures. The effect of different morphologies on the performance of supercapacitors has been found in CV (cyclic voltammetry) and GCD (galvanic charge discharge) investigations. The specific capacitances have been obtained 156 (±5) Fg^?1, 168(±5) Fg^?1 and 186 (±5) Fg^?1 for CuO, Co-doped CuO and Fe-doped CuO electrodes, respectively at scan rate of 5 mVs^?1, while it is found to be 114 (±5) Fg^?1, 136 (±5) Fg^?1 and 170 (±5) Fg^?1 for CuO, Co–CuO and Fe–CuO, respectively at 0.5 Ag^-1 as calculated from the GCD. The super capacitive performance of the Fe–CuO nanorods is mainly attributed to the synergism that evolves between CuO and Fe metal ion. The Fe-doped CuO with its nanorods like morphology provides superior specific capacitance value and excellent cyclic stability among all studied nanostructured electrodes. Consequently, it motivates to the use of Fe-doped CuO nanostructures as electrode material in the next generation energy storage devices.     

Role of additives in fabrication of soy-based rigid polyurethane foam for structural and thermal insulation applications

Environmental concerns continue to pose the challenge to replace petroleum-based products with renewable ones completely or at least partially while maintaining comparable properties. Herein, rigid polyurethane (PU) foams were prepared using soy-based polyol for structural and thermal insulation applications. Cell size, density, thermal resistivity, and compression force deflection (CFD) values were evaluated and compared with that of petroleum-based PU foam Baydur 683. The roles of different additives, that is, catalyst, blowing agent, surfactants, and different functionalities of polyol on the properties of fabricated foam were also investigated. For this study, dibutyltin dilaurate was employed as catalyst and water as environment friendly blowing agent. Their competitive effect on density and cell size of the PU foams were evaluated. Five different silicone-based surfactants were employed to study the effect of surface tension on cell size of foam. It was also found that 5 g of surfactant per 100 g of polyol produced a foam with minimum surface tension and highest thermal resistivity (R value: 26.11 m²·K/W). However, CFD values were compromised for higher surfactant loading. Additionally, blending of 5 g of higher functionality soy-based polyol improved the CFD values to 328.19 kPa, which was comparable to that of petroleum-based foam Baydur 683.