Comparison of Force Fields on the Basis of Various Model Approaches—How To Design the Best Model for the [CnMIM][NTf2] Family of Ionic Liquids

In this contribution, we present two new united‐atom force fields (UA‐FFs) for 1‐alkyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide [C_nMIM][NTf₂] (n=1, 2, 4, 6, 8) ionic liquids (ILs). One is parametrized manually, and the other is developed with the gradient‐based optimization workflow (GROW). By doing so, we wanted to perform a hard test to determine how researchers could benefit from semiautomated optimization procedures. As with our already published all‐atom force field (AA‐FF) for [C_nMIM][NTf₂] (T. Köddermann, D. Paschek, R. Ludwig, ChemPhysChem­ 2007, 8, 2464 ), the new force fields were derived to fit experimental densities, self‐diffusion coefficients, and NMR rotational correlation times for the IL cation and for water molecules dissolved in [C₂MIM][NTf₂]. In the manual force field, the alkyl chains of the cation and the CF₃ groups of the anion were treated as united atoms. In the GROW force field, only the alkyl chains of the cation were united. All other parts of the structures of the ions remained unchanged to prevent any loss of physical information. Structural, dynamic, and thermodynamic properties such as viscosity, cation rotational correlation times, and heats of vaporization calculated with the new force fields were compared with values simulated with the previous AA‐FF and the experimental data. All simulated properties were in excellent agreement with the experimental values. Altogether, the UA‐FFs are slightly superior for speed‐up reasons. The UA‐FF speeds up the simulation by about 100 % and reduces the demanded disk space by about 78 %. More importantly, real time and efforts to generate force fields could be significantly reduced by utilizing GROW. The real time for the GROW parametrization in this work was 2 months. Manual parametrization, in contrast, may take up to 12 months, and this is, therefore, a significant increase in speed, though it is difficult to estimate the duration of manual parametrization.     

Ratio-conjugation tool and its application in linear optimization models†

The ratio-conjugation-tool (RC) is constructed systematically, and its applicability for analysis of economic models is demonstrated. One of the main results establishes a general formula for RC of aggregative function. This tool is applied to the analysis of linear economic dynamics models of Neumann–Gale type which can be solved by a dynamic programming method: for each direct problem we construct the corresponding dual RC-problem. Moreover, we consider three examples of the most important economic dynamics models and look at these now from a unified general position.     

A numerical algorithm for pricing electricity derivatives for jump-diffusion processes based on continuous time lattices

We present a numerical algorithm for pricing derivatives on electricity prices. The algorithm is based on approximating the generator of the underlying price process on a lattice of prices, resulting in an approximation of the stochastic process by a continuous time Markov chain. We numerically study the rate of convergence of the algorithm for the case of the Merton jump-diffusion model and apply the algorithm to calculate prices and sensitivities of both European and Bermudan electricity derivatives when the underlying price follows a stochastic process which exhibits both fast mean-reversion and jumps of large magnitude.     

Hopf bifurcation control via a dynamic state-feedback control

To relocate two Hopf bifurcation points, simultaneously, to any desired locations in n-dimensional nonlinear systems, a novel dynamic state-feedback control law is proposed. Analytical schemes to determine the control gains according to the conditions for the emergence of Hopf bifurcation are derived. To verify the effectiveness of the proposed control law, numerical examples are provided.     

A preliminary approach of dynamic identification of slender buildings by neuronal networks

The study of the dynamic behavior of slender masonry structures is usually related to the preservation of the historic heritage. This study, for bell towers and industrial masonry chimneys, is particularly relevant in areas with an important seismic hazard. The analysis of the dynamic behavior of masonry structures is particularly complex due to the multiple effects that can affect the variation of its main frequencies along the seasons of the year: temperature and humidity. Moreover, these dynamic properties also vary considerably in structures built in areas where land subsidence due to the variation of the phreatic level along the year is particularly evident: the stiffness of the soil–structure interaction also varies. This paper presents a study to evaluate the possibility of detecting the variation of groundwater level based on the readings obtained using accelerometers in different positions on the structure. To do this a general case study was considered: a 3D numerical model of a bellower. The variation of the phreatic level was evaluated between 0 and −20 m, and 81 cases studies were developed modifying the rigidity of the soil–structure interaction associated to a position of the phreatic level. To simulate the dispositions of accelerometers on a real construction, 16 points of the numerical model were selected along the structure to obtain modal displacements in two orthogonal directions. Through an adjustment by using neural networks, a good correlation has been observed between the predicted position of the water table and acceleration readings obtained from the numerical model. It is possible to conclude that with a discrete register of accelerations on the tower it is possible to predict the water table depth.     

Morphology and properties of super-toughened bio-based poly(lactic acid)/poly(ethylene-co-vinyl acetate) blends by peroxide-induced dynamic vulcanization and interfacial compatibilization

Super-toughened poly(lactic acid) (PLA)/poly(ethylene-co-vinyl acetate) (EVA) blends were prepared via 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD) induced dynamic vulcanization and in situ interfacial compatibilization. The effects of AD on the morphology and properties of PLA/EVA blends were studied using a Brabender torque rheometer, gel content test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) thermogravimetric analysis (TGA) and mechanical properties test. The torque and gel content demonstrated that EVA and PLA was successfully vulcanized in the presence of free radicals obtained by the decomposition of the 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD). Additionally, the gel content results indicated that, compared with PLA, EVA is more aggressive with free radicals. The SEM revealed that a relatively uniform phase morphology and good interfacial compatibilization were achieved in the dynamically vulcanized PLA/EVA/AD blends. The interfacial reaction and compatibilization between the component polymers resulted in the formation of super-toughened PLA/EVA blended materials.     

Asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through dynamic covalent kinetic resolution

The asymmetric synthesis of 1,3-oxathiolan-5-one derivatives through an enzyme-catalyzed, dynamic covalent kinetic resolution strategy is presented. Dynamic hemithioacetal formation combined with intramolecular, lipase-catalyzed lactonization resulted in good conversions with moderate to good enantiomeric excess (ee) for the final products. The process was evaluated for different lipase preparations, solvents, bases, and reaction temperatures, where lipase B from Candida antarctica (CAL-B) proved most efficient. The substrate scope was furthermore explored for a range of aldehyde structures, together with the potential access to nucleoside analog inhibitor core structures.