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.     

Electroactive Polymers: Developments of and Perspectives for Dielectric Elastomers

We present the development and applications of dielectric elastomers. For the last 10 years the significance of this class of polymers has risen as more applications seem possible and first products have been commercialized.     

A data-driven quadratic stability condition and its application for stabilizing unknown nonlinear systems

This paper proposes a data-driven stability criterion for quadratic stabilization of unknown nonlinear discrete-time systems. The novelty of this quadratic stability criterion lies in the direct use of the time series of system states, instead of using mathematical models. The data-driven stability criterion is utilized to design a control for stabilizing unknown nonlinear systems using online black-box system identification. The effectiveness and the adaptability of the proposed approach are compared with those of adaptive feedback linearization method with an example of stabilizing a nonlinear aeroelastic system.     

Reactivity of urethanes at high temperature: Transurethanization and side reactions

The reactivity of urethanes based on 1,6‐hexamethylene diisocyanate (HDI) and 4,4′‐methylene diphenyl diisocyanate (MDI) was investigated at temperatures between 190 °C and 235 °C. Diurethane model compounds end‐capped with either 1‐dodecanol (D‐core‐D) or 1‐hexadecanol (H‐core‐H) were mixed and annealed at high temperature. The core was either MDI or HDI. The transurethanization reaction was followed based on the formation of the compounds (H‐core‐D). The amount of H‐core‐D and of side products, which had formed after variable annealing times, were identified with ¹H NMR, FTIR, SEC, and MALDI‐TOF. Transurethanization was considerably faster for MDI‐based urethanes than for HDI‐based urethanes. Only traces of side products were formed during annealing of MDI‐based urethanes, whereas a significant amount of allophanates was formed from HDI‐based urethanes under the same conditions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 621–629     

Water‐soluble metalated and non‐metalated A2B‐ and A3‐corrole/amino acid conjugates: syntheses,characterization and properties

In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A₂B‐ and A₃‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A₃‐corrole towards O₂ evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A₃‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A₃‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd.     

An Anthracene-Based Metal-Organic Framework for Selective Photo-Reduction of Carbon Dioxide to Formic Acid Coupled with Water Oxidation

A Zr-based metal-organic framework has been synthesized and employed as a catalyst for photochemical carbon dioxide reduction coupled with water oxidation. The catalyst shows significant carbon dioxide reduction property with concomitant water oxidation. The catalyst has broad visible light as well as UV light absorption property, which is further confirmed from electronic absorption spectroscopy. Formic acid was the only reduced product from carbon dioxide with a turn-over frequency (TOF) of 0.69 h⁻¹ in addition to oxygen, which was produced with a TOF of 0.54 h⁻¹. No external photosensitizer is used and the ligand itself acts as the light harvester. The efficient and selective photochemical carbon dioxide reduction to formic acid with concomitant water oxidation using Zr-based MOF as catalyst is thus demonstrated here.     

Investigation into the structural composition of hydroalcoholic solutions as basis for the development of multiple suppression pulse sequences for NMR measurement of alcoholic beverages

An eight‐fold suppression pulse sequence was recently developed to improve sensitivity in ¹H NMR measurements of alcoholic beverages [Magn. Res. Chem. 2011 (49): 734–739]. To ensure that only one combined hydroxyl peak from water and ethanol appears in the spectrum, adjustment to a certain range of ethanol concentrations was required. To explain this observation, the structure of water–ethanol solutions was studied. Hydroalcoholic solutions showed extreme behavior at 25% vol, 46% vol, and 83% vol ethanol according to ¹H NMR experiments. Near‐infrared spectroscopy confirmed the occurrence of four significant compounds (‘individual’ ethanol and water structures as well as two water–ethanol complexes of defined composition – 1 : 1 and 1 : 3). The successful multiple suppression can be achieved for every kind of alcoholic beverage with different alcoholic strengths, when the final ethanol concentration is adjusted to a range between 25% vol and 46% vol (e.g. using dilution or pure ethanol addition). In this optimum region, an individual ethanol peak was not detected, because the ‘individual’ water structure and the 1 : 1 ethanol–water complex predominate. The nature of molecular association in ethanol–water solutions is essential to elucidate NMR method development for measurement of alcoholic beverages. The presented approach can be used to optimize other NMR suppression protocols for binary water–organic solvent mixtures, where hydrogen bonding plays a dominant role. Copyright © 2014 John Wiley & Sons, Ltd.