Poly(ionic liquid)s derived from 3‐octyl‐1‐vinylimidazolium bromide and N‐isopropylacrylamide with tunable properties

A new series of linear and crosslinked copolymers, obtained from 3‐octyl‐1‐vinylimidazolium bromide (VImBr) and N‐isopropylacrylamide (NIPAAm), were prepared by radical polymerization. Namely, VImBr was synthesized from 1‐bromooctane and an ionic liquid such as 1‐vinylimidazole. NIPAAm was used because it gives raise to well known thermoresponsive (co‐)polymers. The copolymers were thoroughly characterized by means of ¹H NMR and ¹³C NMR spectroscopies. Besides, differential scanning calorimetry, Fourier transform infrared spectroscopy, and scanning electron microscopy were also used. Moreover, the swelling behavior and the thermoresponsive properties of the corresponding hydrogels were studied. It was found that the VImBr incorporation into the copolymers does have a dramatic influence on both the thermal properties of the dried materials and the lower critical solution temperature of the corresponding hydrogels. In detail, the glass transition temperature was dependent on the monomer ratios, and ranged from 5 to 155 °C. Analogously, the lower critical solution temperature of the resulting hydrogels ranged from less than 10 up to 38 °C, thus including the physiological temperature. NMR spectroscopies, which were performed on the linear polymers, indicated that the monomers exhibit an alternating tendency resulting in a microstructure in which blocks are not present, at least when the two monomers are in equimolar amounts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3521–3532     

Strengthened splitting methods for computing resolvents

Computational Optimization and Applications - In this work, we develop a systematic framework for computing the resolvent of the sum of two or more monotone operators which only activates each...     

A new class of conformable spectral observers for signal reconstruction

In this work, the design of spectral observers for signal reconstruction based on Kalman filters is performed and evaluated. The conformable derivative and the beta‐derivative were used to design the Kalman filters. Both derivatives satisfy the same formulas of the classical derivation, eg, the chain rule. The derivative order, the Ricatti equation parameters, and the observers tuning parameters were optimized using an optimization algorithm based on the bat's echolocation behavior (Bat algorithm). The simulation results showed the advantages of using the proposed observers for the signal reconstruction.     

Using genetic programming to evolve action selection rules in traversal-based automated software testing: results obtained with the TESTAR tool

Traversal-based automated software testing involves testing an application via its graphical user interface (GUI) and thereby taking the user’s point of view and executing actions in a human-like manner. These actions are decided on the fly, as the software under test (SUT) is being run, as opposed to being set up in the form of a sequence prior to the testing, a sequence that is then used to exercise the SUT. In practice, random choice is commonly used to decide which action to execute at each state (a procedure commonly referred to as monkey testing), but a number of alternative mechanisms have also been proposed in the literature. Here we propose using genetic programming (GP) to evolve such an action selection strategy, defined as a list of IF-THEN rules. Genetic programming has proved to be suited for evolving all sorts of programs, and rules in particular, provided adequate primitives (functions and terminals) are defined. These primitives must aim to extract the most relevant information from the SUT and the dynamics of the testing process. We introduce a number of such primitives suited to the problem at hand and evaluate their usefulness based on various metrics. We carry out experiments and compare the results with those obtained by random selection and also by Q-learning, a reinforcement learning technique. Three applications are used as Software Under Test (SUT) in the experiments. The analysis shows the potential of GP to evolve action selection strategies.     

Structural distortion,charge modulation and local anisotropies in magnetite below the Verwey transition using resonant X‐ray scattering

The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe₃O₄ single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e^? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms.     

Highly Homogeneous Stereocontrolled Construction of Quaternary Hydroxyesters by Addition of Dimethylzinc to α‐Ketoesters Promoted by Chiral Perhydrobenzoxazines and B(OEt)3

A highly efficient enantioselective addition of Me₂Zn to α‐ketoesters, assisted by a chiral perhydro‐1,3‐benzoxazine ligand, is described. This novel catalytic system offers homogeneous elevated enantioselectivities in the preparation of α‐hydroxyesters that bear a quaternary stereocenter, with a minor dependence on electronic and steric effects when aromatic, heteroaromatic, or aliphatic α‐ketoesters are employed. The catalyst can be recovered and reused without loss of activity.     

Established and emerging strategies for polymer chain-end modification

The development of “controlled” and “living” polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chain-end functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2903–2914