Synthesis of central functionalized asymmetric triblock copolymers for surface modification and switchable surface properties

Well‐defined central functionalized asymmetric triblock copolymers (CFABC) were designed as a new type of polymer‐brush surface modifier with a short central functionalized block that could form chemical bonds with a suitable substrate surface. A combination of sequential living anionic polymerization and polymer modification reactions was used for the synthesis of two CFABCs: polystyrene‐b‐poly(4‐hydroxystyrene)‐b‐poly(methyl methacrylate) (3) and polystyrene‐b‐poly(4‐urethanopropyl triethoxysilylstyrene)‐b‐poly(methyl methacrylate) (4). The central block of 3, poly(4‐hydroxystyrene), was synthesized with a protected monomer, p‐[(tert‐butyldimethylsilyl)oxy]styrene, for the polymerization step, and this synthesis was followed by the hydrolysis of the silyl protecting group. To obtain polymer 4, the phenol functionality in 3 was converted to triethoxysilyl groups by a quantitative reaction with isocyanato propyl triethoxysilane. Gel permeation chromatography and NMR characterization indicated that the block copolymers possessed controlled molecular weights and narrow molecular weight distributions. Preliminary atomic force microscopy and X‐ray photoelectron spectroscopy analysis of the polymer brushes were reported. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3742–3750, 2000     

Adaptive type-2 neural fuzzy sliding mode control of a class of nonlinear systems

Nonlinear Dynamics - The objective of this study is to design an optimal control scheme for the control of a class of nonlinear flexible multi-body systems with extremely coupled dynamics and...     

The solvation structure,transport properties and reduction behavior of carbonate-based electrolytes of lithium-ion batteries

Despite the extensive employment of binary/ternary mixed-carbonate electrolytes (MCEs) for Li-ion batteries, the role of each ingredient with regards to the solvation structure, transport properties, and reduction behavior is not fully understood. Herein, we report the atomistic modeling and transport property measurements of the Gen2 (1.2 M LiPF₆ in ethylene carbonate (EC) and ethyl methyl carbonate (EMC)) and EC-base (1.2 M LiPF₆ in EC) electrolytes, as well as their mixtures with 10 mol% fluoroethylene carbonate (FEC). Due to the mixing of cyclic and linear carbonates, the Gen2 electrolyte is found to have a 60% lower ion dissociation rate and a 44% faster Li⁺ self-diffusion rate than the EC-base electrolyte, while the total ionic conductivities are similar. Moreover, we propose for the first time the anion–solvent exchange mechanism in MCEs with identified energetic and electrostatic origins. For electrolytes with additive, up to 25% FEC coordinates with Li⁺, which exhibits a preferential reduction that helps passivate the anode and facilitates an improved solid electrolyte interphase. The work provides a coherent computational framework for evaluating mixed electrolyte systems.

The different roles of the anion, cyclic and linear carbonates, and additive in mixed-carbonate electrolytes are revealed. The anion–solvent exchange mechanism and factors influencing the solid electrolyte interphase (SEI) formation are deciphered.     

Carbon dioxide production in the oxidation of organic acids by Cerium(IV) under aerobic and anaerobic conditions

The stoichiometry of CO₂ production during the ceric oxidation of various organic acids is measured under conditions with organic acid excess. Measurements utilize a photometric methodology. For anaerobic conditions stoichiometries [CO₂]_produced:[Ce(IV)]_reduced of about 0 (malonic acid), 0.5 (e.g., glyoxylic acid), and 1.0 (oxalic acid) are found. Oxalic acid showed an oxygen-induced decrease of CO₂ production, while other compounds such as malonic acid increased the amount of produced CO₂ or showed no changes (e.g., tartronic acid). In the case of mesoxalic acid the stoichiometry is increased from about 0.5 to 2.0 due to the presence of molecular oxygen. The results are discussed on the basis of simple reaction mechanisms demonstrating that useful information on reaction pathways and intermediates can be extracted from these simple measurements. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 899–902, 1998     

Catena-Poly[[[2,4-dichloro-6-{[(2-hydroxyethyl)imino]methyl}phenolato-κ3N,O,O']-copper(II)]-μ-chlorido]monohydrate]: Synthesis,structural, spectroscopic and luminescent properties

A new chloride bridged polymeric Cu(II) complex, [Cu(HL)(μ-Cl).H₂O]_n, 1, (H₂L = 2,4-dichloro-6-{[(2-hydroxyethyl)imino]methyl}phenol) has been synthesized and characterized by elemental-spectral analysis, crystal structure analysis and photoluminescence measurements. The Copper(II) atom is five-coordinate in a slightly distorted square-pyramidal geometry (τ = 0.085), with one N and two O atoms of the Schiff base ligand and one Cl atom defining the basal plane and a symmetry-related Cl atom occupying the apical position. The bridging Cl atom lies in apical position for one Cu(II) ion and basal for the other, and it makes this structural arrangement unusual. The linked moieties form polymeric zigzag chains running along the c axis. This zigzag chains connect each other with intramolecular and intermolecular O–H···O hydrogen bonds, which form 3D structure through π?π interactions. Furthermore, the photoluminescence properties of H₂L and 1 were investigated, they exhibit unique bright green visible emissions in the solid state, under the excitation of 349 nm UV light. The strong luminescence emission of them makes 1 a potentially useful photoactive material in photo-physical chemistry.     

Experimental and Mathematical Modelling of Factors Influencing Carbon Dioxide Absorption into the Aqueous Solution of Monoethanolamine and 1-Butyl-3-methylimidazolium Dibutylphosphate Using Response Surface Methodology (RSM)

This paper investigated the solubility of carbon dioxide (CO₂) in an aqueous solution of monoethanolamine (MEA) and 1-butyl-3-methylimidazolium dibutylphosphate ((BMIM)(DBP)) ionic liquid (IL) hybrid solvents. Aqueous solutions of MEA-(BMIM)(DBP) hybrid solvents containing different concentrations of (BMIM)(DBP) were prepared to exploit the amine’s reactive nature, combined with the IL’s non-volatile nature for CO₂ absorption. Response surface methodology (RSM) based on central composite design (CCD) was used to design the CO₂ solubility experiments and to investigate the effects of three independent factors on the solubility of CO₂ in the aqueous MEA-(BMIM)(DBP) hybrid solvent. The three independent factors were the concentration of (BMIM)(DBP) (0–20 wt.%), temperature (30 °C–60 °C) and pressure of CO₂ (2–30 bar). The experimental data were fitted to a quadratic model with a coefficient of determination (R²) value of 0.9791. The accuracy of the developed model was confirmed through additional experiments where the experimental values were found to be within the 95% confidence interval. From the RSM-generated model, the optimum conditions for CO₂ absorption in aqueous 30 wt% MEA-(BMIM)(DBP) were 20 wt% of (BMIM)(DBP), a temperature of 41.1 °C and a pressure of 30 bar.     

Electron–Phonon Superconductivity in Boron-Based Chalcogenide (X= S,Se) Monolayers

Electron–phonon mediated superconductivity is deeply investigated in two boron based monolayer materials, namely, $B_{3}S$, a metal exhibiting the ability to superconduct, and a new metal, $B_{3}Se$, presenting perfect kinetic stability. Calculations based on density functional perturbation theory combined with the maximally localized Wannier function also reveal that both materials exhibit anisotropic planar hexagonal structure like graphene. The key parameters involved in the superconductor behavior are all calculated. The electronic density in the Fermi surface is given to provide the environment for enhanced electron–phonon coupling. The longitudinal and transverse vibration modes of optical phonons mainly contribute to the electron–phonon coupling strength. Furthermore, the binding energy between the bosonic Cooper pair superfluid is quantified and determined. The critical temperature for the two materials is 20 and 10.5 K, respectively. The results obtained show the potential use of such materials for superconducting applications.     

Ballistic performance of novel design of bulletproof plates inspired by biomimetic approaches

Metal and polymer matrix composite materials are preferred in bulletproof applications due to their high-impact resistance and lightness. Personal/demand-specific designs that have become possible with the developing additive manufacturing technologies have brought a new perspective to armor technologies. At the same time, parts with complex structures designed with biomimetic approaches can be easily manufactured with additive manufacturing. In this study, biomimetic armors obtained from standard Carbon fiber reinforced polymer (CFRP) and Inconel 718 materials were compared with traditional armor structures. Within the scope of the study, 9 × 19 mm² parabellum and 7.62 mm NATO bullets were impacted at 275 m/s and 600 m/s speeds on biomimetic and conventional armor consisting of three and five layers. Bullet velocities during impact, deformation of bullets, deformation of armor, and harmonic behavior are discussed. The results obtained were also used to calculate the damped impact energies. In the study, it was determined that biomimetic plates could absorb 22%–38% more impact energy. It has been determined that CFRP materials can absorb 45% more impact energy compared to Inconel 718.     

Separation and identification of different therapeutic pharmaceutical drugs on humic acid-based HPLC column: Method optimization using central composite design

Multimode chromatographic separations are highly desirable in pharmaceutical and environmental sciences. Current study deals with the application of newly developed mixed-mode end capped-immobilized humic acid onto an aminopropyl silica based chromatographic column for separation and identification of six drugs belonging to different therapeutic groups for its applicability in pharmaceutical industries. For this, central composite design was used to evaluate the separation and resolution by optimization of three most effective parameters (acetonitrile%, flow rate, and pH of mobile phase). Second-order quadratic model was used to evaluate their effect on resolution of peaks; the probability value (<0.05) obtained from analysis of variance suggested the best applicability of the model. Desirability function was applied to calculate optimum conditions (44.8% acetonitrile, 1.75 mL/min of flow rate, and 7.5 pH) required to achieve maximum separation with good resolution within 11 min. The method was validated for linearity, precision accuracy, selectivity, and sensitivity. The results revealed a highly precise (coefficient of variance > 1%), linear (R² = 0.99), and highly selective method. Moreover, the limit of detection/quantification values revealed acceptable sensitivity of the method. The developed column was compared for its efficiency with a commercially available column and found to be highly applicable for industrial applications.