Anion Exchange Renders Hydrophobic Capsules and Cargoes Water-Soluble

Control over the solubility properties of container molecules is a central challenge in host–guest chemistry. Herein we present a simple anion-exchange protocol that allows the dissolution in water of various hydrophobic metal–organic container molecules prepared by iron(II)-templated subcomponent self-assembly. Our process involved the exchange of less hydrophilic trifluoromethanesulfonate anions for hydrophilic sulfate; the resulting water-soluble cages could be rendered water-insoluble through reverse anion exchange. Notably, this strategy allowed cargoes within capsules, including polycyclic aromatic compounds and complex organic drugs, to be brought into water. Hydrophobic effects appeared to enhance binding, as many of these cargoes were not bound in non-aqueous media. Studies of the scope of this method revealed that cages containing tetratopic and tritopic ligands were more stable in water, whereas cages with ditopic ligands disassembled.     

A rheological study of cationic micro- and nanofibrillated cellulose: quaternization reaction optimization and fibril characteristic effects

Driven by the demand for various cationic biopolymers in recent years, the quaternization of cellulose nanofibers was carefully investigated to have tight control over their final characteristics. The addition of sodium hydroxide (NaOH) to the reaction mixture is crucial as it catalyzes the conversion of alcohol groups of cellulose into more reactive alcoholate groups. On the other hand, excessive concentration proves to inhibit the reactivity of hydroxyl groups. The addition of glycidyltrimethylammonium chloride (GTMAC) increases the yield of the trimethylammonium chloride content (TMAC) reaction, while in excess it affects the rheological properties of the quaternizated cellulose nanofibers. The effects of NaOH and GTMAC on the TMAC content and rheological properties have been investigated in detail and mathematically evaluated. Furthermore, a comparison of the viscoelastic behavior and shear thinning character of commercial cationic micro- and nanofibrillated cellulose is presented. The research allows to extend the possibility of using cellulose in many applications of cationic biopolymers.

     

Electrolysis energy efficiency of highly concentrated FeCl2 solutions for power-to-solid energy storage technology

An electrochemical cycle for the grid energy storage in the redox potential of Fe involves the electrolysis of a highly concentrated aqueous FeCl₂ solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial to maximize the energy efficiency of the electrolysis process. Here we present a study of the influence of electrolysis parameters on the energy efficiency of such electrolysis, performed in an industrial-type electrolyzer. We studied the conductivity of the FeCl₂ solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency. The deviation from the correlation indicated an important contribution from the conductivity of the ion-exchange membrane. Another important studied parameter was the applied current density. We quantitatively showed how the contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ± 3% was achieved using 2.5 mol L⁻¹ FeCl₂ solution at 70 °C and a current density of 0.1 kA m⁻². In terms of the energy input per Fe mass, this means 1.88 Wh g⁻¹. The limiting energy input per mass of the Fe deposit was found to be 1.76 Wh g⁻¹_.

Graphical abstract

     

Epistemological Skepticism, Semantic Blindness, and Competence-Based Performance Errors

The semantic blindness objection to contextualism challenges the view that there is no incompatibility between (i) denials of external-world knowledge in contexts where radical-deception scenarios are salient, and (ii) affirmations of external-world knowledge in contexts where such scenarios are not salient. Contextualism allegedly attributes a gross and implausible form of semantic incompetence in the use of the concept of knowledge to people who are otherwise quite competent in its use; this blindness supposedly consists in wrongly judging that there is genuine conflict between claims of type (i) and type (ii). We distinguish two broad versions of contextualism: relativistic-content contextualism and categorical-content contextualism. We argue that although the semantic blindness objection evidently is applicable to the former, it does not apply to the latter. We describe a subtle form of conflict between claims of types (i) and (ii), which we call différance-based affirmatory conflict. We argue that people confronted with radical-deception scenarios are prone to experience a form of semantic myopia (as we call it): a failure to distinguish between différance-based affirmatory conflict and outright inconsistency. Attributing such semantic myopia to people who are otherwise competent with the concept of knowledge explains the bafflement about knowledge-claims that so often arises when radical-deception scenarios are made salient. Such myopia is not some crude form of semantic blindness at all; rather, it is an understandable mistake grounded in semantic competence itself: what we call a competence-based performance error.     

Complexes of Eu(III), Tb(III) and Cu(II) with proton transfer compound between 2,6-pyridinedicarboxylic acid and 2-aminobenzothiazole: characterization of the structures and physical properties

A proton transfer compound, (ABTH)⁺(PydcH)^? (1), obtained from 2-aminobenzothiazole (ABT) and 2,6-pyridinedicarboxylic acid (Pydc) as well as its Eu(III), Tb(III), and Cu(II) complexes (ABT)₃[Eu(Pydc)₃]·5H₂O (2), (ABT)₃[Tb(Pydc)₃]·5H₂O (3), and (ABT)[Cu(Pydc)(PydcH)]·3H₂O (4) were obtained under ambient conditions and structurally verified by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and magnetic measurements. Compounds 2–4 are the first known solids containing complex anions with Pydc ligands, 2-aminobenzothiazole cations (ABT), and solvate water molecules. During the synthesis of 3, a secondary phase with the formula ABTCl?H₂O was obtained and characterized by elemental analysis and single-crystal X-ray diffraction. The asymmetric unit of 5 consists of six symmetry independent ABT cations, six chlorides, and six water molecules. The two lanthanide complexes showed characteristic emissions of Eu³⁺ and Tb³⁺ ions. The good solubilities of these complexes in water and their luminescence properties make them attractive luminescent labels of biological molecules.     

Two new nickel(II) carboxylates with 3- and 4-aminopyridine: syntheses,structures, and magnetic properties

Abstract  

The synthesis and characterization of two new nickel(II) coordination compounds with 3- and 4-aminopyridine are reported. They were obtained after dissolving Ni(CH₃COO)₂·4H₂O in different solutions of 3- and 4-aminopyridine. The products were characterized magnetically, structurally by single-crystal X-ray diffraction analysis, and spectrally by FT-IR spectroscopy. Dark green crystals of the polymeric coordination complex {[Ni(O₂CCH₃)₂(3-apy)₂]·H₂O} _n were synthesized by the reaction of Ni(CH₃COO)₂·4H₂O and 3-aminopyridine (3-apy). The molecular structure of this complex consists of a zigzag chain in which nickel(II) ions are connected by bridging 3-aminopyridine ligands. The Ni(II) ion is six-coordinated by three oxygen atoms from two acetate ligands, one chelating and one monodenate, and by three nitrogen atoms from three 3-aminopyridine ligands, one terminal and two bridging ones. The blue crystals obtained by the reaction of Ni(CH₃COO)₂·4H₂O with 4-aminopyridine (4-apy) consist of the monomeric complex [Ni(O₂CCH₃)₂(4-apy)₂(H₂O)₂], in which the ligands possess trans geometry around the Ni(II) ion. The interactions including intra- and intermolecular hydrogen bonds in the crystal structures of both complexes are discussed. Magnetic properties of both compounds were studied between 2 and 300 K giving the result of μ _eff = 3.1 BM in the paramagnetic region.     

Elimination of spiral waves in excitable media by magnetic induction

Nonlinear Dynamics - The formation of spiral waves in excitable media is a fascinating example of the beauty of nonlinear dynamics in spatiotemporal systems. Apart from the beauty of the patterns,...