Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4′-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.     

Switchable Enzyme/DNAzyme Cascades by the Reconfiguration of DNA Nanostructures

Mimicking cellular transformations and signal transduction pathways by means of biocatalytic cascades proceeding in organized media is a scientific challenge. We describe two DNA machines that enable the “ON/OFF” switchable activation and deactivation of three‐component biocatalytic cascades. One system consists of a reconfigurable DNA tweezers‐type structure, whereas in the second system the catalytic cascade proceeds on a switchable DNA clamp scaffold. The three‐component catalytic cascades consist of β‐galactosidase (β‐Gal), glucose oxidase (GOx), and the K⁺‐ion‐stabilized hemin‐G‐quadruplex horseradish peroxidase (HRP)‐mimicking DNAzyme. The hemin‐G‐quadruplex‐bridged closed structure of the tweezers or clamp allows the biocatalytic cascades to operate (switched “ON′′), whereas separation of the hemin‐G‐quadruplex by means of 18‐crown‐6‐ether opens the tweezers/clamp structures, thus blocking the catalytic cascade (switched ”OFF“). This study is complemented by two‐component, switchable biocatalytic cascades composed of GOx and hemin‐G‐quadruplex assembled on hairpin‐bridged DNA tweezers or clamp nanostructures.     

Cerium-Catalyzed Selective Oxidation of Alkylbenzenes with Bromate Salts

Cerium(IV) ammonium nitrate (CAN)-catalyzed oxidation of alkyl aromatics with potassium bromate affords aldehydes, ketones acids or alcohols in high yields.     

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal–organic frameworks (MOFs) that contain the three‐dimensional cubane‐1,4‐dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB‐30), comprising cdc, 4,4′‐biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π–π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.     

Crystals of Benzamide,the First Polymorphous Molecular Compound,Are Helicoidal

The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X‐ray diffraction reveal a complex lamellar structure of benzamide form II needle‐like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non‐classical morphologies.     

Crystals of Benzamide,the First Polymorphous Molecular Compound,Are Helicoidal

The growth of spontaneously twisted crystals is a common but poorly understood phenomenon. An analysis of the formation of twisted crystals of a metastable benzamide polymorph (form II ) crystallizing from highly supersaturated aqueous and ethanol solutions is given here. Benzamide, the first polymorphic molecular crystal reported (1832), would have been the first helicoidal crystal observed had the original authors undertaken an analysis by light microscopy. Polymorphism and twisting frequently concur as they are both associated with high thermodynamic driving forces for crystallization. Optical and electron microscopies as well as electron and powder X-ray diffraction reveal a complex lamellar structure of benzamide form II needle-like crystals. The internal stress produced by the overgrowth of lamellae is shown to be able to create a twist moment that is responsible for the observed non-classical morphologies.     

Signal amplification in NbN superconducting resonators via stochastic resonance

We exploit nonlinearity in NbN superconducting stripline resonators, which originates from local thermal instability, for studying stochastic resonance. As the resonators are driven into instability, small amplitude modulation (AM) signals are amplified with the aid of injected white noise. Simulation results based on the equations of motion for the system yield a good agreement with the experimental data both in the frequency and time domains.     

On the Degenerate Crossing Number

The degenerate crossing number ${\text{ cr}^{*}}(G)$ of a graph $G$ is the minimum number of crossing points of edges in any drawing of $G$ as a simple topological graph in the plane. This notion was introduced by Pach and Tóth who showed that for a graph $G$ with $n$ vertices and $e \ge 4n$ edges ${\text{ cr}^{*}}(G)=\Omega \big (e^4 / n^4\big )$ . In this paper we completely resolve the main open question about degenerate crossing numbers and show that ${\text{ cr}^{*}}(G)=\Omega \big (e^3 / n^2 \big )$ , provided that $e \ge 4n$ . This bound is best possible (apart for the multiplicative constant) as it matches the tight lower bound for the standard crossing number of a graph.     

pH‐Controlled network formation in a mixture of oppositely charged cellulose nanocrystals and poly(allylamine)

The behavior of a mixture of negatively charged cellulose nanocrystals (CNCs) and positively charged poly(allylamine) (PAAm) is examined in aqueous media. By modulating the pH, the acting Coulomb forces can be varied that can lead not only to adsorption of PAAm chains on the CNC surface but also to the development of a supermolecular structure by bridging of CNC rods by extended PAAm chains. This bridging can result in the formation of CNC clusters, which was demonstrated experimentally. Light scattering and rheological studies showed that these clusters begin to grow and merge, ultimately forming a global percolated network above a critical degree of PAAm ionization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1527–1536