Strengthening Aqueous Electrolytes without Strengthening Water

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions—25 wt.% LiCl and 62 wt.% H₃PO₄—cooled to −78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li⁺ ions become less hydrated and pair up with Cl⁻, ice-like water clusters form, and H⋅⋅⋅Cl⁻ bonding strengthens. Surprisingly, this low-temperature solvation structure does not strengthen water molecules’ O−H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O−H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH⁻ and H⁺, the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li-ion battery using LiMn₂O₄ cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.     

Hypsochromically-shifted Emission of Metal-organic Frameworks Generated through Post-synthetic Ligand Reduction

Luminescent materials with tunable emission are becoming increasingly desirable as we move towards needing efficient Light Emitting Diodes (LEDs) for displays. Key to developing better displays is the advancement of strategies for rationally designing emissive materials that are tunable and efficient. We report a series of emissive metal-organic frameworks (MOFs) generated using BUT-10 (BUT: Beijing University of Technology) that emits green light with λ_max at 525 nm. Post-synthetic reduction of the ketone on the fluorenone ligand in BUT-10 generates new materials, BUT-10-M and BUT-10-R. The emission for BUT-10-R is hypsochromically-shifted by 113 nm. Multivariate BUT-10-M structures demonstrate emission with two maxima corresponding to the emission of both fluorenol and fluorenone moieties present in their structures. Our study represents a novel post-synthetic ligand reduction strategy for producing emissive MOFs with tunable emission ranging from green, white-blue to deep blue.     

Top quark mass in exophobic Pati-Salam heterotic string model

We analyse the phenomenology of an exemplary exophobic Pati-Salam heterotic string vacuum, in which no exotic fractionally charged states exist in the massless string spectrum. Our model also contains the Higgs representations that are needed to break the gauge symmetry to that of the Standard Model and to generate fermion masses at the electroweak scale. We show that the requirement of a leading mass term for the heavy generation, which is not degenerate with the mass terms of the lighter generations, places an additional strong constraint on the viability of the models. In many models a top quark Yukawa may not exist at all, whereas in others two or more generations may obtain a mass term at leading order. In our exemplary model a mass term at leading order exist only for one family. Additionally, we demonstrate the existence of supersymmetric F- and D-flat directions that give heavy mass to all the colour triplets beyond those of the Standard Model and leave one pair of electroweak Higgs doublets light. Hence, below the Pati-Salam breaking scale, the matter states in our model that are charged under the observable gauge symmetries, consist solely of those of the Minimal Supersymmetric Standard Model.     

A characterization of {\square(\kappa^{+})} in extender models

We prove that, in any fine structural extender model with Jensen’s λ-indexing, there is a ${\square(\kappa^{+})}$ -sequence if and only if there is a pair of stationary subsets of ${\kappa^{+} \cap {\rm {cof}}( < \kappa)}$ without common reflection point of cofinality ${ < \kappa}$ which, in turn, is equivalent to the existence of a family of size ${ < \kappa}$ of stationary subsets of ${\kappa^{+} \cap {\rm {cof}}( < \kappa)}$ without common reflection point of cofinality ${ < \kappa}$ . By a result of Burke/Jensen, ${\square_\kappa}$ fails whenever ${\kappa}$ is a subcompact cardinal. Our result shows that in extender models, it is still possible to construct a canonical ${\square(\kappa^{+})}$ -sequence where ${\kappa}$ is the first subcompact.     

Multiaxial ratcheting with advanced kinematic and directional distortional hardening rules

Ratcheting is defined as the accumulation of plastic strains during cyclic plastic loading. Modeling this behavior is extremely difficult because any small error in plastic strain during a single cycle will add to become a large error after many cycles. As is typical with metals, most constitutive models use the associative flow rule which states that the plastic strain increment is in the direction normal to the yield surface. When the associative flow rule is used, it is important to have the shape of the yield surface modeled accurately because small deviations in shape may result in large deviations in the normal to the yield surface and thus the plastic strain increment in multi-axial loading. During cyclic plastic loading these deviations will accumulate and may result in large errors to predicted strains.This paper compares the bi-axial ratcheting simulations of two classes of plasticity models. The first class of models consists of the classical von Mises model with various kinematic hardening (KH) rules. The second class of models introduce directional distortional hardening (DDH) in addition to these various kinematic hardening rules. Directional distortion describes the formation of a region of high curvature on the yield surface approximately in the direction of loading and a region of flattened curvature approximately in the opposite direction. Results indicate that the addition of directional distortional hardening improves ratcheting predictions, particularly under biaxial stress controlled loading, over kinematic hardening alone.     

Paracompactness of Metric Spaces and the Axiom of Multiple Choice

The axiom of multiple choice implies that metric spaces are paracompact but the reverse implication cannot be proved in set theory without the axiom of choice.     

TOPOLOGICAL FRAMEWORK FOR FINITE INJURY

We formulate an abstract version of the finite injury method in the form of the Baire category theorem. The theorem has the following corollaries: The Friedberg-Muchnik pair of recursively enumerable degrees, the Sacks splitting theorem, the existence of a minimal degree below 0′ and the Shoenfield jump theorem.     

A new mechanism for electron spin echo envelope modulation

Electron spin echo envelope modulation (ESEEM) has been observed for the first time from a coupled heterospin pair of electron and nucleus in liquid solution. Previously, modulation effects in spin-echo experiments have only been described in liquid solutions for a coupled pair of homonuclear spins in nuclear magnetic resonance or a pair of resonant electron spins in electron paramagnetic resonance. We observe low-frequency ESEEM (26 and 52 kHz) due to a new mechanism present for any electron spin with S > 12 that is hyperfine coupled to a nuclear spin. In our case these are electron spin (S = 32) and nuclear spin (I = 1) in the endohedral fullerene N@C(60). The modulation is shown to arise from second-order effects in the isotropic hyperfine coupling of an electron and (14)N nucleus.