High-resolution phase-sensitive sum frequency generation spectroscopy by time-domain ptychography.

We demonstrate that time-domain ptychography, when applied to a set of broadband vibrational sum frequency spectra, reconstructs amplitude and phase of the vibrational free induction decay from an interfacial sample with a resolution that is independent of up-converting pulse bandwidth and spectrometer resolution. These important improvements require no modifications to most standard homodyne setups, and the method is applicable to other coherent homodyne spectroscopies such as coherent anti-Stokes Raman spectroscopy and transient grating spectroscopy.

Origin of Enhanced Cyclability in Covalently Modified LiMn1.5Ni0.5O4 Cathodes.

High-voltage lithium-ion cathode materials exhibit exceptional energy densities; however, rapid capacity fade during cell cycling prohibits their widespread utilization. Surface modification of cathode-active materials by organic self-assembled monolayers (SAMs) has emerged as an approach to improve the longevity of high-voltage electrodes; however, the surface chemistry at the electrode/electrolyte interphase and its dependence on monolayer structure remains unclear. Herein, we investigate the interplay between monolayer structure, electrochemical performance, and surface chemistry of high-voltage LiMn1.5Ni0.5O4 (LMNO) electrodes by the application of silane-based SAMs of variable length and chemical composition. We demonstrate that the application of both hydrophobic and hydrophilic monolayers results in improved galvanostatic capacity retention relative to unmodified LMNO. The extent of this improvement is tied to the structure of the monolayer with fluorinated alkyl-silanes exhibiting the greatest overall capacity retention, above 96% after 100 charge/discharge cycles. Postmortem surface analysis reveals that the presence of the monolayer enhances the deposition of LiF at the electrode surface during cell cycling and that the total surface concentration correlates with the overall improvements in capacity retention. We propose that the enhanced deposition of highly insulating LiF increases the anodic stability of the interphase, contributing to the improved galvanostatic performance of modified electrodes. Moreover, this work demonstrates that the modification of the electrode surface by the selection of an appropriate monolayer is an effective approach to tune the properties and behavior of the electrode/electrolyte interphase formed during battery operation.

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10-3 S cm-1. With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li+. This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.

Three-dimensional mesostructures as high-temperature growth templates, electronic cellular scaffolds, and self-propelled microrobots.

Recent work demonstrates that processes of stress release in prestrained elastomeric substrates can guide the assembly of sophisticated 3D micro/nanostructures in advanced materials. Reported application examples include soft electronic components, tunable electromagnetic and optical devices, vibrational metrology platforms, and other unusual technologies, each enabled by uniquely engineered 3D architectures. A significant disadvantage of these systems is that the elastomeric substrates, while essential to the assembly process, can impose significant engineering constraints in terms of operating temperatures and levels of dimensional stability; they also prevent the realization of 3D structures in freestanding forms. Here, we introduce concepts in interfacial photopolymerization, nonlinear mechanics, and physical transfer that bypass these limitations. The results enable 3D mesostructures in fully or partially freestanding forms, with additional capabilities in integration onto nearly any class of substrate, from planar, hard inorganic materials to textured, soft biological tissues, all via mechanisms quantitatively described by theoretical modeling. Illustrations of these ideas include their use in 3D structures as frameworks for templated growth of organized lamellae from AgCl-KCl eutectics and of atomic layers of WSe2 from vapor-phase precursors, as open-architecture electronic scaffolds for formation of dorsal root ganglion (DRG) neural networks, and as catalyst supports for propulsive systems in 3D microswimmers with geometrically controlled dynamics. Taken together, these methodologies establish a set of enabling options in 3D micro/nanomanufacturing that lie outside of the scope of existing alternatives.

Restored iron transport by a small molecule promotes absorption and hemoglobinization in animals.

Multiple human diseases ensue from a hereditary or acquired deficiency of iron-transporting protein function that diminishes transmembrane iron flux in distinct sites and directions. Because other iron-transport proteins remain active, labile iron gradients build up across the corresponding protein-deficient membranes. Here we report that a small-molecule natural product, hinokitiol, can harness such gradients to restore iron transport into, within, and/or out of cells. The same compound promotes gut iron absorption in DMT1-deficient rats and ferroportin-deficient mice, as well as hemoglobinization in DMT1- and mitoferrin-deficient zebrafish. These findings illuminate a general mechanistic framework for small molecule-mediated site- and direction-selective restoration of iron transport. They also suggest that small molecules that partially mimic the function of missing protein transporters of iron, and possibly other ions, may have potential in treating human diseases.

Influence of the water content on the structure and physicochemical properties of an ionic liquid and its Li+ mixture.

The effect of water on the hydrophobic ionic liquid (IL) 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonylimide) and its Li(+) mixture was evaluated. The electrochemical stability, density, viscosity, and ionic conductivity were measured for both systems in different concentrations of water. The presence of Li(+) causes a large increase in the water absorption ability of the IL. The experimental results suggest a break of the interactions between Li(+) and Tf2N(-) anions in the strong aggregates formed in dried Li(+) mixtures, modifying the size and physicochemical nature of these aggregates. It is also observed that the size of the ions aggregates with formal charge increases at high temperature and decreases the mobility of the charge carrier, explaining the break in the Walden rules at high temperature. Raman spectroscopy and molecular dynamic simulations show the structural change of these systems. In neat ILs, the water molecules interact mainly among each other, while in the Li(+) mixtures, water interacts preferentially with the metallic cation, causing an important change in the aggregates present in this system.

Room temperature ionic liquid-lithium salt mixtures: optical Kerr effect dynamical measurements.

The addition of lithium salts to ionic liquids causes an increase in viscosity and a decrease in ionic mobility that hinders their possible application as an alternative solvent in lithium ion batteries. Optically heterodyne-detected optical Kerr effect spectroscopy was used to study the change in dynamics, principally orientational relaxation, caused by the addition of lithium bis(trifluoromethylsulfonyl)imide to the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Over the time scales studied (1 ps-16 ns) for the pure ionic liquid, two temperature-independent power laws were observed: the intermediate power law (1 ps to approximately 1 ns), followed by the von Schweidler power law. The von Schweidler power law is followed by the final complete exponential relaxation, which is highly sensitive to temperature. The lithium salt concentration, however, was found to affect both power laws, and a discontinuity could be found in the trend observed for the intermediate power law when the concentration (mole fraction) of lithium salt is close to chi(LiTf(2)N) = 0.2. A mode coupling theory (MCT) schematic model was also used to fit the data for both the pure ionic liquid and the different salt concentration mixtures. It was found that dynamics in both types of liquids are described very well by MCT.