Extending insertion electrochemistry to soluble layered halides with superconcentrated electrolytes.

Insertion compounds provide the fundamental basis of today's commercialized Li-ion batteries. Throughout history, intense research has focused on the design of stellar electrodes mainly relying on layered oxides or sulfides, and leaving aside the corresponding halides because of solubility issues. This is no longer true. In this work, we show the feasibility of reversibly intercalating Li+ electrochemically into VX3 compounds (X = Cl, Br, I) via the use of superconcentrated electrolytes (5 M LiFSI in dimethyl carbonate), hence opening access to a family of LixVX3 phases. Moreover, through an electrolyte engineering approach, we unambiguously prove that the positive attribute of superconcentrated electrolytes against the solubility of inorganic compounds is rooted in a thermodynamic rather than a kinetic effect. The mechanism and corresponding impact of our findings enrich the fundamental understanding of superconcentrated electrolytes and constitute a crucial step in the design of novel insertion compounds with tunable properties for a wide range of applications including Li-ion batteries and beyond.

pH-Sensitive Visible or Shortwave Infrared Quantum Dot Nanoprobes Using Conformation-Switchable Copolymeric Ligands.

Intracellular and extracellular pH are key parameters in many physiological processes and diseases. For example, the extracellular pH of the tumor micro-environment is slightly more acidic than in healthy tissue. In vivo mapping of the extracellular pH within the tumor would therefore improve our understanding of the tumor physiology. Fluorescent semiconductor quantum dots (QDs) represent interesting probes for in vivo imaging, in particular in the shortwave infrared (SWIR) range. Here, pH-sensitive QD nanoprobes are developed using a conformation-switchable surface chemistry. The central fluorescent QD is coated with a copolymer ligand and conjugated to gold nanoparticle quenchers. As the pH decreases from physiological (7.5) to slightly acidic (5.5-6), the copolymer reversibly shrinks, which increases the energy transfer between the QD and the gold quenchers and modulates the QD fluorescence signal. This enables the design of ratiometric QD probes for biological pH range emitting in the visible or SWIR range. In addition, these probes can be easily encapsulated and remain functional within ghost erythrocyte membranes, which facilitate their in vivo application.

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles.

Nanophase segregation of a bicomponent thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of interchain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography, using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast, supports simulations and highlights patchy nanoparticles with a trend toward Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization.

Fluorescent and Electroactive Low-Viscosity Tetrazine-Based Organic Liquids.

New fluorescent molecular liquids with a tetrazine core have been prepared. These compounds remain liquid at least down to -60 °C and display very low viscosities (28 mPa.s for liquid 1, 58 mPa.s for liquid 2). Both compounds remain fluorescent in the condensed phase. For liquid 1, intermolecular quenching is observed to a certain extent, whereas liquid 2 displays similar photophysical properties in dilute solution and in neat film.