Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2S3@CNT/SS Cathode towards a Flexible Li-CO2 Battery

A photoinduced flexible Li-CO₂ battery with well-designed, hierarchical porous, and free-standing In₂S₃@CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO₂ reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li-CO₂ battery achieved a record-high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra-low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (<80 %) so far. These excellent properties can be ascribed to the hierarchical porous and free-standing structure of ICS, as well as the key role of photogenerated electrons and holes during discharging and charging processes. A mechanism is proposed for pre-activating CO₂ by reducing In³⁺ to In⁺ under light illumination. The mechanism of the bifunctional light-assisted process provides insight into photoinduced Li-CO₂ batteries and contributes to resolving the major setbacks of the system.     

Hierarchically Structured Allotropes of Phosphorus from Data-Driven Exploration

The discovery of materials is increasingly guided by quantum-mechanical crystal-structure prediction, but the structural complexity in bulk and nanoscale materials remains a bottleneck. Here we demonstrate how data-driven approaches can vastly accelerate the search for complex structures, combining a machine-learning (ML) model for the potential-energy surface with efficient, fragment-based searching. We use the characteristic building units observed in Hittorf's and fibrous phosphorus to seed stochastic (“random”) structure searches over hundreds of thousands of runs. Our study identifies a family of hierarchically structured allotropes based on a P8 cage as principal building unit, including one-dimensional (1D) single and double helix structures, nanowires, and two-dimensional (2D) phosphorene allotropes with square-lattice and kagome topologies. These findings yield new insight into the intriguingly diverse structural chemistry of phosphorus, and they provide an example for how ML methods may, in the long run, be expected to accelerate the discovery of hierarchical nanostructures.     

Mechanochromic Delayed Fluorescence Switching in Propeller-Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli-Responsive Intramolecular Charge-Transfer Excited States

Herein, the universal design of high-efficiency stimuli-responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli-triggered TADF switching for a series of carbazole–isophthalonitrile-based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X-ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited-state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light-emitting diodes using a single TADF emitter.     

Optimizing Charge Switching in Membrane Lytic Peptides for Endosomal Release of Biomacromolecules

Endocytic pathways are practical routes for the intracellular delivery of biomacromolecules. Along with this, effective strategies for endosomal cargo release into the cytosol are desired to achieve successful delivery. Focusing on compositional differences between the cell and endosomal membranes and the pH decrease within endosomes, we designed the lipid-sensitive and pH-responsive endosome-lytic peptide HAad. This peptide contains aminoadipic acid (Aad) residues, which serve as a safety catch for preferential permeabilization of endosomal membranes over cell membranes, and His-to-Ala substitutions enhance the endosomolytic activity. The ability of HAad to destabilize endosomal membranes was supported by model studies using large unilamellar vesicles (LUVs) and by increased intracellular delivery of biomacromolecules (including antibodies) into live cells. Cerebral ventricle injection of Cre recombinase with HAad led to Cre/loxP recombination in a mouse model, thus demonstrating potential applicability of HAad in vivo.     

One-Pot Synthesis of Chiral N-Arylamines by Combining Biocatalytic Aminations with Buchwald–Hartwig N-Arylation

The combination of biocatalysis and chemo-catalysis increasingly offers chemists access to more diverse chemical architectures. Here, we describe the combination of a toolbox of chiral-amine-producing biocatalysts with a Buchwald–Hartwig cross-coupling reaction, affording a variety of α-chiral aniline derivatives. The use of a surfactant allowed reactions to be performed sequentially in the same flask, preventing the palladium catalyst from being inhibited by the high concentrations of ammonia, salts, or buffers present in the aqueous media in most cases. The methodology was further extended by combining with a dual-enzyme biocatalytic hydrogen-borrowing cascade in one pot to allow for the conversion of a racemic alcohol to a chiral aniline.     

Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post-polymerization Ligation and Conjugation

We report the synthesis of monomers for atom-transfer radical polymerization (ATRP) and a reversible addition-fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT-containing polymers are suitable for rapid amide-forming ligations for both post-polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star-shaped block copolymers. In addition, we applied post-polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT-containing copolymer. Cellular assays revealed that the polymer–antibiotic conjugate is biocompatible and provides efficient light-controlled release of the antibiotic on demand.