Functional Nanoparticles with a Reducible Tetrasulfide Motif to Upregulate mRNA Translation and Enhance Transfection in Hard‐to‐Transfect Cells

Effective messenger RNA (mRNA) transfection in hard‐to‐transfect cells delivered by vectors is a long‐standing challenge. Now it is hypothesized that the high intracellular glutathione level is associated with suppressed mRNA translation. This theory leads to a new design principle of next‐generation mRNA vectors: nanoparticles with glutathione depletion chemistry upregulate mRNA translation and enhance transfection, which is beneficial for mRNA delivery in hard‐to‐transfect cells in vitro and in vivo.     

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]‐Hydrogenase

[Fe]‐hydrogenase is an efficient biological hydrogenation catalyst. Despite intense research, Fe complexes mimicking the active site of [Fe]‐hydrogenase have not achieved turnovers in hydrogenation reactions. Herein, we describe the design and development of a manganese(I) mimic of [Fe]‐hydrogenase. This complex exhibits the highest activity and broadest scope in catalytic hydrogenation among known mimics. Thanks to its biomimetic nature, the complex exhibits unique activity in the hydrogenation of compounds analogous to methenyl‐H₄MPT⁺, the natural substrate of [Fe]‐hydrogenase. This activity enables asymmetric relay hydrogenation of benzoxazinones and benzoxazines, involving the hydrogenation of a chiral hydride transfer agent using our catalyst coupled to Lewis acid‐catalyzed hydride transfer from this agent to the substrates.     

Enabling High‐Voltage Lithium Metal Batteries by Manipulating Solvation Structure in Ester Electrolyte

Lithium metal is an ideal electrode material for future rechargeable lithium metal batteries. However, the widespread deployment of metallic lithium anode is significantly hindered by its dendritic growth and low Coulombic efficiency, especially in ester solvents. Herein, by rationally manipulating the electrolyte solvation structure with a high donor number solvent, enhancement of the solubility of lithium nitrate in an ester‐based electrolyte is successfully demonstrated, which enables high‐voltage lithium metal batteries. Remarkably, the electrolyte with a high concentration of LiNO₃ additive presents an excellent Coulombic efficiency up to 98.8 % during stable galvanostatic lithium plating/stripping cycles. A full‐cell lithium metal battery with a lithium nickel manganese cobalt oxide cathode exhibits a stable cycling performance showing limited capacity decay. This approach provides an effective electrolyte manipulation strategy to develop high‐voltage lithium metal batteries.     

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[Fe^II(2‐Me₂‐BQPN)(OTf)₂], which bears a tetradentate N₄ ligand (Me₂‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H₂O₂) as oxidant under mild conditions. Experimental studies (including ¹⁸O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐Fe^V(O)₂ reaction intermediate as an active oxidant. This cis‐[Fe^II(chiral N₄ ligand)]²⁺/H₂O₂ method could be a viable green alternative/complement to the existing OsO₄‐based methods for asymmetric alkene dihydroxylation reactions.     

Building an Air Stable and Lithium Deposition Regulable Garnet Interface from Moderate‐Temperature Conversion Chemistry

Garnet‐type electrolytes suffer from unstable chemistry against air exposure, which generates contaminants on electrolyte surface and accounts for poor interfacial contact with the Li metal. Thermal treatment of the garnet at >700 °C could remove the surface contaminants, yet it regenerates the contaminants in the air, and aggravates the Li dendrite issue as more electron‐conducting defective sites are exposed. In a departure from the removal approach, here we report a new surface chemistry that converts the contaminants into a fluorinated interface at moderate temperature <180 °C. The modified interface shows a high electron tunneling barrier and a low energy barrier for Li⁺ surface diffusion, so that it enables dendrite‐proof Li plating/stripping at a high critical current density of 1.4 mA cm^?2. Moreover, the modified interface exhibits high chemical and electrochemical stability against air exposure, which prevents regeneration of contaminants and keeps high critical current density of 1.1 mA cm^?2. The new chemistry presents a practical solution for realization of high‐energy solid‐state Li metal batteries.     

Highly Enantioselective Synthesis of Propargyl Amide with Vicinal Stereocenters through Ir‐Catalyzed Hydroalkynylation

Chiral propargyl amines are valuable synthetic intermediates for the preparation of biologically active compounds and functionalized amines. Catalytic methods to access propargyl amines containing vicinal stereocenters with high diastereoselectivity are particularly rare. We report an unprecedented strategy for the synthesis of enantioenriched propargyl amines with two stereogenic centres. An iridium complex, ligated by a phosphoramidite ligand, catalyzes the hydroalkynylation of β,β‐disubstituted enamides to afford propargyl amides in a highly regio‐, diastereo‐, and enantioselective fashion. Stereodivergent synthesis of all four possible stereoisomers was achieved using this strategy.     

Adjusting the chromatographic properties of poly(ionic liquid)‐modified stationary phases by substitution on the imidazolium cation

Poly(ionic liquid)‐modified stationary phases can have multiple interactions with solutes. However, in most stationary phases, separation selectivity is adjusted by changing the poly(ionic liquid) anions. In this work, two poly(ionic liquid)‐modified silica stationary phases were prepared by introducing the cyano or tetrazolyl group on the pendant imidazolium cation on the polymer chains. Various analytes were selected to investigate their mechanism of retention in the stationary phases using different mobile phases. Two poly(ionic liquid)‐modified stationary phases can provide various interactions toward solutes. Compared to the cyano‐functionalized poly(ionic liquid) stationary phase, the tetrazolyl‐functionalized poly(ionic liquid) stationary phase provides additional cation‐exchange and π‐π interactions, resulting in different separation selectivity toward analytes. Finally, applicability of the developed stationary phases was demonstrated by the efficient separation of nonsteroidal anti‐inflammatory drugs.     

Polymer Transformers: Interdigitating Reaction Networks of Fueled Monomer Species to Reconfigure Functional Polymer States

Adaptivity is an essential trait of life. One type of adaptivity is the reconfiguration of a functional system states by correlating sensory inputs. We report polymer transformers, which can adaptively reconfigure their composition from a state of a mixed copolymer to being enriched in either monomer A or B. This is achieved by embedding and hierarchically interconnecting two chemically fueled activation/deactivation enzymatic reaction networks for both monomers via a joint activation pathway (network level) and an AB linker monomer reactive to both A and B (species level). The ratio of enzymes governing the individual deactivation pathways (our external signals) control the enrichment behavior in the dynamic state. The method shows high programmability of the reconfigured state, rejuvenation of transformation cycles, and quick in situ adaptation. As a proof‐of‐concept, we showcase this dynamic reconfiguration for colloidal surface functionalities.