Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na_0.44Co_0.1Mn_0.9O₂ cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.     

Strategy for the Construction of Diverse Poly‐NHC‐Derived Assemblies and Their Photoinduced Transformations

A series of supramolecular assemblies of types [Ag₈( L )₄](PF₆)₈ and [Ag₄( L )₂](PF₆)₄, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H₄‐L(PF₆)₄ and Ag^I ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H₄‐L(PF₆)₄. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag₄( L )₂](PF₆)₄ or [Ag₈( L )₄](PF₆)₈ stoichiometry. The molecular structures of selected [Ag₈( L )₄](PF₆)₈ and [Ag₄( L )₂](PF₆)₄ assemblies were determined by X‐ray diffraction analyses. While H₄‐ L (PF₆)₄ does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties.     

Covalent Organic Framework for Improving Near‐Infrared Light Induced Fluorescence Imaging through Two‐Photon Induction

Fluorescent materials exhibiting two‐photon induction (TPI) are used for nonlinear optics, bioimaging, and phototherapy. Polymerizations of molecular chromophores to form π‐conjugated structures were hindered by the lack of long‐range ordering in the structure and strong π–π stacking between the chromophores. Reported here is the rational design of a benzothiadiazole‐based covalent organic framework (COF) for promoting TPI and obtaining efficient two‐photon induced fluorescence emissions. Characterization and spectroscopic data revealed that the enhancement in TPI performance is attributed to the donor‐π‐acceptor‐π‐donor configuration and regular intervals of the chromophores, the large π‐conjugation domain, and the long‐range order of COF crystals. The crystalline structure of TPI‐COF attenuates the π–π stacking interactions between the layers, and overcomes aggregation‐caused emission quenching of the chromophores for improving near‐infrared two‐photon induced fluorescence imaging.     

Quantitative Design of Bright Fluorophores and AIEgens by the Accurate Prediction of Twisted Intramolecular Charge Transfer (TICT)

Inhibition of TICT can significantly increase the brightness of fluorescent materials. Accurate prediction of TICT is thus critical for the quantitative design of high‐performance fluorophores and AIEgens. TICT of 14 types of popular organic fluorophores were modeled with time‐dependent density functional theory (TD‐DFT). A reliable and generalizable computational approach for modeling TICT formations was established. To demonstrate the prediction power of our approach, we quantitatively designed a boron dipyrromethene (BODIPY)‐based AIEgen which exhibits (almost) barrierless TICT rotations in monomers. Subsequent experiments validated our molecular design and showed that the aggregation of this compound turns on bright emissions with ca. 27‐fold fluorescence enhancement, as TICT formation is inhibited in molecular aggregates.     

Modular Synthesis of Nona‐Decasaccharide Motif from Psidium guajava Polysaccharides: Orthogonal One‐Pot Glycosylation Strategy

The synthesis of long, branched, and complex carbohydrate sequences remains a challenging task in chemical synthesis. Reported here is an efficient and modular one‐pot synthesis of a nona‐decasaccharide and shorter sequences from Psidium guajava polysaccharides, which have the potent α‐glucosidase inhibitory activity. The synthetic strategy features: 1) several one‐pot glycosylation reactions on the basis of N‐phenyltrifluoroacetimidate (PTFAI) and Yu glycosylation to streamline the chemical synthesis of oligosaccharides, 2) the successful and efficient assembly sequences (first O3′, second O5′, final O2′) toward the challenging 2,3,5‐branched Araf motif, 3) the stereoselective 1,2‐cis‐glucosylation by reagent control, and 4) the convergent [6+6+7] one‐pot coupling reaction for the final assembly of the target nona‐decasaccharide. This orthogonal one‐pot glycosylation strategy can streamline the chemical synthesis of long, branched, and complicated carbohydrate chains.     

Enantioselective Catalytic Aldehyde α‐Alkylation/Semipinacol Rearrangement: Construction of α‐Quaternary‐δ‐Carbonyl Cycloketones and Total Synthesis of (+)‐Cerapicol

An enantioselective aldehyde α‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α‐quaternary‐δ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol.     

3‐O‐Sulfation of Heparan Sulfate Enhances Tau Interaction and Cellular Uptake

Prion‐like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3‐O‐sulfation (3‐O‐S) of HS significantly enhances tau binding. In Hs3st1^?/? (HS 3‐O‐sulfotransferase‐1 knockout) cells, reduced 3‐O‐S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3‐O‐S HS 12‐mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3‐O‐S binding sites to the microtubule binding repeat 2 (R2) and proline‐rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3‐O‐sulfation. Our work demonstrates that this rare 3‐O‐sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease‐modifying treatment of AD and other tauopathies.     

Molecular‐Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In Situ Polymerization

Commercial ultrafiltration membranes have proliferated globally for water treatment. However, their pore sizes are too large to sieve gases. Conjugated microporous polymers (CMPs) feature well‐developed microporosity yet are difficult to be fabricated into membranes. Herein, we report a strategy to prepare molecular‐sieving membranes by partitioning the mesoscopic channels in water ultrafiltration membrane (PSU) into ultra‐micropores by space‐confined polymerization of multi‐functionalized rigid building units. Nine CMP@PSU membranes were obtained, and their separation performance for H₂/CO₂, H₂/N₂, and H₂/CH₄ pairs surpass the Robeson upper bound and rival against the best of those reported membranes. Furthermore, highly crosslinked skeletons inside the channels result in the structural robustness and transfer into the excellent aging resistance of the CMP@PSU. This strategy may shed light on the design and fabrication of high‐performance polymeric gas separation membranes.     

Photoinduced Single‐Electron Transfer as an Enabling Principle in the Radical Borylation of Alkenes with NHC–Borane

A photoinduced SET process enables the direct B?H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway.     

2-(Diphenylphosphino)benzoate-functionalized diiron ethane-1,2-dithiolate complexes with uncoordinated or coordinated phosphine ligand

Abstract

Treatment of the starting complex [Fe₂(CO)₆{μ-SCH₂CH(CH₂OH)S}] (1) with 2-(diphenylphosphino)benzoic acid in the presence of N,N’-dicyclohexylcarbodiimide and 4-dimethylaminopyridine gave the corresponding ester derivative [Fe₂(CO)₆{μ-SCH₂CH(CH₂O₂CC₆H₄PPh₂-2)S}] (2) in 92% yield. Further treatment of complex 2 with one equivalent of Me₃NO · 2?H₂O as the decarbonylating agent yielded diphenylphosphino-substituted complex [Fe₂(CO)₅{μ-SCH₂CH(CH₂O₂CC₆H₄PPh₂-2)S}] (3) in 79% yield. Both complexes were characterized by elemental analysis, spectroscopy, as well as by X-ray crystallography. Additionally, the electrochemical properties of these complexes were studied by cyclic voltammetry.