Developing fluorescent sensors for small-molecule phosphates offers opportunities in optically detecting biorelevant reactions and events. However, it remains elusive how to identify phosphates from other anions, such as carboxylates and sulfates, because current synthetic phosphate receptors lack selectivity. Here we report the construction of a multicolor fluorescent sensor that can identify phosphates from other analogous anions. The key design principle is to take advantage of the highly sensitive conformation-dependent emissive wavelength of diphenyl-9,14-dihydrodibenzo[a,c]phenazine fluorophores to sense the minor structural differences between phosphates and other anions, for example, sulfates and carboxylates. The effect of structural factors such as spacer length and urea versus thiourea has been investigated by comparing the optical properties and binding affinities with the phosphate receptors. This strategy provides a simple and robust fluorescent sensing solution to optically analyze small-molecule phosphates with anti-interference performance.

Rapid halide anion exchange easily occurring in metal-halide perovskite nanoparticles (NPs) makes it nearly impossible to create a single three-dimensional (3D) CsPbX3 (X = Cl, Br, I) NP that simultaneously comprises two separate perovskite components. To circumvent this problem, we first propose a Ni2+-mediated halide anion-exchange strategy in zero-dimensional (0D) Ni2+-doped Cs4PbBr6 (Cs4PbBr6:Ni) perovskites to achieve ultra-stable 3D CsPbX3 NPs with two coexisting different perovskite individuals of CsPbCl3 and/or CsPbBr3. By combining the experimental results with first-principles calculations, we confirm that the completely isolated [PbBr6]4− octahedra in 0D Cs4PbBr6:Ni NPs can restrict rapid halide anion exchange and the anion diffusion preferentially proceeds in the proximity of substitutional NiPb centers, namely [NiBr6]4− octahedra in a meta-stable state, rather than in the 0D Cs4PbBr6 and residual 3D CsPbBr3 regions, thereby delivering intrinsic dual-band excitonic luminescence from a single 3D CsPbX3 NP with a more stable and efficient CsPbCl3 component as compared to its counterparts synthesized using conventional methods. These new insights regarding the precise control of halide anion exchange enable the preparation of a new type of high-efficiency perovskite materials with suppressed anion interdiffusion for prospective optoelectronic devices.

Amide is essential in biologically active compounds, synthetic materials, and building blocks. However, conventional amide production relies on energy-intensive consumption and activating agents that modulate processes to construct the C–N bond. Herein, for the first time, we have successfully realized the formation of amides at industrial current density via the anodic coelectrolysis of alcohol and ammonia under ambient conditions. We have proved that modulation of the interface microenvironment concentration of nucleophile by electrolyte engineering can regulate the reaction pathways of amides rather than acetic acids. The C–N coupling strategy can be further extended to the electrosynthesis of the long-chain and aryl-ring amide with high selectivity by replacing ammonia with amine. Our work opens up a vast store of information on the utilization of biomass alcohol for high-value N-containing chemicals via an electrocatalytic C–N coupling reaction.

Targeted protein degradation (TPD) is an emerging tool for degrading proteins of interest, which affords an attractive modality for cancer therapy. However, the present TPD technologies must engage a proteolysis-specific actuator to initiate degradation of targeted proteins in the proteasome or lysosome. Herein, we report an artificial tractor that can induce endocytosis-mediated protein depletion without hijacking a proteolysis-specific actuator. In this design, bispecific aptamer chimeras (BSACs) are established, which can bridge human epidermal growth factor receptor 2 (ErbB-2), an important biomarker in a common important biomarker in cancer, with membrane proteins of interest. Taking advantage of the property of aptamer-induced endocytosis and digestion of ErbB-2, another membrane protein is translocated into the lysosome in a hitchhike-like manner, resulting in lysosomal proteolysis along with ErbB-2. This strategy frees the TPD from the fundamental limitation of proteolysis-specific actuator and allows simultaneous regulation of the quantity and function of two oncogenic receptors in a cell-type-specific manner, expanding the application scope of TPD-based therapeutics.

In natural systems, water transport across the cellular plasma membranes is mainly mediated by naturally occurring channel protein aquaporins (AQPs), which lead to a series of important physiological functions including cell migration. The construction of artificial analogs of the natural AQPs would generate a new strategy for treating AQP-related diseases. In this report, an artificial water channel has been developed from a unimolecular tubular molecule, which featured structural encapsulation of a single-file water wire composed of oppositely orientated dipolar water molecules. This AQP-like structure endowed the artificial channel in living cells with AQP-like water permeability and selectivity. Interestingly, the artificial channel coupled with cell protrusion formation by mediating water transmembrane transport, leading to cell shape change and migration acceleration. The artificial channel-facilitated cell migration showed application in enhancing in vivo healing of traumatic injury.

Asymmetric hydrogenation of all-carbon aromatics is still a long-standing challenge in the area of asymmetric catalysis. To date, asymmetric (transfer) hydrogenation of naphthols and phenols remains unexplored. Here, we describe a new strategy for such asymmetric transformation via a bimetallic cooperative heterogeneous and homogeneous catalysis. By using HCOONa as the hydrogen source, various naphthols and phenols were partially hydrogenated in HFIP catalyzed by commercial Pd/C catalyst to give ketone intermediates. Further adding the second chiral Ru-tethered-TsDPEN catalyst and MeOH realized the asymmetric reduction of the resulting ketones in a one-pot manner, furnishing chiral alcohols with good to excellent enantioselectivity (up to 99% ee). The use of HFIP is crucial for suppressing ketone over-reduction via heterogeneous catalysis. More importantly, tandem asymmetric transfer hydrogenation of naphthols was also achieved by tuning the volume ratio of mixed HFIP/MeOH solvent, affording chiral 1,2,3,4-tetrahyronaphthols with excellent enantioselectivity but relatively low yield and limited substrate scope.

Lipoteichoic acids (LTAs) are macroamphiphiles composed of alditol, lipid, phosphate, and carbohydrate units. Due to their inherent complexity, it is a severe challenge to access LTAs with structural integrity from natural sources for biological or immunological evaluation. Here, we describe the first total synthesis of Lactococcus garvieae LTA (type II LTA), containing five distinct 1,2-cis gluco/galactopyranosidic linkages, via a novel additive-modulated O-glycosyl trichloroacetimidate preactivation glycosidation strategy. This strategy features (1) high glycosidation yields and excellent 1,2-cis stereoselectivities independent of the donor anomeric configuration, (2) common and inexpensive reagents as promoters and additives, (3) application to standard glycosyl imidate donors without resorting to participating protection, and (4) general application to reactive and less reactive glycosyl acceptors. Thus, via the precise stereocontrolled construction of three galactopyranosidic and two glucopyranosidic bonds on a multigram scale, a series of structurally well-defined LTA molecules were successfully assembled. Immunological evaluation of these type II synthetic LTAs showed a structure–activity relationship in the stimulation of a proinflammatory response.

Nonconjugated clusteroluminogens (CLgens), such as proteins and polystyrene, have become increasingly important in photophysics. They show many advantages over traditional conjugated dyes with fused aromatic rings in biological applications. However, CLgens have historically been unheeded because of their weak visible emissions in the aggregate state, namely clusteroluminescence (CL). Changing the electronic structures of CLgens by precisely regulating the intramolecular through-space interaction (TSI) to improve their photophysical properties remains an enormous challenge. Herein, we propose a general strategy to construct a higher-level intramolecular TSI, namely secondary TSI constructed by the primary TSI and a TSI linker, in multi-aryl-substituted alkanes (MAAs). By introducing methyl and phenyl into 1,1,3,3-tetraphenylpropane, the modified MAAs show efficient CL with high luminescence quantum yield (∼40%) and long emission wavelength (∼530 nm). Then, comprehensive experiments and theoretical studies demonstrate that molecular rigidity and overlap of subunits play pivotal roles in improving these hierarchical TSIs. This work not only provides a feasible strategy to achieve controllable manipulation of hierarchical TSIs and CL but also establishes comprehensive TSI-based aggregate photophysics.

As open substructures of fullerenes, aromatic π-bowls are promising candidates as new organic semiconductors, as well as attractive hosts for fullerenes. We demonstrate herein the synthesis and characterization of a novel C2v symmetric π-bowl, pyracyleno[6,5,4,3,2,1-pqrstuv]pentaphene ( 3). Bowl 3 was equipped with two distinctive reactive sites, allowing for bromination and cross-coupling reactions to readily yield functionalized bowls with two 2,4,6-trimethylphenyl ( 5) and triethylsilyl (TES)-ethynyl ( 6) substituents, respectively. Variable-temperature 1H NMR analysis and density functional theory (DFT) calculations indicated bowl-to-bowl inversions of 3, 5, and 6 at room temperature. By alternating the substituents, the crystal structures of the three π-bowls 3, 5, and 6 could be controlled from 1D linear to 1D slipped to 2D herringbone packing motifs, providing insight into the packing behavior of π-bowls. 1H NMR titration study indicated that the TES-ethynyl substituent enhanced the ability of π-bowl to bind C70 with an association constant of 2485 M−1. The C70 molecules with π-bowls 3 and 6 formed 1:1 complexes, in which C70 molecules aggregated into zig-zag and 1D linear arrays, respectively. The hole mobility of 2.3 cm2 V−1 s−1 and electron mobility of 0.16 cm2 V−1 s−1 of π-bowl 3 and its complex with C70 were demonstrated, respectively, which proved a great value for the development of aromatic π-bowl semiconductors with tunable properties for organic electronic devices.

Difluoromethyl ethers are formed through mechanochemical reactions of alcohols with difluorocarbene in a mixer mill. The protocol could be applied to primary, secondary, and tertiary alcohols, yielding the corresponding products in excellent yields (up to 99%) after 1 h reaction time at room temperature. The transformations proceeded under solvent-free reaction conditions, followed by product purification by filtration, which drastically reduced the amount of waste generated during the process.

Organic photovoltaic (OPV) cells have demonstrated remarkable performance in small, spin-coated areas. Nevertheless significant challenges persist in the form of large efficiency losses due to the fact that the ideal morphology cannot be preserved in the transition of small-area cells to large-scale panels. Herein, the ternary strategy of incorporating the third component FTCC-Br into the active layer of PB2:BTP-eC9 is employed to improve absorption response, optimize morphology, and reduce charge recombination, leading to a power conversion efficiency (PCE) of 19.5% (certified as 19.1% by the National Institute of Metrology, China). Moreover, the addition of FTCC-Br can control the aggregation kinetics of the active layer during the film formation process, transferring the optimal morphology to the blade-coated large-area films. Based on the highly efficient ternary bulk heterojunction, the 50 cm2 OPV modules exhibited a PCE of 15.2% with respect to the active area. Importantly, the ternary OPV cells retain 80% of its initial PCE after 4000 h under continuous illumination. Our work demonstrates that the addition of a third component has the potential to improve the efficiency and stability of large-area organic solar cells.

A general method for the synthesis of bench-stable bis(difluoromethyl) pentacoordinate phosphoranes has been developed. The reaction is rapid, operationally simple, and easily scalable. The pentacoordinate phosphoranes can generate both difluoromethyl radical (·CF2H) and difluorocarbene (:CF2) intermediates. Thus, a variety of fluoroalkylation transformations have been achieved by ·CF2H, such as oxidative difluoromethylation of electron-deficient heterocycles, nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides, and photoredox difluoromethylation of alkenes, or by :CF2, such as gem-difluorocyclopropanation of alkenes, base-promoted difluoromethylation of heteroatom nucleophiles, Pd-catalyzed difluoromethylation of arylboronic acids, and Cu-mediated trifluoromethylation of aryl iodides (via :CF2 and recombined CF3−). These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.

Organic electrode materials have attracted much attention for lithium batteries because of their high capacity, flexible designability, and environmental friendliness. Understanding the redox chemistry of organic electrode materials is essential for optimizing electrochemical performance and designing new molecules. This review aims to summarize the redox chemistry of different organic electrode materials in lithium batteries, including carbonyl compounds, conductive polymers, organosulfur compounds, organic radicals, imine compounds, compounds with superlithiation ability, and azo compounds. The discussions are focused on the evolution of their molecular and crystal structures during discharge/charge processes utilizing various characterization approaches. To date, carbonyl compounds based on the conversion between C=O and C–OLi have been proven to be one of the most promising organic electrode materials for lithium batteries. Future works should pay more attention to the detection of redox intermediates through operando techniques and the further combination of theoretical calculations. This review provides insights into the redox chemistry of organic electrode materials in lithium batteries.

Owing to the shortcomings of traditional electrode materials in alkali metal-ion batteries (AIBs), such as limited reversible specific capacity, low power density, and poor cycling performance, it is particularly important to develop new electrode materials. Covalent organic frameworks (COFs) are crystalline porous polymers that incorporate organic building blocks into their periodic structures through dynamic covalent bonds. COFs are superior to organic materials because of their high designability, regular channels, and stable topology. Since the first report of DTP-ANDI-COF as a cathode material for lithium-ion batteries in 2015, research on COF electrode materials has made continuous progress and breakthroughs. This review briefly introduces the characteristics and current challenges associated with COF electrode materials. Furthermore, we summarize the basic reaction types and active sites according to the categories of covalent bonds, including B–O, C=N, C–N, and C=C. Finally, we emphasize the perspectives on basic structure and morphology design, dimension and size design, and conductivity improvement of COFs based on the latest progress in AIBs. We believe that this review provides important guidelines for the development of high-efficiency COF electrode materials and devices for AIBs.

Light-induced recognition, assemblies, and materials are intensive areas of research due to their high spatiotemporal resolution. Herein, we demonstrated photoswitchable molecular recognition via dithienylethene-triggered reversible structural regulation of dynamic covalent hydrazone bonds. By combining dithienylethenes and cyclic hemiacetals, the photochemical open-ring and closed-ring forms enabled turning off and on the creation of a wide range of hydrazones when desired. Light-induced bidirectional switching between hydrazones and their cyclization structures promoted by a neighboring carboxyl group was further achieved. By taking advantage of reversible structural changes to toggle on and off the binding pocket, photoswitchable recognition of metal ions was realized. Finally, the construction of an acylhydrazone polymer offered a facile way for light-mediated selective extraction/release. The strategies and results reported here should find applications in many contexts, such as dynamic assemblies, molecular switches, and smart materials.

Although dynamic covalent chemistry (DCvC) has been widely utilized to synthesize small molecules and polymers, it remains challenging to construct highly ordered polymeric architectures via DCvC. Further exploration of novel dynamic linkages (in addition to commonly used imine and boronate ester) will expand the library of readily accessible dynamic linkages, diversify the polymeric structures, and unlock new functionality. In this mini-review, the DCvC-based synthetic strategies for enhancing the structural orders of polymeric architectures will be discussed from both thermodynamic control and kinetic control aspects. The relationship between the structure, stability, and dynamic behavior of a DCvC bond will be presented. Then recent examples of constructing polymers with DCvC and supramolecular bonding interactions, such as metal-ligand coordination, host–guest binding, and hydrogen bonding, will be reviewed to demonstrate their synergistic relationship. Furthermore, polymers featuring relatively unexplored DCvC will be highlighted to underscore how developing novel dynamic linkages and fundamental DCvC studies can broaden the scope of functional polymeric architectures. In the end, the challenges in the current field and possible future directions will also be discussed. Advancements in using these design principles will undoubtedly lead to the development of intriguing chemistries, polymeric architectures, and functionality.

In artificial photosynthesis systems, synthetic diiron complexes are popular [FeFe]-hydrogenase mimics, which are attractive for the fabrication of photocatalyst-protein hybrid structures to amplify hydrogen (H2) generation capability. However, constructing a highly bionic and efficient catalytic hybrid system is a major challenge. Notably, we designed an ideal hybrid nanofibrils system that incorporates the crucial components: (1) a [FeFe]-H2ase mimic, which has a three-arm architecture (named triFeFe) for more interaction sites and higher catalytic activity and (2) uniform hybrid nanofibrils as the biological environment in which cysteine-catalyst coordination and the hydrogen-bonding network play a vital role in both catalyst binding and hydrogen evolution reaction activity. The assembled hybrid nanofibrils achieve efficient H2 generation with a turnover number of 2.3 × 103, outperforming previously reported diiron catalyst-protein hybrid systems. Additionally, the hybrid nanofibrils work with photosynthetic thylakoids to produce H2, without extra photosensitizers or electron shuttle proteins, which advances the bioengineering of living systems for solar-driven biofuel production.

Halide perovskites have become a hot topic in materials research due to their potential applications in a variety of fields, from optoelectronic and thermoelectric devices to solar cells. Doping of halide perovskites can be achieved by introducing different types of dopants, such as metal cations, anions, and organic molecules, leading to increased stability and improved optoelectronic properties. Moreover, doping can introduce new functionalities, such as increased spin lifetime and thermal stability. These features make doped halide perovskites a highly promising candidate for optoelectronic applications. In this mini-review, we highlight the latest advances in ion-doped halide perovskites and their immense potential for various applications.

Conducting polymers (CPs) have long been studied as cathode materials for lithium-ion batteries, but the low doping level (maximum: 30–50% or even lower) and poor cycling stability limit their applications. Herein, we have developed a method of nanopore-confined in situ electropolymerization to prepare nanostructured polythiophene-type porous cathodes, achieving significantly improved doping availability and long cycle life. It was verified that the nanosized polymer formed in situ and loose porous structure are conducive to the doping reaction and maintain high electrochemical stability. The constructed thieno[3,2-b]thiophene (TtTP)/active carbon cathode delivers an ultrahigh reversible capacity of 309.2 mAh g−1 (doping level up to 80.9%) along with an ultrahigh energy density of 1252.3 Wh Kg−1, and an ultrahigh rate capability (172.4 mAh g−1 at 30 A g−1), which far exceed all the CPs and even all the p-type organic cathode materials reported. Moreover, an excellent long cycle life of 2000 cycles at 5 A g−1 is also revealed, which is a new record for CPs-based cathode materials in nonaqueous lithium-ion batteries. Our method provides an effective strategy to improve the doping level and cycling stability of CP-based cathode materials.

Interface engineering in device fabrication is a significant but complicated issue. Although great successes have been achieved by conventional physical in situ or ex situ methods, it still suffers from complicated procedures. In this work, we present a facile method for fabricating phthalocyanine (Pc)-based two-dimensional conductive metal–organic framework (MOF) films. Based on PcM-Cu (M = Ni, Cu, H2) MOF films, spin valves with a vertical configuration of La0.67Sr0.33MnO3/PcM-Cu MOFs/Co were constructed successfully, and exhibited notably high negative magnetoresistance (MR) up to −22% at 50 K. The penetrated Co atoms coordinated with the dehydrogenated hydroxy groups in the MOFs resulting in an antiferromagnetic layer of the PcM-Cu-Co hybrid structure. Interestingly, a significant exchange bias effect was demonstrated at the PcM-Cu MOF/Co interface, beneficial for the MR behavior. Thus, our present study provides new insights into developing high-performance organic spin valves via de novo molecular design.