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Supramolecular assembly frameworks (SAFs) represent a new category of porous materials, utilizing non‐covalent interactions, setting them apart from metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This category includes but is not restricted to hydrogen‐bonded organic frameworks and supramolecular organic frameworks. SAFs stand out for their outstanding porosity, crystallinity, and stability, alongside unique dissolution‐recrystallization dynamics that enable significant structural and functional modifications. Crucially, their non‐covalent assembly strategies allow for a balanced manipulation of porosity, symmetry, crystallinity, and dimensions, facilitating the creation of advanced crystalline porous materials unattainable through conventional covalent or coordination bond synthesis. Despite their considerable promise in overcoming several limitations inherent to MOFs and COFs, particularly in terms of solution‐processability, SAFs have received relatively little attention in recent literature. This Minireview aims to shed light on standout SAFs, exploring their design principles, synthesis strategies, and characterization methods. It emphasizes their distinctive features and the broad spectrum of potential applications across various domains, aiming to catalyze further development and practical application within the scientific community. [ABSTRACT FROM AUTHOR]

Covalent polymerization of organic molecules into crystalline one‐dimensional (1D) polymers is effective for achieving desired thermal, optical, and electrical properties, yet it remains a persistent synthetic challenge for their inherent tendency to adopt amorphous or semicrystalline phases. Here we report a strategy to synthesize crystalline 1D covalent organic frameworks (COFs) composing quasi‐conjugated chains with benzoxazine linkages via the one‐pot Mannich reaction. Through [4+2] and [2+2] type Mannich condensation reactions, we fabricated stoichiometric and sub‐stoichiometric 1D covalent polymeric chains, respectively, using doubly and singly linked benzoxazine rings. The validity of their crystal structures has been directly visualized through state‐of‐the‐art cryogenic low‐dose electron microscopy techniques. Post‐synthetic functionalizations of them with a chiral MacMillan catalyst produce crystalline organic photocatalysts that demonstrated excellent catalytic and recyclable performance in light‐driven asymmetric alkylation of aldehydes, affording up to 94 % enantiomeric excess [ABSTRACT FROM AUTHOR]

Exocytosis involving the fusion of intracellular vesicles with cell membrane, is thought to be modulated by the mechanical cues in the microenvironment. Single‐cell electrochemistry can offer unique information about the quantification and kinetics of exocytotic events; however, the effects of mechanical force on vesicular release have been poorly explored. Herein, we developed a stretchable microelectrode with excellent electrochemical stability under mechanical deformation by microfabrication of functionalized poly(3,4‐ethylenedioxythiophene) conductive ink, which achieved real‐time quantitation of strain‐induced vesicular exocytosis from a single cell for the first time. We found that mechanical strain could cause calcium influx via the activation of Piezo1 channels in chromaffin cell, initiating the vesicular exocytosis process. Interestingly, mechanical strain increases the amount of catecholamines released by accelerating the opening and prolonging the closing of fusion pore during exocytosis. This work is expected to provide revealing insights into the regulatory effects of mechanical stimuli on vesicular exocytosis. [ABSTRACT FROM AUTHOR]

Optically active π‐conjugated polymers (OACPs) have garnered increasing research interest for their resemblance to biological helices and intriguing chirality‐related functions. Traditional methods for synthesizing involve decorating achiral conjugated polymer architectures with enantiopure side substituents through complex organic synthesis. Here, we report a new approach: the templated synthesis of unsubstituted OACPs via supramolecularly confined polymerizations of achiral monomers within nanopores of 2D or 3D chiral covalent organic frameworks (CCOFs). We show that the chiral π‐rich nanospaces facilitate the in situ enantiospecific polymerization and self‐propagation, akin to nonenzymatic polymerase chain reaction (PCR) system, resulting in chiral imprinting. The stacked polymer chains are kinetically inert enough to memorize the chiral information after liberating from CCOFs, and even after treatment at temperature up to 200 °C. The isolated OACPs demonstrate robust enantiodiscrimination, achieving up to 85 % ee in separating racemic amino acids. This underscores the potential of utilizing CCOFs as templates for supramolecularly imprinting optical activity into CPs, paving the way for synthetic evolution and advanced functional exploration of OACPs. [ABSTRACT FROM AUTHOR]

During multivalent ions insertion processes, intense electrostatic interaction between charge carriers and host makes the high‐performance reversible Al3+ storage remains an elusive target. On account of the strong electrostatic repulsion and poor robustness, Prussian Blue analogues (PBAs) suffer severely from the inevitable and large strain and phase change during reversible Al3+ insertion. Herein, we demonstrate an entropy‐driven strategy to realize ultralong life aqueous Al‐ion batteries (AIBs) based on medium entropy PBAs (ME‐PBAs) host. By multiple redox active centers introduction, the intrinsic poor conductivity can be enhanced simultaneously, resulting in outstanding capabilities of electrochemical Al3+ storage. Meanwhile, the co‐occupation at metal sites in PBA frameworks can also increase the M−N bond intensity, which is beneficial for constraining the phase change during consecutive Al3+ reversible insertion, to realize an extended lifespan over 10,000 cycles. Based on the calculation at different operation states, the fluctuation of ME‐PBA lattice parameters is only 1.2 %. Assembled with MoO3 anodes, the full cells can also deliver outstanding electrochemical properties. The findings highlight that, the entropy regulation strategy could uncover the isochronous constraint on both strain and phase transition for long‐term reversible Al3+ storage, providing a promising design for advanced electrode materials for aqueous multivalent ions batteries. [ABSTRACT FROM AUTHOR]

Bridged benzazepine scaffolds, possessing unique structural and physicochemical activities, are widespread in various natural products and drugs. The construction of these skeletons often requires elaborate synthetic effort with low efficiency. Herein, we develop a simple and divergent approach for constructing various bridged benzazepines by a photocatalytic intermolecular dearomatization of naphthalene derivatives with readily available α‐amino acids. The bridged motif is created via a cascade sequence involving photocatalytic 1,4‐hydroaminoalkylation, alkene isomerization and cyclization. Interestingly, the diastereoselectivity can be regulated through different reaction modes in the cyclization step. Moreover, aminohydroxylation and its further bromination have also been demonstrated to access highly functionalized bridged benzazepines. Preliminary mechanistic studies have been performed to get insights into the mechanism. This method provides a divergent synthetic approach for construction of highly functionalized bridged benzazepines, which have been otherwise difficult to access. [ABSTRACT FROM AUTHOR]

The catalytic bis‐allylation of alkynes is an important but challenging protocol to construct all‐carbon tetra‐substituted alkenes. Particularly, the catalytic unsymmetrical bis‐allylation of alkynes remains as an underexplored task to date. We herein report an unprecedented unsymmetrical bis‐allylation by simultaneously utilizing electrophilic trifluoromethyl alkene and nucleophilic allylboronate as the allylic reagents. With the aid of robust Ni0/NHC catalysis, valuable skipped trienes can be obtained in high regio‐ and stereo‐selectivities under mild conditions. Mechanistic studies indicate that the reaction may proceed through a β‐fluorine elimination of a nickelacycle followed by a transmetalation step with allylboronate. The present method exhibits a good tolerance of various functional groups. Besides, the skipped triene products can undergo an array of elaborate transformations, which highlights the potential applications of this strategy. [ABSTRACT FROM AUTHOR]

Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ultra‐low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2‐tetrafluoro‐3‐methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li+ to induce self‐assembly of the electrolyte solution to form a peculiar core‐shell‐solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li+ transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to −40 °C at high current densities. Meanwhile, anode‐free high‐voltage cell retains 87 % capacity after 100 cycles. [ABSTRACT FROM AUTHOR]

Construction of supramolecular structures with internal functionalities is a promising approach to build enzyme‐like cavities. The endo‐functionalized [Pd12L24] and [Pd2L4] coordination cages represent the most successful systems in this regard. However, these systems mainly contain one type of endo‐moiety. We herein provide a solution for the controlled endo‐functionalization of [Pd2L4] cages. Site‐selective introduction of the endo‐functional group was achieved through the formation of heteroleptic [Pd2(LA)2(LB)(LC)] cages. Using two orthogonal steric control elements is the key for the selective formation of the hetero‐assemblies. We demonstrated the construction of two hetero‐cages with a single internal functional group as well as a hetero‐cage with two distinct endohedral functionalities. The endo‐functionalized hetero‐cages bound sulfonate guests with fast‐exchange dynamics. This strategy provides a new solution for the controlled endo‐functionalization of supramolecular cavities. [ABSTRACT FROM AUTHOR]

Non‐invasive dynamic tracking of lysosomes and their interactions with other organelles is important for the study of lysosomal function and related diseases. However, many fluorescent dyes developed so far to target lysosomes cannot be used to monitor these processes due to the high concentrations required for imaging, long cell penetration times, and non‐ideal photostability. In this regard, we synthesized three lysosomal targeting probes with large Stokes shifts, good stability, and high brightness. The Q‐P‐ARh dye, developed by us for the first time, can stain lysosomes at ultra‐low concentrations (1.0 nM) without affecting the physiological functions of the lysosomes. More importantly, its excellent anti‐interference ability and ultrafast lysosomal staining ability (within 1.0 min) clearly monitored the entire dynamic process of lipophagy. Ultimately, this method can greatly contribute to the study of autophagy pathways. This novel fluorescence platform shows great promise for the development of biological probes for application in pathological environments. [ABSTRACT FROM AUTHOR]

Chiral imidodiphosphates (IDPs) have emerged as strong Brønsted acid catalysts for many enantioselective processes. However, the dynamic transformation between O,O‐syn and O,O‐anti conformers typically results in low enantioselectivity. Here we demonstrate that topologies of metal‐organic frameworks (MOFs) can be exploited to control IDP conformations and local chiral microenvironments for enantioselective catalysis. Two porous Dy‐MOFs with different topologies are obtained from an enantiopure 1,1′‐biphenol IDP‐based tetracarboxylate ligand. While the ligand adopts a 4‐ or 3‐connected (c) binding mode, all IDPs are rigidified to get only a single O,O‐syn conformation and display greatly enhanced Brønsted acidity relative to the free IDP. The MOF with the 4‐c IDP that has a relatively less compact shape than the 3‐c IDP can be an efficient and recyclable heterogeneous Brønsted acid catalysing the challenging asymmetric O,O‐acetalization reaction with up to 96 % enantiomeric excess. [ABSTRACT FROM AUTHOR]

Nucleic acid (NA) computation has been widely developed in the past years to solve kinds of logic and mathematic issues in both information technologies and biomedical analysis. However, the difficulty to integrate non‐NA molecules limits its power as a universal platform for molecular computation. Here, we report a versatile prototype of hybridized computation integrated with both nucleic acids and non‐NA molecules. Employing the conformationally controlled ligand converters, we demonstrate that non‐NA molecules, including both small molecules and proteins, can be computed as nucleic acid strands to construct the circuitry with increased complexity and scalability, and can be even programmed to solve arithmetical calculations within the computational nucleic acid system. This study opens a new door for molecular computation in which all‐NA circuits can be expanded with integration of various ligands, and meanwhile, ligands can be precisely programmed by the nuclei acid computation. [ABSTRACT FROM AUTHOR]

Photosynthetic organisms organize discrete light‐harvesting complexes into large‐scale networks to facilitate efficient light collection and utilization. Inspired by nature, herein, synthetic DNA templates were used to direct the formation of dye aggregates with a cyanine dye, K21, into discrete branched photonic complexes, and two‐dimensional (2D) excitonic networks. The DNA templates ranged from four‐arm DNA tiles, ≈10 nm in each arm, to 2D wireframe DNA origami nanostructures with different geometries and varying dimensions up to 100×100 nm. These DNA‐templated dye aggregates presented strongly coupled spectral features and delocalized exciton characteristics, enabling efficient photon collection and energy transfer. Compared to the discrete branched photonic systems templated on individual DNA tiles, the interconnected excitonic networks showed approximately a 2‐fold increase in energy transfer efficiency. This bottom‐up assembly strategy paves the way to create 2D excitonic systems with complex geometries and engineered energy pathways. [ABSTRACT FROM AUTHOR]

Organic molecules which can undergo excited‐state intramolecular proton transfer (ESIPT) process have been considered as ideal gain materials for near‐infrared organic lasers owing to their effective four‐level systems. However, extending lasing wavelength beyond 800 nm with present ESIPT‐active gain materials is still in challenge. Herein, we established a molecular design strategy that operates via extending the π‐conjugated system of the ESIPT parent core to enhance the cascaded double ESIPT process and thus to achieve the red‐shifted six‐level system lasing. Concretely, a model molecule with 1,9‐dihydroxyanthracene as the ESIPT parent core was designed and synthesized, which was proved to undergo twice cascaded ESIPT processes while the 1,8‐dihydroxynaphthalene‐based analogue can only undergo once ESIPT process based on DFT calculations and ultrafast dynamics analyses. Finally, a six‐level system lasing toward 900 nm was achieved with a low threshold of 27.4 μJ cm−2. [ABSTRACT FROM AUTHOR]

Developing practical and mild strategies for the direct functionalization of white phosphorus (P4) without chlorination is an appealing but formidable challenge. To this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon‐centered radicals from N‐hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P4 molecule under transition‐metal‐ and photocatalyst‐free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one‐pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct P−F, P−C, P−N, and P−O bonds was also demonstrated. [ABSTRACT FROM AUTHOR]

Oxidative N‐heterocyclic carbene (NHC) organocatalysis, typically leading to the formation of acyl azolium reactive intermediates, constitutes one of the most important activation strategies for the NHC‐catalyzed chemical transformations. Here, we report an unprecedented oxidative radical NHC catalysis by using peroxyester as the external single‐electron oxidant to realize divergent difunctionalization of olefins. The key to success of this chemistry is the catalytic generation of oxygen radicals that could trigger an intermolecular hydrogen atom transfer to activate the inert C−H bonds, thereby enabling the productive radical relay process. With this protocol, commonly used general chemicals could serve as radical precursors to allow efficient synthesis of value‐added products in a straightforward and cost‐effective manner. Preliminary mechanistic investigations, including control experiments and DFT calculations, shed light on the NHC organocatalytic radical reaction mechanism. [ABSTRACT FROM AUTHOR]

Electroreduction of CO2 to CO is a promising approach for the cycling use of CO2, while it still suffers from impractical current density and durability. Here we report a single‐atom nanozyme (Ni−N5−C) that achieves industrial‐scale performance for CO2‐to‐CO conversion with a Faradaic efficiency (FE) exceeded 97 % over −0.8–−2.4 V vs. RHE. The current density at −2.4 V vs. RHE reached a maximum of 1.23 A cm−2 (turnover frequency of 69.7 s−1) with an FE of 99.6 %. No obvious degradation was observed over 100 hours of continuous operation. Compared with the planar Ni−N4 site, the square‐pyramidal Ni−N5 site has an increase and a decrease in the dz2 ${{{\rm d}}_{{z}^{2}}}$ and dxz/yz orbital energy levels, respectively, as revealed by density functional theory calculations. Thus, the Ni−N5 catalytic site is more superior to activate CO2 molecule and reduce the energy barriers as well as promote the CO desorption, thus boosting the kinetic activation process and catalytic activity. [ABSTRACT FROM AUTHOR]

A versatile terpene synthase (LcTPS2) producing unconventional macrocyclic terpenoids was characterized from Leucosceptrum canum. Engineered Escherichia coli and Nicotiana benthamiana expressing LcTPS2 produced six 18‐/14‐membered sesterterpenoids including five new ones and two 14‐membered diterpenoids. These products represent the first macrocyclic sesterterpenoids from plants and the largest sesterterpenoid ring system identified to date. Two variants F516A and F516G producing approximately 3.3‐ and 2.5‐fold, respectively, more sesterterpenoids than the wild‐type enzyme were engineered. Both 18‐ and 14‐membered ring sesterterpenoids displayed significant inhibitory activity on the IL‐2 and IFN‐γ production of T cells probably via inhibition of the MAPK pathway. The findings will contribute to the development of efficient biocatalysts to create bioactive macrocyclic sesterterpenoids, and also herald a new potential in the well‐trodden territory of plant terpenoid biosynthesis. [ABSTRACT FROM AUTHOR]

Many cells in vivo have their inherent motions, which involve numerous biochemical and biophysical signals synergistically regulating cell behavior and function. However, existing methods offer little information about the concurrently chemical and physical responses of dynamically pulsing cells. Here, we report a soft electrode with an electrospun poly(3,4‐ethylenedioxythiophene) (PEDOT)‐based nanomesh to fully comply with spontaneous motions of cells. Moreover, this electrode demonstrated excellent electrical conductivity, electrochemical performance and cellular biocompatibility. Cardiomyocytes cultured thereon exhibited autonomous and rhythmic contractility, and synchronously induced mechanical deformation of the underlying electrode, which allowed real‐time monitoring of nitric oxide release and electrophysiological activity of cardiomyocytes. This work provides a promising way toward recording chemical and electrical signals of biological systems with their natural motions. [ABSTRACT FROM AUTHOR]

Tandem catalysts can divide the reaction into distinct steps by local multiple sites and thus are attractive to trigger CO2RR to C2+ products. However, the evolution of catalysts generally exists during CO2RR, thus a closer investigation of the reconstitution, interplay, and active origin of dual components in tandem catalysts is warranted. Here, taking AgI−CuO as a conceptual tandem catalyst, we uncovered the interaction of two phases during the electrochemical reconstruction. Multiple operando techniques unraveled that in situ iodine ions leaching from AgI restrained the entire reduction of CuO to acquire stable active Cu0/Cu+ species during the CO2RR. This way, the residual iodine species of the Ag matrix accelerated CO generation and iodine‐induced Cu0/Cu+ promotes C−C coupling. This self‐adaptive dual‐optimization endowed our catalysts with an excellent C2+ Faradaic efficiency of 68.9 %. Material operando changes in this work offer a new approach for manipulating active species towards enhancing C2+ products. [ABSTRACT FROM AUTHOR]

Pd‐based molecular square Pd4L4 and triangle Pd3L3 represent the molecular ancestors of metal‐coordination polyhedra that have been an integral part of the field for the last 30 years. Conventional solution‐based reactions between cis‐protected Pd ions and 2,2′‐bipyridine exclusively give Pd4L4 and/or Pd3L3 as the sole products. We herein show that, under solvent‐free mechanochemical conditions, the self‐assembly energy landscape can be thermodynamically manipulated to form an elusive cyclic dimer Pd2L2 for the first time. In the absence of solvent, Pd2L2 is indefinitely stable in the solid‐state, but converts rapidly to its thermodynamic products Pd3L3 and Pd4L4 in solution, confirming Pd2L2 as a short‐lived kinetic species in the solution‐based self‐assembly process. Our results highlight how mechanochemistry grants access to a vastly different chemical space than available under conventional solution conditions. This provides a unique opportunity to isolate elusive species in self‐assembly processes that are too reactive to both "see" and "capture". [ABSTRACT FROM AUTHOR]

Recently, polymer mechanochemistry has attracted much scientific interest due to its potential to develop degradable polymers. When the two ends of a polymer chain experience a linear pulling stress, molecular strain builds up, at sufficiently strong force, a bond scission of the weakest covalent bond results. In contrast, bond‐breaking events triggered by conformational stress are much less explored. Here, we discovered that a Zn salen complex would undergo conformational switching upon allosteric complexation with alkanediammonium guests. By controlling the guest chain length, the torsional strain experienced by Zn complex can be modulated to induce bond cleavage with chemical stimulus, and reactivity trend is predicted by conformational analysis derived by DFT calculation. Such strain‐release reactivity by a Zn(salen) complex initiated by guest binding is reminiscent of conformation‐induced reactivity of enzymes to enable chemical events that are otherwise inhibited. [ABSTRACT FROM AUTHOR]

Pd‐based molecular square Pd4L4 and triangle Pd3L3 represent the molecular ancestors of metal‐coordination polyhedra that have been an integral part of the field for the last 30 years. Conventional solution‐based reactions between cis‐protected Pd ions and 2,2′‐bipyridine exclusively give Pd4L4 and/or Pd3L3 as the sole products. We herein show that, under solvent‐free mechanochemical conditions, the self‐assembly energy landscape can be thermodynamically manipulated to form an elusive cyclic dimer Pd2L2 for the first time. In the absence of solvent, Pd2L2 is indefinitely stable in the solid‐state, but converts rapidly to its thermodynamic products Pd3L3 and Pd4L4 in solution, confirming Pd2L2 as a short‐lived kinetic species in the solution‐based self‐assembly process. Our results highlight how mechanochemistry grants access to a vastly different chemical space than available under conventional solution conditions. This provides a unique opportunity to isolate elusive species in self‐assembly processes that are too reactive to both "see" and "capture". [ABSTRACT FROM AUTHOR]

The direct functionalization of inert C(sp3)−H bonds under environmentally benign catalytic conditions remains a challenging task in synthetic chemistry. Here, we report an organocatalytic remote C(sp3)−H acylation of amides and cascade cyclization through a radical‐mediated 1,5‐hydrogen atom transfer mechanism using N‐heterocyclic carbene as the catalyst. Notably, a diversity of nitrogen‐containing substrates, including simple linear aliphatic carbamates and ortho‐alkyl benzamides, can be successfully applied to this organocatalytic system. With the established protocol, over 120 examples of functionalized δ‐amino ketones and isoquinolinones with diverse substituents were easily synthesized in up to 99 % yield under mild conditions. The robustness and generality of the organocatalytic strategy were further highlighted by the successful acylation of unactivated C(sp3)−H bonds and late‐stage modification of pharmaceutical molecules. Then, the asymmetric control of the radical reaction was attempted and proven feasible by using a newly designed chiral thiazolium catalyst, and moderate enantioselectivity was obtained at the current stage. Preliminary mechanistic investigations including several control reactions, KIE experiments, and computational studies shed light on the organocatalytic radical reaction mechanism. [ABSTRACT FROM AUTHOR]

The current strategies for nanoelectrode functionalization usually involve sophisticated modification procedures, uncontrollable and unstable modifier assembly, as well as a limited variety of modifiers. To address this issue, we propose a versatile strategy for large‐scale synthesis of biomimetic molecular catalysts (BMCs) modified nanowires (NWs) to construct functionalized electrochemical nanosensors. This design protocol employs an easy, controllable and stable assembly of diverse BMCs‐poly(3,4‐ethylenedioxythiophene) (PEDOT) composites on conductive NWs. The intrinsic catalytic activity of BMCs combined with outstanding electron transfer ability of conductive polymer enables the nanosensors to sensitively and selectively detect various biomolecules. Further application of sulfonated cobalt phthalocyanine functionalized nanosensors achieves real‐time electrochemical monitoring of intracellular glutathione levels and its redox homeostasis in single living cells for the first time. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive nanoagents, which simultaneously satisfy normal tissue clearance and tumor‐specific responsive treatment, are highly attractive for precise cancer theranostics. Herein, we develop a unique template‐induced self‐assembly strategy for the exquisitely controlled synthesis of self‐assembled lanthanide (Ln3+) nucleotide nanoparticles (LNNPs) with amorphous structure and tunable size from sub‐5 nm to 105 nm. By virtue of the low‐temperature (10 K) and high‐resolution spectroscopy, the local site symmetry of Ln3+ in LNNPs is unraveled for the first time. The proposed LNNPs are further demonstrated to possess the ability for highly efficient loading and tumor‐microenvironment‐responsive release of doxorubicin. Particularly, sub‐5 nm LNNPs not only exhibit excellent biocompatibility and predominant renal‐clearance performance, but also enable efficient tumor retention. These findings reveal the great potential of LNNPs as a new generation of therapeutic platform to overcome the dilemma between efficient therapy and long‐term toxicity of nanoagents for future clinical applications. [ABSTRACT FROM AUTHOR]

Inspired by efficient biomolecular reactions in the cell, versatile DNA nanostructures have been explored for manipulating the spatial position and regulating reactions at the molecular level. Spatially controlled arrangement of molecules on the artificial scaffolds generally leads to enhanced reaction activities. Especially, the rich toolset of dynamic DNA nanostructures provides a potential route towards more sophisticated and vigorous regulation of molecular reactions. Herein, a reconfigurable DNA origami domino array (DODA) as a dynamic scaffold was adopted in this work for temporal‐controlled and switchable molecular cascade reactions. Dynamic regulation of the assembly of G‐quadruplex, hybridization of parallel‐stranded duplex and assembly of binary DNAzyme were demonstrated. Molecular cascade reactions on the triggered reconfiguration of DODAs were realized, resulting in more complex, dynamic, and switchable control over the reactions. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) hold great potentials for addressing the challenge of highly efficient oil–water separation, but they are restricted by the poor wettability and processability as crystalline membranes. Here we report the design and synthesis of two‐dimensional (2D) robust COFs with controllable hydrophobicity and processability, allowing the COF layers to be directly grown on the support surfaces. Three 2D COFs with AA or ABC stacking are prepared by condensation of triamines with fluorine and/or isopropyl groups and perfluorodialdehyde. They all show excellent tolerance to water, acid, and base, with water contact angles (CA) of 111.5–145.8°. The two COFs with isopropyl and fluorine mixtures can grow as a coating on a stainless‐steel net (SSN) substrate, whereas the one with only fluorine substituents cannot. The superhydrophobic COF@SSN coating with water CA of up to 150.1° displays high water‐resistance and self‐cleaning properties, enabling high oil–water separation performances with an efficiency of over 99.5 % and a permeation flux of 2.84×105 L m−2 h−1, which are among the highest values reported for state‐of‐the‐art membranes. [ABSTRACT FROM AUTHOR]