Precise catalysis is critical for the high-quality catalysis industry. However, it remains challenging to fundamentally understand precise catalysis at the atomic orbital level. Herein, we propose a new strategy to unravel the role of specific d orbitals in catalysis. The oxygen reduction reaction (ORR) catalyzed by atomically dispersed Pt/Co-doped Ti1−xO2 nanosheets (Pt1/Co1–Ti1−xO2) is used as a

Understanding the origin of the catalytic activity for the development of efficient catalysts is critical yet challenging. Herein, we report a simple strategy for the synthesis of chromium nitride nanoparticles (CrNNPs) encapsulated into hollow chromium–nitrogen–carbon capsules ([email protected]–Cr–Nx–C). The [email protected]–Cr–Nx–C demonstrated excellent electrocatalytic activity for the oxygen

Electroreduction of CO2 to target products with high activity and selectivity has techno-economic importance for renewable energy storage and CO2 utilization. Herein, we report a hierarchical CuS hollow polyhedron (CuS-HP) for electrocatalytic CO2 reduction (E-CO2R) in neutral pH aqueous media. Under E-CO2R conditions, CuS-HP undergoes structural reconstruction into sulfur-doped metallic Cu catalyst

Zeolites are of great industrial relevance as catalysts, adsorbents, and ion-exchangers and typically synthesized under hydrothermal conditions. Rational regulation of their crystallization process is of great significance for zeolite production. In this work, we systematically investigate the role of anions in tuning zeolite crystallization via anion introduction including SO42−, F−, Cl−, Br−, I−

Biofouling is a major obstacle to the efficient extraction of uranium from seawater due to the numerous marine microorganisms in the ocean. Herein, we report a novel amidoxime (AO) crystalline covalent organic framework (BD-TN-AO) by Knoevenagel condensation reaction of 2,2′,2″-(benzene-1,3,5-triyl)triacetonitrile (TN) and 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzaldehyde (BD) that is highly conjugated

The widespread use of antibiotics causes the accumulation of a large amount of antibiotics in the environment. Excessively active antibiotics in the environment results in the emergence of bacterial resistance. Building smart antibiotics capable of reversible regulation between active and inactive states on demand is a promising approach to address this issue. Herein, a ferrocene-containing quaternary

Direct introduction of a carboxyl group into molecules is one of the most useful methods for the preparation of carboxylic acids, which avoids the conversion of various preexisting functional groups and features good step- and atom-economy. However, the methods for the direct synthesis of two-carbon added carboxylic acids from the precursors remain rare. Herein, we first report a general and mild method

A multicomponent reductive cross-coupling of unactivated alkyl halides and alkyl tosylates connected via sodium metabisulfite was established for the general construction of alkyl–alkyl sulfones. Neither a metal catalyst nor a metal reductant is required in this “green” reductive cross-coupling. Inorganic sodium metabisulfite served as both the sulfur dioxide source and the robust connector. Safe formate

Herein, we report a novel palladium (Pd)-catalyzed asymmetric domino Heck/carbocyclization/Suzuki reaction of N-(2-bromoaryl)-2-naphthylacrylamides. The reaction involves a novel and enantioselective dearomative 1,2-insertion of the naphthalene group, thus providing a unique dearomatization strategy of nonactivated naphthalenes. A new phosphoramidite ligand L12, which displayed excellent reactivity

Controllable assembly of organic semiconductors has opened an avenue for an in-depth perception of their structure–property relationships; however, a detailed investigation of their molecular controllability remains challenging. Discerning the assembly of organic semiconductors could enable the attainment of a significant improvement of performance. Here, we report the fabrication of efficient nonfullerene

An accurate description of catalytic selectivity poses an enormous challenge for theoretical simulations. Due to the absence of a well-defined benchmark set on the catalytic selectivity, the performance of even the widely used density functional approximations (DFAs) is yet to be validated. This work reports a test set based on the selective hydrogenation of α,β-unsaturated aldehydes catalyzed by ruthenium

Molecular chaperones are widely employed as additives in nature to trap proteins in the kinetic state, which inspire the development of kinetically trapped artificial supramolecular systems. Till now, such additive-controlled approaches have enabled the stabilization of extended supramolecular structures in the kinetically trapped state, while discrete assemblies with sufficient kinetic persistence

Nitric oxide (NO) participates in various pathways and revealing its dynamics is critical for resolving its pathophysiology. While there are methods available for detecting biological NO, few are capable of tracking NO dynamics. Herein, inspired by the cellular machinery of reversible thiol modification by NO, we have successfully designed a family of cysteine analogues tagged with fluorophores for

Light-responsive proton conductors might find applications in both traditional fields (fuel cells, chemical sensors, bio-ionic functions, etc.) and modern high-speed switchable smart systems (Internet of things, robotics, etc.). Previous synthetic methods resulted in low switching contrasts (

The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions. Here, we report directed phase transitions of dipeptide supramolecular gel to crystals with excellent selectivity and tunable mechanical properties. To be specific, lamellar-to-orthorhombic rearrangement of dipeptide molecules in the supramolecular assembly was guided by application

Metallic-phase transition-metal dichalcogenides (TMDCs) exhibit unusual physicochemical properties compared with their semiconducting counterparts. However, they are thermodynamically unstable to access and it is even more challenging to construct their metastable-phase heterostructures. Herein, we demonstrate a general solution protocol for phase-controlled synthesis of distorted octahedral 1T WS2-based

An electron collection layer (ECL) between a photoactive overlay and an electrode plays a crucial role in optimizing the light field and charge extraction in bulk-heterojunction (BHJ) polymer solar cells (PSCs). However, the typical thickness of the photoactive layer is thinner than its optical path lengths, limiting further improvement of light absorption and device performance. Herein, we modulated

The formation of undersaturated lead or iodide ions and I2 on the perovskite surface can decrease the performance and stability of perovskite solar cells (PSCs). Additionally, the leakage of noxious lead limits the application of PSCs. Here, we develop a strategy for molecular modulation of a perovskite surface using thiol copper(II) porphyrin (CuP) to post-treat the perovskite film. The Raman spectra

Potassium-ion (K+) batteries (PIBs) show great potential in large-scale energy storage applications owing to their low-cost and high-operating voltage. However, the development of practical PIBs remains hindered by their poor performance rate due to the large ionic radius of the K+ (1.38 Å). Herein, we report an ionic-drill strategy using smaller lithium ions (Li+) to open diffusion channels for K+

When carbon-containing species are involved in reactions catalyzed by transition metals at high temperature, the diffusion of carbon on or in catalysts dramatically influences the catalytic performance. Acquiring information on the carbon-diffusion-involved evolution of catalysts at the atomic level is crucial for understanding the reaction mechanism yet also challenging. For the chemical vapor deposition

Transmembrane transport plays an important role in many physiological functions, and mimicking this biological process in artificial systems has potential applications in biosensing, drug delivery, and bionic science. Here, a lipophilic split aptamer was developed as a novel transmembrane carrier for adenosine triphosphate (ATP) transport. The ATP carrier comprises two split aptamer fragments and cholesterol

Direct introduction of a carboxyl group into molecules is one of the most useful methods for the preparation of carboxylic acids, which avoids the conversion of various preexisting functional groups and features good step- and atom-economy. However, the methods for the direct synthesis of two-carbon added carboxylic acids from the precursors remain rare. Herein, we first report a general and mild method

The widespread use of antibiotics causes the accumulation of a large amount of antibiotics in the environment. Excessively active antibiotics in the environment results in the emergence of bacterial resistance. Building smart antibiotics capable of reversible regulation between active and inactive states on demand is a promising approach to address this issue. Herein, a ferrocene-containing quaternary

Direct introduction of a carboxyl group into molecules is one of the most useful methods for the preparation of carboxylic acids, which avoids the conversion of various preexisting functional groups and features good step- and atom-economy. However, the methods for the direct synthesis of two-carbon added carboxylic acids from the precursors remain rare. Herein, we first report a general and mild method

Molecular chaperones are widely employed as additives in nature to trap proteins in the kinetic state, which inspire the development of kinetically trapped artificial supramolecular systems. Till now, such additive-controlled approaches have enabled the stabilization of extended supramolecular structures in the kinetically trapped state, while discrete assemblies with sufficient kinetic persistence

Nitric oxide (NO) participates in various pathways and revealing its dynamics is critical for resolving its pathophysiology. While there are methods available for detecting biological NO, few are capable of tracking NO dynamics. Herein, inspired by the cellular machinery of reversible thiol modification by NO, we have successfully designed a family of cysteine analogues tagged with fluorophores for

Potassium-ion (K+) batteries (PIBs) show great potential in large-scale energy storage applications owing to their low-cost and high-operating voltage. However, the development of practical PIBs remains hindered by their poor performance rate due to the large ionic radius of the K+ (1.38 Å). Herein, we report an ionic-drill strategy using smaller lithium ions (Li+) to open diffusion channels for K+

CCS Chemistry, Ahead of Print.

CCS Chemistry, Ahead of Print.

A multicomponent reductive cross-coupling of unactivated alkyl halides and alkyl tosylates connected via sodium metabisulfite was established for the general construction of alkyl–alkyl sulfones. Neither a metal catalyst nor a metal reductant is required in this “green” reductive cross-coupling. Inorganic sodium metabisulfite served as both the sulfur dioxide source and the robust connector. Safe formate

Herein, we report a novel palladium (Pd)-catalyzed asymmetric domino Heck/carbocyclization/Suzuki reaction of N-(2-bromoaryl)-2-naphthylacrylamides. The reaction involves a novel and enantioselective dearomative 1,2-insertion of the naphthalene group, thus providing a unique dearomatization strategy of nonactivated naphthalenes. A new phosphoramidite ligand L12, which displayed excellent reactivity

Controllable assembly of organic semiconductors has opened an avenue for an in-depth perception of their structure–property relationships; however, a detailed investigation of their molecular controllability remains challenging. Discerning the assembly of organic semiconductors could enable the attainment of a significant improvement of performance. Here, we report the fabrication of efficient nonfullerene

Light-responsive proton conductors might find applications in both traditional fields (fuel cells, chemical sensors, bio-ionic functions, etc.) and modern high-speed switchable smart systems (Internet of things, robotics, etc.). Previous synthetic methods resulted in low switching contrasts (

The manipulation of supramolecular assembly enables single-component architectures to possess diverse structures and functions. Here, we report directed phase transitions of dipeptide supramolecular gel to crystals with excellent selectivity and tunable mechanical properties. To be specific, lamellar-to-orthorhombic rearrangement of dipeptide molecules in the supramolecular assembly was guided by application

Metallic-phase transition-metal dichalcogenides (TMDCs) exhibit unusual physicochemical properties compared with their semiconducting counterparts. However, they are thermodynamically unstable to access and it is even more challenging to construct their metastable-phase heterostructures. Herein, we demonstrate a general solution protocol for phase-controlled synthesis of distorted octahedral 1T WS2-based

An electron collection layer (ECL) between a photoactive overlay and an electrode plays a crucial role in optimizing the light field and charge extraction in bulk-heterojunction (BHJ) polymer solar cells (PSCs). However, the typical thickness of the photoactive layer is thinner than its optical path lengths, limiting further improvement of light absorption and device performance. Herein, we modulated

The formation of undersaturated lead or iodide ions and I2 on the perovskite surface can decrease the performance and stability of perovskite solar cells (PSCs). Additionally, the leakage of noxious lead limits the application of PSCs. Here, we develop a strategy for molecular modulation of a perovskite surface using thiol copper(II) porphyrin (CuP) to post-treat the perovskite film. The Raman spectra

A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substitution cascade. Unlike the known polyene-type cyclization strategies for the construction of abietane-type diterpene skeletons, propargylic ester groups were used for the cyclization process

Chemical systems that can replicate cellular behaviors are gaining increasing attention and are being used to study various biological processes. Here, a protein- or amylose-based assembly at an oil/water interface was employed to construct a large compartmentalized adipocyte-like structure, and a lipid droplet-like microcompartment (amylose-polymer-stabilized 2-ethyl-1-hexanol microcompartment), which

Rare-earth metal boroxides are not only rare and of great synthetic challenge but also important theoretically due to their unrevealed bonding characteristics. In this paper, we report the synthesis, characterization, and bonding characteristics of the 4f-block metal boroxide complexes MesDAD2 LuOB(C6F5)X ( 4-Lu, X = C6F5; 5-Lu, X = NC13H10) with two chelating radical-anionic 1,4-diazabutadiene (DAD)

Water and moisture stability have been recognized as one of the most important characteristics of metal–organic frameworks (MOFs) in regards to their future applications. Nonetheless, most MOFs are water-labile to some degree. One promising solution for the collapse of MOFs toward water is surface hydrophobic modification. Herein, a facile, mild, and general one-step surface polymerization approach

A green and sustainable synthetic strategy for amide bond formation utilizing a visible light-promoted nitrone formation/rearrangement cascade was developed. This method utilized visible light as the sole and clean energy source without the need for an exogenous photoredox catalyst or additive. Moreover, nitrones are generated in situ, bypassing the isolation process and producing only nitrogen gas

Despite the extensive study of the Fe-based Fischer–Tropsch synthesis (FTS) over the past 90 years, its active phases and reaction mechanisms are still unclear due to the coexistence of metals, oxides, and carbide phases presented under realistic FTS reaction conditions and the complex reaction network involving CO activation, C–C coupling, and methane formation. To address these issues, we successfully

Chirality transfer, induction, and circularly polarized luminescence (CPL) using supramolecular hosts, such as macrocycles and cages, have been explored for wide-ranging applications in chiral recognition, sensing, catalysis, and chiroptical functional materials. Herein, we report the adaptive chirality of an achiral tetraphenylethene (TPE)-based octacationic cage ( 1) induced by binding with enantiopure

The nucleolus, the locus of ribosome biogenesis, was found to be the predominant intracellular target of a new fluorescent probe, V-P1. In solution, the probe demonstrated both a selectivity to RNA G-quadruplexes and a sensitivity to the viscosity, while G-quadruplex binding did not disturb the viscosity sensing. In cells, confocal and fluorescence lifetime imaging, combined with digestion and competition

As two pivotal functional segments, triazine and porphyrin can be coupled to form a highly cross-linked conjugated polymer. Although the obtained conjugated polymers are almost insoluble in most solvents, a small amount of protonic acid can cause the formation of a colloidal solution of polymers. The dissolution process has proved to be a surface charge effect induced by protonation of porphyrin units

We present a controlled fabrication of selective ultrathin metal–organic framework (MOF) nanosheets as preassembling platforms, yolk–shell structured with a few-layered N-doped carbon (NC) shell-encapsulated Ni0.85Se core (denoted as Ni0.85[email protected]) via an oriented phase modulation (OPM) strategy. The ultrathin nature of the MOF nanosheets gave rise to the modification of structure at the

During the utilization of structural and functional advantages of polyoxometalates (POMs) for enhanced applications, a suitable assembly of these clusters in framework materials to act as binding nodes represents a promising approach. In contrast to well-developed coordination/covalent combinations, we have developed a convenient strategy to build porous structures of POMs with smaller-sized counterions

Deuterated compounds are valuable in synthetic, pharmaceutical, and analytical chemistry. The deuteration of halides is a widespread method for highly site-selective deuterium installation. However, the facile, efficient, and economical deuterium incorporation remains challenging. In this work, we introduced a practical deuteration of (hetero)aryl halides through an electrochemical reduction method

Living organisms rely on materials sequestration from the environment to strengthen their bodies. Such constant activity provides necessary supplies for critical biological functions, which is difficult by man-made structures due to the lack of a dynamic sequestration mechanism. In this study, it is shown that an epidermis-like smart coating can respond to changes in salinity to allow a spontaneous

Nanogels hold promise as soft and functional carriers and nanoreactors, but whether they will ever reach the stage of large-scale application depends crucially on efficient production methods, and on what interesting properties and functionalities they can have. In particular, nanogels consisting of highly charged polyelectrolyte have not yet been very much explored. Here, the authors present a novel

Due to the critical bacterial resistance and antibiotic crisis, the discovery of new antibiotics is an urgent need in the clinic than ever. Naturally occurring antibiotics have proven to be an indispensable source of the development of new antibacterial agents. Herein, we report the total synthesis of three families of biogenetically related natural antibiotics, including anthrabenzoxocinones (ABXs)

Oligonucleotide drugs have been used widely as therapeutic agents for gene therapy, while their instability in biological media and inefficiency for intracellular delivery remain major hurdles for practical in vivo applications. Herein, we report a circular Y-shaped aptamer–DNAzyme conjugate (cYAD) for highly efficient in vivo gene silencing via RNA cleavage, which can been employed in various disease

Planar chiral ferrocenes are widely applied in organic synthesis, materials science, and medicinal chemistry, but their synthesis is not trivial. Herein, a highly efficient synthesis of planar chiral ferrocene-based pyridine derivatives via Rh(I)-catalyzed direct coupling of pyridylferrocenes with aryl halides was developed. Good yields and excellent enantioselectivity (95– >99% ee) are obtained for

The purpose of achieving the long-lasting fragrance perception leads to nanocarrier-based profragrances in perfume applications. Herein, we report a family of novel profragrance systems based on polyhedral oligomeric silsesquioxane (POSS) derivatized thioureas (POSS thioureas) that enable linkage of volatile carbonyl fragrances with the spontaneous formation of fragile hydrogen bonds. This profragrance

High-temperature reactions widely exist in nature. However, they are difficult to characterize either experimentally or computationally. The minimum energy path (MEP) model routinely used in computational modeling of chemical reactions is not justified to describe high-temperature reactions since high-energy structures are actively involved at high temperatures. In this study, we used methane (CH4)

Enantioselective recognition in water remains an ongoing challenge in supramolecular chemistry but is routine in nature. Herein, we report the first enantiopure pair of biomimetic macrocyclic receptors with hydrogen bonding donors in their deep hydrophobic cavities. The chiral naphthotubes can be efficiently synthesized through a chirality-directed macrocyclization strategy and are able to discriminate

Laser displays, benefiting from the characteristic merits of lasers, have led to the revolution of next-generation display technologies owing to their superior color expression. However, the acquisition of pixelated laser arrays as self-emissive panels for flat-panel laser displays remains challenging. Liquid crystal (LC) materials with excellent processability and optoelectronic properties offer considerable

Tumor-promoting inflammation is accompanied by cancer initiation, progression, and metastasis. Cyclooxygenase-2 (COX-2) and its downstream product, prostaglandin E2 (PGE2), play critical roles in tumor-promoting inflammation. Several studies have revealed the potential of COX-2 inhibition in improving cancer response to chemotherapy, as well as immunotherapy. Aspirin, a nonsteroidal anti-inflammatory

Fuller-rylenes is a useful model to tailor the properties of cross-dimensional molecular carbons to define their scope for specific applications. Herein we present a straightforward synthetic strategy to hybridize planar rylene dyes and spherical fullerene into esthetic nanostructures containing features from both subunits via one-pot Pd-catalyzed [3 + 2] or [4 + 2] cyclization reactions. Single-crystal