We report a non-biomimetic total synthesis of (+)-daphnepapytone A, an unprecedented member of the guaiane-derived sesquiterpenoids that displays moderate inhibitory activity against -glycosidase (IC50 = 159 ± 2.1 M) and possesses a highly strained bridging cyclobutane motif. Our de novo approach provided expedient access to the tetracyclic core of (+)-daphnepapytone A through an intramolecular allenyl

We report an iridium-catalyzed stereoselective cyclization of aryl alkynes with tethered esters and imides to give silyl-protected O,O- and N,O-acetals. The optimized conditions afford chiral 5- and 6-membered heterocycles in excellent ee and moderate to high dr and can be isolated chromatographically as single diastereomers. A variety of esters, including acetates, formates, benzoates, and pivalates

Precise control over spatiotemporal release of cancer therapeutics remains a significant challenge in developing effective combination therapies. Herein, we report a hydrogen peroxide (H₂O₂)-activatable unimolecular platform (ICy-Cb) that integrates cancer imaging and synchronized dual-modal therapy. An iodized hemicyanine photosensitizer and chlorambucil are integrated into a single molecular structure

Single-carbon-atom transfer reaction offers a powerful strategy for constructing complex molecular architectures by sequential assembly of substituents around the atomic carbon core. However, the limited availability of atomic carbon sources has significantly hindered progress in this field. Herein, we demonstrate a single-carbon atom transfer reaction utilizing commercially available TMSCF2Br as an

A new “P3N” ligand, (n-Bu2N)3P, derived from PCl3 and three equivalents of n-Bu2NH is reported. When complexed to palladium, it readily participates in homogeneous (copper-free) Heck-Cassar-Sonogashira and Suzuki-Miyaura couplings. Reliance on relatively low loadings of Pd is documented under aqueous micellar conditions; i.e., in water containing micelles using the well-established and inexpensive

Ring-strain-enabled transformations have made significant progress, pushed the boundaries of unexplored chemical space, and emerged as a powerful tool for constructing complex molecules selectively and efficiently. Among the strained ring systems, [1.1.1]propellane, bicyclobutane (BCB), and azabicyclobutane (ABB) have garnered substantial attention and found numerous synthetic applications. In contrast

Exploring infrared (IR) birefringent materials with both large birefringence (Δn) and wide band gaps (Eg) is urgently demanded for high-power optoelectronic applications and has long been a tough challenge due to the intrinsic contradictory relationship between the two metrics. Herein, we developed a target-driven closed-loop framework in coupling with functional motif and crystal structure screening

Recent studies highlight the importance and application of parts per million (ppm) palladium concentration in catalytic reactions. Lowering catalyst loading minimizes costs, simplifies purification, and reduces metal contamination, making it highly attractive for pharmaceutical and fine chemical manufacturing. Here, we report a ppm level Pd-catalyzed remote arylation reaction of alkenols, achieving

Methane pyrolysis has been proposed as a cost-competitive route to produce low-CO2-emissions hydrogen that can utilize today’s infrastructure to supply feedstock and manage waste, and thereby be rapidly scalable. However, this process faces challenges such as catalyst deactivation and carbon build-up that hinder its large-scale implementation. Pyrolysis is usually conducted in the absence of oxidizers

Rechargeable aqueous batteries are regarded as promising candidates for large-scale energy storage with the advantages of cost-effectiveness, environmentally friendliness, and innate safety. However, to date, most of the aqueous ion batteries that have been reported are equipped with metal cation charge carriers and encounter either poor sustainability or low reaction activity. Here, we first reported

Threshold switching memristors exhibit significant potential for developing artificial nociceptors as their working principles and electrical characteristics closely mimic biological nociceptors. However, the development of high-performance artificial nociceptors is hindered by the randomness of conductive filament (CF) formation/rupture, caused by low-quality resistive switching (RS) films and complex

Abstract : The emergence of wearable devices has led to a greater need for battery materials that are safe, resilient, exhibit high levels of ionic conductivity. Here, we present a supramolecular design as a useful tactic through fine tuning of the noncovalent interactions to overcome the standard trade-off in solid state Li-ion conductors between ionic conductivity and mechanical resilience. We report

The global spread of antimicrobial resistance (AMR) underscores the critical need for the rapid development of new drugs. Particularly alarming are the surge in metallo-β-lactamases (MBLs) - broad spectrum enzymes able to inactivate penicillins, cephalosporins, and carbapenems. Cefiderocol (FDC), a siderophore-containing cephalosporin, was initially reported as resistant to MBL hydrolysis. Indeed,

Protonation/deprotonation is the major ionization mechanism of organic molecules in current electrospray ionization (ESI) and matrix assisted laser desorption ionization mass spectrometric (MALDI MS) imaging. But cellular complexities are far beyond protonated or deprotonated organic molecules. There are tremendous endogenous organic and metallic metabolites that regulate oxidization-reduction homeostasis

Although two-dimensional (2D) electrically conducting metal-organic frameworks (cMOFs) have become prominent due to their numerous potential applications, their structures are often implied or assumed from rather crude powder X-ray diffrac-tion data. Indeed, exceedingly few examples exist of atomic-level structural details coming from single crystal diffraction experiments. Most widely studied among

Identifying and tailoring active sulfur configurations in heteroatom-doped carbon electrocatalysts for selective 2e– oxygen reduction reaction (ORR) pathway remains a significant challenge. Here we designed and synthesized sulfur-doped reduced graphene oxide electrocatalysts containing C−S and C−SOx moieties (denoted as SxRGO, x = 1, 10, 20) for promising ORR into hydrogen peroxide (H2O2). The optimized

The growing global demand for critical metals has intensified the search for sustainable and efficient extraction methods. Passive adsorption from seawater using advanced sorbent materials has emerged as a promising alternative, offering a renewable and environmentally responsible resource. Metal–organic frameworks (MOFs), with their high surface area and tunable pore structures, offer great potential

Anisotropic nanostructures offer a promising pathway to modulate structure-function relationships of materials. However, the correlation between growth direction of high-quality anisotropic nanostructures, the synthesis conditions and mechanisms controlling their growth, and their magnetic and optical properties remain underexplored. In this study, we developed an iron-assisted anisotropic growth method

Two-dimensional (2D) non-layered semiconductors have attracted tremendous research interest due to the exotic structural and electronic properties compared with their layered counterparts. However, the lack of large-scale growth method greatly hinders their application. In this work, we have proposed a gas-liquid heterogeneous reaction strategy to suppress the diffusion of the involved reactants, resulting

UV light generation is generally not very efficient, expensive, or may even require toxic elements such as mercury. In contrast, blue light (λ = 450 nm) is cheaply available from semiconductor LEDs and its use in phosphor-converted LEDs technologically mature and could be envisioned as an intense, sustainable light source in an upconversion scheme. The electronic energy level landscape of the 4f2 ion

The arrangement of amino acids within crystalline porous materials represents a unique approach to enhance their functionalities such as catalysis, separation and sensing. In particular, the simultaneous arrangement of distinct residues in crystalline frameworks, i.e., shape sorting, remains one of the most important challenges. Here, we demonstrate the shape sorting of two distinct amino acid residues

The starting point of this study is the solid state structure of a complex between human carbonic anhydrase II (HCAII) and a helically folded tetradecaamide aromatic foldamer with a nanomolar HCAII ligand appended at the N terminus of the helix. In this complex, the foldamer is achiral but its handedness is biased by diastereoselective interaction with the protein. Computational analysis of the HCAII

The electrochemical reconstruction of metal-organic frameworks (MOFs) offers a promising approach for in situ fabrication of high-performance electrocatalysts. However, this innovation is often hindered by unpredictable structural transformations due to the complex thermodynamic and kinetic interplay of such multiple electrochemical and chemical processes. Herein, the reaction-atmosphere (Ar or CO2)

Light olefins, such as ethylene (C2H4) and propylene (C3H6), are essential feedstocks for the production of chemical products. However, the current purification strategy of distillation is energy-intensive and results in high carbon emissions. Adsorptive separation, the selective capture of gas from mixtures by porous materials, is considered a promising alternative or transitional technology. Metal-organic

Over the past decade, covalent organic frameworks (COFs) have garnered significant attention as supporting materials for the immobilization of radical species, showing great promise in applications such as catalysis, energy storage, and dynamic nuclear polarization. While considerable progress has been made in developing monoradical COFs, the creation of biradically embedded COFs remains a substantial

Cell wall-deficient bacteria (CWDB) are key contributors to antimicrobial resistance (AMR), enabling persistent infections by evading antibiotics through their transition to L-form states. Therefore, molecular tools for detecting L-form conversion and AMR mechanisms are crucial for developing novel strategies against bacterial infections. Herein, we present the development of small-sized, peptidoglycan-specific

Constructing sulfonate-coordinated coordination polymers (CPs) with high stability remains a significant challenge due to the relatively weak coordination ability of the sulfonate group, especially when paired with highly inert Cr3+ ion. In this study, we designed solvent-free methods to enhance Cr(III)-sulfonate coordination and further advances its reticular chemistry. For the first time, two Cr

We report a method for the direct palladium-catalyzed cross coupling reactions of cyclopropenyl esters bearing a variety of substitution patterns with Csp2 iodides. This reaction is largely insensitive to the electronic nature of the coupling partner. Tetramethylammonium acetate, a halide sequestrant, was exceptionally effective as an organic base. An observed KIE of 2.5 revealed C–H bond cleavage

Large polyazamacrocycles are used for the complexation of large metal ions. However, their coordination chemistry has not been frequently studied until now. An eighteen-membered macrocycle with two rigidifing pyridine rings and four aliphatic amino groups substituted with four acetic acid pendants, H4pyta, provides a large ligand cavity and coordination number (CN) up to 10. Trivalent lanthanides were

Among the several exceptional properties of fullerene, C60, its electron acceptor property is a highly studied topic. This work demonstrates the superior electron acceptor property of C60, even in the presence of a stronger electron acceptor(s) in multi-modular donor-acceptor constructs. For this, novel bis-phenothiazine-C60 donor-acceptor conjugates incorporating strong electron acceptors, tetracyanobutadiene

Radicals are highly reactive for coupling reactions while the applications are normally limited by the uncontrollable initiation and chaotic conversions. Although transition metal-based single electron transfer (SET) shows potential for controllable radical initiations, the detailed mechanism is still insufficient, especially for the roles of spin state transition on SET-based radical initiation. Herein

Hybrid water electrolysis is a promising approach to achieve energy-saving hydrogen (H2) generation by replacing oxygen evolution reaction with thermodynamically advantageous sulfion oxidation reaction (SOR). Herein, we design iron-modified nickel selenide nanosheet arrays (Fe-Ni0.85Se) as a bifunctional hydrogen evolution reaction (HER) and SOR electrocatalyst to simultaneous facilitate H2 production

Endohedral metallofullerenes (EMFs) are promising platforms for single-molecule magnets (SMMs) due to their internal cavities, which enable effective coupling of magnetically anisotropic metal ions through direct covalent bonding. However, the practical application of EMF-SMMs remains to be challenging, particularly in the robust assembly of the cage structures. In this study, we propose a strategy

Rare earth elements (REEs), which include the 15 lanthanides plus scandium and yttrium, are critical components commonly used in permanent magnets and play a significant role in electronics and green energy technologies. Due to the similarities of these ions, conventional separation processes are chemically- and energy-intensive and generate large quantities of waste. The lanthanides share physical

Photocyclization of N-substituted carbazole derivatives of benzo[e][1,2,4]triazine gave two carbazole-fused Blatter radicals with a novel heterocyclic skeleton. No photocyclization was observed for the analogous dibenzocarbazole, indole, benzimidazole, and phenoxazine precursors, which was rationalized with DFT computational methods. The two carbazole-derived radicals were characterized by spectroscopic

The preparation of active and CO-tolerant platinum-free electrocatalysts toward hydrogen oxidation reaction (HOR) under alkaline condition is significant for the practical development of anion exchange membrane fuel cells. Herein, nitrogen atoms intercalated into the interstitial void of rhodium (N-Rh/C) nanocrystal is fabricated, which constructs electron-deficient and electron-rich Rh sites simultaneously

Precisely controlling the spatial arrangement of nanostructures offers unique opportunities for tuning physical and chemical properties, however, it remains a great challenge due to the lack of effective synthetic methods. Herein, we present a wet-chemistry strategy for the synthesis of three-dimensional (3D) Pd superstructures (Pd SSs) by manipulating the growth kinetics. The strategy consists of

Development of new synthetic strategies in the synthesis of preparing C(sp3)-rich arene bioisosteres, especially their heteroatom incorporated analogs are less explored, but highly in demand. Here we report a photocatalytic [2π+2σ] cycloaddition reaction between bicyclo[1.1.0]butanes and aldehydes enabled by cobalt under visible light irradiation. The key step is that bicyclo[1.1.0]butanes could be

Studies on the chemistry of highly active rare-earth (RE) metal ambiphilic carbenes face challenges due to the lack of appropriate model molecular platforms because the corresponding ambiphilic carbenes have empty p-orbital. Here, the synthesis of novel multi-chelated amidate rare-earth metal pincer complexes the ambiphilic carbenes is realized by using indol−2−yl−based ligands. The ambiphilic carbene

We report the diastereoselective and enantioselective synthesis of thio-substituted cyclobutanes via a thio-Michael addition on cyclobutenes. In presence of DBU, various thio-cyclobutane esters and amides were obtained in up to quantitative yield and >95:5 dr. Using a chiral chinchona-based squaramide bifunctional acid-base catalyst and a N-acyl-oxazolidinone substituted cyclobutene, thio-cyclobutanes

The physical and chemical properties of molecular crystals are a combined function of molecular structure and the molecular crystal packing. Specific crystal packings can enable applications such as pharmaceuticals, organic electronics, and porous materials for gas storage. However, to design such materials, we need to predict both crystal structure and the resulting physical properties, and this is

Porous liquids are a sub-class of porous materials that combine permanent porosity, typically associated with solids, with the fluidity and fast mass-transfer capabilities of liquids, making them ideal candidates for gas storage and separation applications. One strategy to form porous liquidsis the dissolution of discrete and permanently porous molecular species at relatively high concentrations in

Chiral macrocycles are attracting growing interest due to their broad applicability as ligands in asymmetric catalysis and as host molecules for chiral recognition. Robustness and high thermodynamic stability can be effectively achieved by strategically linking aromatic panels to construct an axially chiral macrocyclic framework. Cyclic concatenation of four quinoline units affords a fully sp²-hybridized

The development of organic light-emitting diodes (OLED) with low efficiency roll-off at high brightness remains a significant challenge. The hot-exciton mechanism may provide the possibility to address this problem owing to its unique high-lying reverse intersystem crossing (hRISC). In this study, two pyrene-based molecules were successfully designed using triphenylamine (TPA) as donor and benzonitrile

Reversible interactions of organic substrates with transition metal compounds are a hallmark of their chemistry and its catalytic applications, but remain uncommon for low-valent p-block compounds. We report here the preparation of amidophosphine-supported gallium(I) compounds that exhibit equilibria between monomeric gallylene and dimeric digallene (Ga=Ga) states. The monomer-dimer equilibrium is

The performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to efficient and frequently used photoinitiators

Rechargeable aluminum-ion batteries have attracted increasing attention owing to the advantageous multivalent ion storage mechanism thus high theoretical capacity as well as inherent safety and low cost of using aluminum. However, their development has been largely impeded by the lack of suitable positive electrodes to provide both sufficient energy density and satisfactory rate capability. Here we

Zinc-ion batteries (ZIBs) have received much research and attention due to their advantages of safety, non-toxicity, simple manufacture, and element abundance. Nevertheless, serious problems still remain for their anodes, with dendrite development, corrosion, passivation, and the parasitic hydrogen evolution reaction due to their unique aqueous electrolyte system constituting the main issues that must

The rates of liquid-phase, acid-catalyzed reactions relevant to the upgrading of biomass into high-value chemicals are highly sensitive to solvent composition and identifying suitable solvent mixtures is theoretically and experimentally challenging. We show that the complex atomistic configurations of reactant-solvent environments generated by classical molecular dynamics simulations can be exploited

We report here cobalt−N-heterocyclic carbene catalytic systems for the intramolecular decarbonylative coupling through the chelation-assisted C−C bond cleavage of acylindoles and diarylketones. The reaction tolerates a wide range of functional groups such as alkyl, aryl, and heteroaryl groups, giving the decarbonylative products in moderate to excellent yields. This transformation involves the cleavage

We present herein an unconventional tandem [3,3]-sigmatropic rearrangement/[2+2] cycloaddition of simple dipropargylphosphonates to deliver a range of bicyclic polysubstituted cyclobutenes and cyclobutanes under Ag/Co relay catalysis. An interesting switch from allene-allene to allene-alkyne cycloaddition was observed based on the substitution of the substrates, which further diversified the range

The deprotonation of propargylic C–H bonds for subsequent functionalization typically requires stoichiometric metal alkyl or amide reagents. In addition to the undesirable generation of stoichiometric metallic waste, these conditions limit the functional group compatibility and versatility of this functionalization strategy and often result in regioisomeric mixtures. In this Article, we report the

Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches, that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application

A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N–C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions

Peri-acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a

A hydroxyalkylation of N-heteroaromatics with aldehydes was achieved using a binary hybrid catalyst system comprising an acridinium photoredox catalyst and a thiophosphoric acid organocatalyst. The reaction proceeded through the following sequence: 1) photoredox-catalyzed single-electron oxidation of a thiophosphoric acid catalyst to generate a thiyl radical, 2) cleavage of the formyl C‒H bond of the

As metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination

The endoplasmic reticulum (ER) is a very important organelle responsible for crucial biosynthetic, sensing, and signalling functions in eukaryotic cells. In this work, we established a strategy of ligand regulation to enhance the singlet oxygen generation capacity and subcellular organelle localization ability of a rhodamine-decorated iridium(III) complex by variation of the cyclometallating ligand

A new family of ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold, where two Ru(bpy)2centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(II)] triads absorbed strongly throughout the visible region