The cyclopropyl group is of great importance in medicinal chemistry, as it can be leveraged to influence a range of pharmaceutical properties in drug molecules. This report describes a Vitamin B12-photocatalyzed approach for the cyclopropanation of electron-deficient alkenes using dichloromethane (CH2Cl2) as the methylene source. The reaction proceeds in good to excellent yields under mild conditions

Polyoxometalates (POMs) represent crucial intermediates in the formation of insoluble metal oxides from soluble metal ions, however, the rapid hydrolysis-condensation kinetics of MoVI or WVI makes the direct characterization of coexisted molecular species in a given medium extremely difficult. Silver nanoclusters have shown versatile capacity to encapsulate diverse POMs, which provides an alternative

The high-entropy approach is applied to monoclinic Prussian White (PW) Na-ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn-based samples with up to six metal species sharing the N-coordinated positions was synthesized. The material of composition Na1.65Mn0.4Fe0.12Ni0.12Cu0.12Co0.12Cd0

3-Deoxy-ᴅ-manno-oct-2-ulosonic acid (Kdo) is an eight-carbon monosaccharide found widely in bacterial lipopolysaccharides (LPS) and capsule polysaccharides (CPS). We developed an indirect methodology for the stereoselective synthesis of α-Kdo glycosides with a C3-p-tolylthio-substituted Kdo phosphite donor. The presence of the p-tolylthio group enhanced the reactivity, suppressed the formation of elimination

Indole-based planar-chiral macrocycles are widely found in natural products and bioactive molecules. However, in sharp contrast to the preparation of indole-based axially chiral structures, the enantioselective catalysis of indole-based planar-chiral macrocycles is still a formidable task so far. Here we report an N-heterocyclic carbene (NHC)-catalyzed intramolecular atroposelective macrocyclization

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO₂RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO₂ solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method

Ultrahigh-molecular-weight (UHMW) polymers with tailored structures are highly desirable for the outstanding properties. In this work, we developed a novel photoorganocatalyzed controlled radical alternating copolymerizations of fluoroalkyl maleimide and diverse vinyl comonomers, enabling efficient preparation of fluorinated copolymers of predetermined UHMWs and well-defined structures at high conversions

Reasonably elevating the working voltage (≥ 4.4 V vs. Li/Li+) of the cathode is one of the efficient approaches to maximize the energy density of lithium-ion batteries (LIBs). As a preferred partner for high-voltage LIB systems, localized high-concentration electrolyte (LHCE), characterized by a stronger Li solvation structure, less free solvent, and robust electrode/electrolyte interphase has attracted

Deep eutectic solvents (DESs), heralded for their synthesis simplicity, economic viability, and reduced volatility and flammability, have found increasing application in biocatalysis. However, challenges persist due to a frequent diminution in enzyme activity and stability. Herein, we developed a general protein engineering strategy, termed corner engineering, to acquire DES-resistant and thermostable

Carbon nanomaterials, specifically carbon dots and carbon nitrides, play a crucial role as heterogeneous photoinitiators in both radical and cationic polymerization processes. These recently introduced materials offer promising solutions to the limitations of current homogeneous systems, presenting a novel approach to photopolymerization. This review highlights the preparation and photocatalytic performance

With its efficient nitrogen fixation kinetics, electrochemical lithium-mediated nitrogen reduction reaction (LMNRR) holds promise for replacing Haber-Bosch process and realizing sustainable and green ammonia production. However, the general interface problem in lithium electrochemistry seriously impedes the further enhancement of LMNRR performance. Inspired by the development history of lithium battery

Molecular profiling of protein markers on small extracellular vesicles (sEVs) is a promising strategy for the precise detection and classification of ovarian cancers. However, this strategy is challenging owing to the lack of simple and practical detection methods. In this work, using an aptamer-based nanoflow cytometry (nFCM) detection strategy, a simple and rapid method for the molecular profiling

Embracing complexity in design, metallo-supramolecular self-assembly presents an opportunity for fabricating materials of economic significance. The array of accessible supramolecules is alluring, along with favourable energy requirements. Implementation is hampered by an inability to efficiently characterise complex mixtures. The stoichiometry, size, shape, guest binding properties and reactivity

Drawing inspiration from allosteric signaling enzymes, whose catalytic and regulatory units are non-covalently linked, we have devised a method to establish unnatural, effector-mediated enzyme activation within native cells. The feasibility of this approach is demonstrated by introducing a synthetic regulatory unit (sRU) onto glycogen synthase kinase 3 (GSK-3) through non-covalent means. Our study

Nitrogen-doped cavities are pervasive in graphenic materials, and represent key sites for catalytic and electrochemical activity. However, their structures are generally heterogeneous. In this study, we present the synthesis of a well-defined molecular cutout of graphene featuring N-doped cavity. The graphitization of a macrocyclic pyridinic precursor was achieved through photochemical cyclodehydrochlorination

Inorganic materials depleted of heavy stable isotopes are known to deviate strongly in some physicochemical properties from their isotopically natural counterparts. Here we explored for the first time the effect of simultaneous depletion of the heavy carbon, hydrogen, oxygen and nitrogen isotopes on the bacterium E. coli and the enzymes expressed in it. Bacteria showed faster growth, with most proteins

Glassy Na-ion solid-state electrolytes (GNSSEs) are an important group of amorphous SSEs. However, the insufficient ionic conductivity of state-of-the-art GNSSEs at room temperature lessens their promise in the development of all-solid-state Na-ion batteries (ASSNIBs) with high energy density and improved safety. Here we report the discovery of a new sodium superionic glass, 0.5Na2O2-TaCl5 (NTOC),

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

Borate crystals can be chemically and functionally modified by fluorination strategy, which encourages the identification of emerging fluorooxoborates with a structure and set of characteristics not seen in any other oxide parents. However, the bulk of fluorooxoborates have been found accidentally, rational methods of synthesis are required, particularly for the infrequently occurring poly-fluorinated

Photocatalytic nitrogen fixation using solar illumination under ambient conditions is a promising strategy for production of the indispensable chemical NH3. However, due to the catalyst's limitations in solar energy utilization, loss of hot electrons during transfer, and low nitrogen adsorption and activation capacity, the unsatisfactory solar-to-chemical conversion (SCC) efficiencies of most photocatalysts

With the increasing demands of X-ray detection and medical diagnosis, organic scintillators with intense and tunable X-ray excited emission have been becoming important. To guarantee the X-ray absorption, heavy atoms were widely added in reported organic scintillators, which led to emission quenching. In this work, we propose a new strategy to realize organic scintillators through the host-guest doping

We report herein a structure-unit based total synthesis of polycyclic norcembranoid diterpenoid, leading to the asymmetric synthesis of sinulochmodin C bearing a transannular strain ether bridge β–keto tetrahydrofuran moiety. Our synthetic route features an intramolecular double Michael addition to construct stereospecifically the [6,7,5,5] tetracyclic skeleton, a vinylogous hydroxylation/oxidation

Aprotic Li-O2 battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O2-) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O2- disproportionation

Chirality is ubiquitous in nature, and homochirality is manifested in many biomolecules. Although β-double helices are rare in peptides and proteins, they consist of alternating L- and D-amino acids. No peptide double helices with homochiral amino acids have been observed. Here, we report chiral β-double helices constructed from γ-peptides consisting of alternating achiral (E)-α,β-unsaturated 4,4-dimethyl

Bone metastasis is a type of metastatic tumors that involves the spreads of malignant tumor cells into skeleton, and its diagnosis and treatment remain a big challenge due to the unique tumor microenvironment. We herein develop osteoclast and tumor cell dual-targeting biomimetic semiconducting polymer nanocomposites (SPFeNOC) for amplified theranostics of bone metastasis. SPFeNOC contain semiconducting

The diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3-diaminopyridine-mediated

Allenoates are versatile building blocks which are primarily activated and controlled using chiral tert. phosphine and tert. amine Lewis bases. We herein report the first example of allenoate activation by using chiral isochalcogenoureas (IChU) for formal (4+2) cycloaddition reactions. Compared to established phosphine and amine catalysis, the use of these easily available Lewis bases enables new stereoselective

The selective formation of homonuclear bonds is of key importance in synthetic chemistry. Especially, dehydrocoupling reactions are attractive as ecologically and economically friendly alternatives to established reductive bond forming reactions, since they do not require the use of stoichiometric amounts of a reducing reagent and produce only valuable dihydrogen as by-product. Here, we report on a

It is now widely accepted that certain effects arising from localised surface plasmon resonance, such as enhanced electromagnetic fields, hot carriers, and thermal effects, can facilitate electrocatalytic processes. This newly emerging field of research is commonly referred to as plasmon-enhanced electrocatalysis (PEEC) and is attracting increasing interest from the research community, particularly

While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications. Herein we demonstrate that this obstacle

Among the list of planar tetracoordinate atoms, the smallest element hydrogen is missing. No experimental and theoretical evidence have ever been put forwarded. Herein, we introduce the first planar tetracoordinate hydrogen atom (ptH) in the global minimum geometry of In4H+ cluster. Bonding analysis indicates that the central hydrogen atom is acting like a proton and significant charge transfer from

One-pot synthesis of methacrylic and acrylic polymers from benzylic alcohols (R−OH) used as initiating moieties was developed. R−OH was converted to alkyl iodide (R−I), and the generated R−I was used as an initiator without purification or isolation in the subsequent reversible complexation mediated polymerization (RCMP), leading to one-pot RCMP from R−OH. As a useful application, this technique was

Acquiring high-performance ultraviolet (UV) nonlinear optical (NLO) materials that simultaneously exhibit a strong second harmonic generation (SHG) coefficients, as short as possible SHG phase-matching (PM) wavelength and non-hygroscopic properties has consistently posed a significant challenge. Herein, through multicomponent modification of KBe2BO3F2 (KBBF), an excellent UV NLO crystal, Mg(C3O4H2)(H2O)2

This report describes the development of a Zn(OTf)2-mediated method for converting α-tertiary haloamides to the corresponding 18F-labelled α-tertiary fluoroamides with no-carrier-added [18F]tetramethylammonium fluoride. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene is an essential additive for achieving high radiochemical conversion. Under the optimised conditions, radiofluorination proceeds at sterically hindered

Single crystallization of LiNixCoyMn1-x-yO2(NCM) is currently an effective strategy to improve the cycling life of NCM cathode, owing to the reduced surface area and enhanced mechanical strength, but the application of single crystal NCM(SC-NCM) is being hindered by severe particle agglomeration and poor C-rate performance. Here, a strategy of three-section-sintering(TSS) with the presence of grain-growth

A significant challenge in creating supramolecular materials is that conjugating molecular functionalities to building blocks often results in dissociation or undesired morphological transformation of their assemblies. Here we present a facile strategy to preserve structurally labile peptide assemblies after molecular modification of the self-assembling peptides. Sheet-forming peptides are designed

Reaction of the tris-hypersilyl nonagermanide Zintl cluster salt, K[Ge9(Hyp)3] (Hyp = Si(SiMe3)3) with [Rh(η2,η2-L)Cl]2 (L = 1,5-cyclooctadiene, COD; norbornadiene, NBD) afforded eleven- and twelve-vertex homo-multimetallic clusters by cluster core expansion. Using a stepwise procedure, starting from the Zintl cluster [Rh(COD){Ge9(Hyp)3}] and [Ir(COD)Cl]2, this methodology was expanded for the synthesis

Asymmetric hydrogenation finds widespread application in academia and industry. And indeed, a number of processes have been implemented for the production of pharma and agro intermediates as well as flavors & fragrances. Although these processes are all based on the use of late transition metals as catalysts, there is an increasing interest in the use of base metal catalysis in view of their lower

Ion-selective membranes are crucial in various chemical and physiological processes. Numerous studies have demonstrated progress in separating monovalent/multivalent ions, but efficient monovalent/monovalent ion sieving remains a great challenge due to their same valence and similar radii. Here, this work reports a two-dimensional (2D) MXene membrane with super-aligned slit-shaped nanochannels with

Concerns over the sustainability and end-of-life properties of fossil-derived surfactants have driven interest in bio-based alternatives. Lignocellulosic biomass with its polar functional groups is an obvious feedstock for surfactant production but its use is limited by process complexity and low yield. Here, we present a simple two-step approach to prepare bio-based amphiphiles directly from hemicellulose

A critical step in photocatalytic water dissociation is the hole-mediated oxidation reaction. Molecular-level insights into the mechanism of this complex reaction under realistic conditions with high temporal resolution are highly desirable. Here, we use femtosecond time-resolved, surface-specific vibrational sum frequency generation spectroscopy to study the photo-induced reaction directly at the

Bio-orthogonal reactions for modification of proteins and unprotected peptides are of high value in chemical biology. The combination of enzymatic halogenation with transition metal catalysed cross-coupling provides a feasible approach for modification of proteins and unprotected peptides. Using a semi-rational protein engineering approach, variants of the tryptophan 6-halogenase Thal were identified

A new generation of soluble phenothiazinyl merocyanine substituted polyacetylenes can be readily synthesized by rhodium-catalyzed polymerization of the corresponding 3-ethynyl phenothiazines, accessible by Sonogashira coupling and Knoevenagel condensation. UV/Vis and fluorescence spectroscopy of 7-acceptor-substituted phenothiazinyl polyacetylenes reveal that these polyacetylenes with conjugatively

Quasiperiodic patterns and crystals - having long range order without translational symmetry - fascinate researchers since their discovery. In this study, we report on new p-terphenyl based T-shaped facial polyphiles with two alkyl end-chains and a glycerol-based hydrogen-bonded side-group, self-assembling into an aperiodic columnar liquid quasicrystal with 12-fold symmetry and its periodic liquid-crystalline

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as unique layer-stacked crystalline coordination polymers that simultaneously possess porous and conductive properties. However, the controlled synthesis of hierarchically nanostructured 2D c-MOFs with high crystallinity and customized morphologies is essential for energy and electronic devices, which remains a great challenge

Now that the chemistry of 1:1 host:guest complexes is well-established, it is surprising to note that higher stoichiometry (oligomeric) complexes, especially those with excess host, remain largely unexplored. Yet, proteins tend to oligomerize, affording new functions for cell machinery. Here, we show that cucurbit[n]uril (CB[n]) macrocycles combined with symmetric, linear di-viologens form unusual

Compared with Zn2+ storage, non-metallic charge carrier with small hydrated size and light weight shows fast dehydration and diffusion kinetics for Zn−organic batteries. Here we first report NH4+/H+ co-storage in self-assembled organic superstructures (OSs) by intermolecular interactions of p-benzoquinone (BQ) and 2, 6-diaminoanthraquinone (DQ) polymer through H-bonding and π-π stacking. BQ-DQ OSs

Due to the ubiquity of chirality in nature, chiral self-assembly involving self-sorting behaviors has remained as one of the most important research topics of interests. Herein, starting from a racemic mixture of SEG-based (SEG = SEGPHOS) chlorogold(I) precursors, a unique chiral butterfly-shape hexadecanuclear gold(I) cluster (Au16) with different ratios of RSEG and SSEG ligands is obtained via homoleptic

The development of environmentally sustainable and highly efficient technologies for ammonia production is crucial for the future advancement of carbon-neutral energy systems. The nitrite reduction reaction (NO2RR) for generating NH3 is a promising alternative to the low-efficiency nitrogen reduction reaction (NRR), owing to the low N=O bond energy and high solubility of nitrite. In this study, we

Direct CO2 electroreduction to valuable chemicals is critical for carbon neutrality, while its main products are limited to simple C1/C2 compounds, and traditionally, the anodic O2 byproduct is not utilized. We herein report a tandem electrothermo-catalytic system that fully utilizes both cathodic (i.e., CO) and anodic (i.e., O2) products during overall CO2 electrolysis to produce valuable organic

Skeletal editing is an important strategy in organic synthesis as it modifies the carbon backbone to tailor molecular structures with precision, enabling access to compounds with specific desired properties. Skeletal editing empowers chemists to transform synthetic approaches of target compounds across diverse applications from drug discovery to materials science. Herein, we introduce a new skeletal

The kinetics of heterogeneous polymerization is determined directly using small-angle X-ray scattering (SAXS). This important advance is exemplified for the synthesis of sterically-stabilized diblock copolymer nanoparticles by reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) in mineral oil at 90 °C. The principle of mass balance is invoked

The controlled grafting of polymers from small- and macro-molecular substrates is an essential process for many advanced polymer applications. This usually requires the pre-functionalisation of substrates with an appropriate functional group, such as a RAFT agent or ATRP initiator, which requires additional synthetic steps. In this paper, we describe the direct grafting of RAFT polymers from carboxylate

An arylation protocol for pyridines is described, via the ring-opened Zincke intermediate. Treatment of pyridines with triflic anhydride and a secondary amine produces an azahexatriene species, which undergoes regioselective Pd-catalyzed arylation at the putative C4 position. Recyclization then provides the pyridine products. Alternatively, metal-free arylation with a diaryliodonium salt is selective

Modulating the surface and spatial structure of the host is associated with the reactivity of the active site, and also enhances the mass transfer effect of the CO2 electroreduction process (CO2RR). Here, we develop two-step ligand etch-pyrolysis to access an asymmetric dual atomic-site catalyst (DASC) composed of S, N-coordinated Zn-Mn dimer anchored on metal-organic frameworks (MOFs) derived yolk-shell

Here we report the development of a method for the electrochemical ultrasensitive detection of antibodies that couples the programmability and versatility of DNA-based systems with the sensitivity provided by enzymatic amplification. The platform, termed Enzyme-Linked DNA Displacement (ELIDIS), is based on the use of antigen-DNA conjugates that, upon the bivalent binding of a specific target antibody

Iron-catalyzed nitrene transfer has emerged as an attractive strategy for constructing N−C and N−heteroatom bonds. However, the ligand control in these Fe-catalyzed nitrene transfer reactions remains underdeveloped. Our previous studies discovered that 1,4,2-dioxazol-5-ones could react with various arylamines or phosphines to give N−N or N−P coupled products respectively under simple FeCl2-catalyzed

The significance of stereoselective C−H bond functionalization thrives on its direct application potential to pharmaceuticals or complex chiral molecule synthesis. Complication arises when there are multiple steregenic elements such as a center and an axis of chirality to control. Over the years cooperative assistance of multiple chiral ligands has been applied to control only chiral centers. In this

Low-voltage-gated calcium channels (LVGCCs; Cav3.1-3.3) represent promising drug targets for epilepsy, pain, and essential tremor. At present, modulators with heightened selectivity for a subtype LVGCCs are still highly desired. Here, we explored three classes of Buxus alkaloids and identified 9(10/19)abeo-artane-type ones Buxusemine H and Buxusemine L (BXSL) as an unprecedented type of Cav3.2 inhibitors