Burkholderiales bacteria have emerged as a promising source of structurally diverse natural products that are expected to play important ecological and industrial roles. This order ranks in the top three in terms of predicted natural product diversity from available genomes, warranting further genome sequencing efforts. However, a major hurdle in obtaining the predicted products is that biosynthetic

Nickel-rich layered oxides have great potential for commercial development applications, so it is critical to address their stability over long cycles. Ensuring long-term cycle stability relies heavily on the stability of the interface between the electrode and electrolyte in Li|LiNi0.8Co0.1Mn0.1O2 (NCM811) batteries. In this work, a denser, more stable and thinner nickel-rich cathode/electrolyte interface

This article describes the first enantioselective synthesis of the Tasmanian marine alkaloid (+)-cylindricine B. The concise construction of the compound hinged on dearomative retrosynthetic logic combined with a tactical advance in the generation of congested, cyclic, alpha-tertiary amine centers. The scope of this key coupling reaction was explored in addition to providing a synthetic application

While hypervalent halogens are versatile reagents enabling diverse reactions in organic synthesis, the utility of hypervalent chlorine compounds, particularly cyclic λ3-chloranes, remains underdeveloped despite their unique electronic properties and innate enhanced reactivity. Herein, we illustrate the elusive ligand coupling reaction of cyclic λ3-chloranes that suppresses the more facile competing

Polymeric carbon nitride (CN) emerged as an alternative, metal-free photoanode material in water-splitting photoelectrochemical cells (PEC). However, the performance of CN photoanodes is limited due to the slow charge separation and water oxidation kinetics due to poor interaction with water oxidation catalysts (WOCs). Moreover, operation under benign, neutral pH conditions is rarely reported. Here

The electronic structure modulation through heterogeneous single-atom doping is an effective strategy to improve electrocatalysis performance of catalysts. Here, Ir single-atom doped RuO2 (IrSA/RuO2) are constructed by substituting Ru sites with mono-disperse Ir atoms in RuO2 crystals. The catalyst shows excellent activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in

Hybrid organic-inorganic perovskite (HOIP) ferroelectrics exhibit polarization reversibility and have a wide range of applications in the fields of smart switches, memorizers, sensors, etc. However, the inherent limitations of small spontaneous polarization (Ps) and large coercive field (Ec) in ferroelectrics have impeded their broader utilization in electronic and data storages. Molecular ferroelectrics

Dynamic Nuclear Polarization (DNP) can significantly enhance the sensitivity of solid-state NMR. In DNP, microwave irradiation induces polarization transfer from unpaired electron spins to 1H nuclear spins via hyperfine couplings and spin-diffusion. The structure of the polarizing agents that host the electron spins is key for DNP efficiency. Currently, only a handful of structures perform well at

Electrophilic water-soluble compounds have proven versatile in reacting selectively with 2'-OH groups in RNA, enabling structure mapping, probing, caging, labeling, crosslinking, and conjugation of RNAs in vitro and in living cells. While early work focused on one or two types of reagents with limited properties, recent studies have greatly diversified the structure, properties, and applications of

Transition metal-catalyzed carbocyclization reactions offer a powerful method for the stereoselective assembly of complex, highly substituted (poly)cyclic scaffolds. Although 1,6-enynes are common substrates for these transformations, using polysubstituted alkene derivatives to construct functionalized cyclic products remains challenging due to significantly lower reactivity. This Perspective highlights

Transferases are enzymes that exhibit multisite migration characteristics. Significantly, enzyme activity undergoes changes during this migration process, which inevitably impacts the physiological function of living organisms and can even lead to related malignant diseases. However, research in this field has been severely hindered by the lack of tools for the simultaneous and differential monitoring

Infrared birefringent crystal that holds significant importance for optoelectronic application has been rarely reported. Traditional tetrahedral PS4, ethane-like P2S6, and octahedral InS6 units in thiophosphates typically manifest near isotropy, often resulting in extremely small birefringence. However, this study prepares -Rb2InP2S7 (1), -Rb2InP2S7 (3) and Cs2InP2S7 (2), consisting of the aforementioned

Two compounds were discovered in the well-studied BaO-Y2O3-SiO2 phase field. Two different experimental routines were used for the exploration of this system due to the differences of synthetic conditions and competition with a glass field. The first phase Ba5Y13[SiO4]8O8.5 was isolated through a combination of energy dispersive X-ray spectroscopy analysis and diffraction techniques which guided the

A novel approach for efficient synthesis of chiral C,O-chelated BINOL/gold(III) complexes by diastereomeric resolution using enantiopure BINOL as chiral resolving agent was demonstrated. The BINOL/gold(III) diastereomers with different solubility were separated by simple filtration, providing optically pure BINOL/gold(III) complexes with up to >99:1 dr. Combining with the efficient BINOL ligand dissociation

Nanohoops, an exciting class of fluorophores with supramolecular binding abilities, have the potential to become innovative tools within biological imaging and sensing. Given the biological importance of cell membranes, incorporation of macrocyclic materials with the dual capability of fluorescence emission and supramolecular complexation would be particularly interesting. A series of different-sized

Evolutionary and machine learning methods have been successfully applied to the generation of molecules and materials exhibiting desired properties. The combination of these two paradigms in inverse design tasks can yield powerful methods that explore massive chemical spaces more efficiently, improving the quality of the generated compounds. However, such synergistic approaches are still an incipient

Scanning electrochemical cell microscopy (SECCM) has been used to explore structure-electrocatalytic activity relationships through high-resolution mapping of local activities of electrocatalysts. However, utilizing SECCM in strongly alkaline conditions presents a significant challenge due to the high wettability of the alkaline electrolyte leading to a substantial instability of the droplet in contact

Organic-inorganic metal halide (OIMH) glass offers the advantages of large-scale production, high transparency, and minimal light scattering. However, undesired crystallization in OIMH glass can occur, leading to deteriorated transparency. Herein, a series of bisphosphonium organic cations were designed to construct Mn-based metal halide crystals with a photoluminescence quantum yield (PLQY) near unity

Despite the excellent performance of three-dimensional (3D) perovskite-based solar cells (PSCs), their poor stability under moisture and heating conditions limits their commercial application. To address the issue, a new pyreneammonium iodide (named as TAPPyI), in which pyrene-based compound 4,4',4'',4'''-(1,8-dihydropyrene-1,3,6,8-tetrayl)tetraaniline (named as TAPPy) acts as the 2D cation, is introduced

Reaction of 4 equiv of Li(N=C(tBu)Ph) with FeIICl2 results in isolation of [Li(Et2O)]2[FeII(N=C(tBu)Ph)4] (1), in good yields. Reaction of 1 with 1 equiv of I2 leads to formation of [FeIV(N=C(tBu)Ph)4] (2), in moderate yields. 57Fe Mössbauer spectroscopy confirms the Fe(IV) oxidation state of 2, and X-ray crystallography reveals that 2 has a square planar coordination geometry along with several intramolecular

Bridge-assisted superexchange coupling capable of long-range electron transfer proves to be effective for charge separation. However, the exploitation of this photochemical process in engineering reactive oxygen species (ROS) production remains unexplored. Herein, piperazine serves as a bridging unit to facilitate a cascade electron transfer from the electron donor site (CO) to the acceptor site (CN)

Porous Si (p-Si) nanomaterials are an exciting class of inexpensive and abundant materials within the field of energy storage. Specifically, porous Si has been explored in battery anodes to improve charge storage capacity, to generate clean fuels through photocatalysis and photoelectrochemical processes, for the stoichiometric conversion of CO2 to value added chemicals, and as a chemical H2 storage

Ribosomally synthesized and posttranslationally modified peptides (RiPPs) constitute a diverse class of natural products. Atropopeptides are a recent addition to the class. Here we developed AtropoFinder, a genome mining algorithm to chart the biosynthetic landscape of the atropopeptides. AtropoFinder identified more than 650 atropopeptide biosynthetic gene clusters (BGCs). We pinpointed crucial motifs

The helical structure is often the key factor for forming and enhancing chiroptical properties such as circular dichroism (CD) and circular polarized luminescence (CPL) effects. However, no matter whether helical molecules or helical aggregates, they usually display modest chiroptical signals, which limit their practical applications. Herein, chiral tetraphenylethylene (TPE) bimacrocycles that are

Chiral hydrazone photoswitch features as its high thermal stability and negative photochromy, making it desirable in fabrication of thermally stable optical device. However, chiral hydrazone capable of reversibly inversing chirality is scarcely reported. Herein, a series of new chiral hydrazone switches HI-1, HI-2 and HI-3 were designed and synthesized. Due to the photoinduced configuration changes

Strain-release driven annulations with bicyclo[1.1.0]butanes (BCBs) have become an attractive area of research for the synthesis of bioisosteric bicyclohexane derivatives, which play a vital role in drug discovery. Interestingly, the utilization of the inherent strain in BCB for the synthesis of functionalized amino bicyclo[2.1.1]hexenes, which can spatially mimic substituted benzenes and anilines

Metal sintering poses significant challenges for developing reliable catalytic systems toward high-temperature reactions, particularly those based on metal clusters with sizes below 3 nm. In this work, electrospun dual-oxide fibril-in-tubes consisting of CeO2 and Al2O3 are rationally designed in an all-in-one manner, to stabilize 2.3-nm Pt clusters with a Tammann temperature (sintering onset temperature)

57Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe4]) clusters based on a multidentate ligand platform (L3-) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertButylamino)pyrazolate ligand (PzNHtBu-). These clusters bear a terminal Fe(III)-O/OH moiety at the apical position and three additional iron centers forming the basal

Polymer microstructures rely on tacticity, yet exploration in polyamines has focused predominantly on atactic polymers. We introduce a method to synthesize a diverse library of ortho and para-cyanobenzenesulfonyl-activated-methyl aziridines using R, S, and racemic alaninol. Living anionic ring-opening polymerization of racemic sulfonyl aziridines yield soluble polymers, while enantiomerically-pure

O2 is an abundant, benign, and thermodynamically potent oxidant. However, it is also kinetically inert which frequently limits its use in synthetic transformations. Correspondingly, direct aerobic reactivity with O2 often requires comparatively harsh or forcing conditions to overcome this kinetic barrier. Forcing conditions limit product selectivity and can lead to over oxidation. Alternatively, O2

This study investigates the enhancement of catalytic activity in single-atom catalysts (SACs) through coordination engineering. By introducing non-metallic atoms (X = N, O, or F) into the basal plane of MoS2 via defect engineering and subsequently anchoring hetero-metallic Ru atoms, we created 10 types of non-metal-coordinated Ru SACs (Ru-X-MoS2). Computations indicate that non-metal atom X significantly

Various prenylated indoline alkaloids with diverse biological activities, including (–)-debromoflustramine B with significant butyrylcholinesterase inhibitory activity, could be synthesized by dearomative prenylation reactions of tryptophan derivatives. However, previously reported dearomative prenylations were limited to batch reactions at milligram scale, requiring multistep reactions and complex

Vancomycin is a crucial last-resort antibiotic for tackling Gram-positive bacterial infections. However, its potency fails against the more difficult-to-treat Gram-negative bacteria (GNB). Vancomycin derivatives have shown promise as broad-spectrum antibacterials but are still underexplored. Toward this, we present a novel strategy wherein we substitute the sugar moiety of vancomycin with a dipicolyl

Herein, we explore the intricate pathway complexity, focusing on the dynamic interplay between kinetic and thermodynamic states, during the supramolecular self-assembly of peptides. We uncover a multiresponsive chiroptical switching phenomenon influenced by temperature, denaturation and content of cosolvent in peptide self-assembly through pathway complexity (kinetic vs thermodynamic state). Particularly

Compounds with heterolayered architecture, as a family of the two-dimensional (2D) materials, are composed of alternating positive and negative layers. Their physical properties are determined not only by the charged constituents, but also by the interaction between the two layers. This kind of materials has been widely used for superconductivity, thermoelectricity, energy storage, etc. In recent years

The oxygen levels in a tumor typically exhibits complex characteristics, ranging from mild hypoxia to moderate and even severe hypoxia. This poses significant challenges for the efficacy of photodynamic therapy, where oxygen is an essential element. Herein, we propose a novel therapeutic strategy and developed a series of lipid droplet-targeting photosensitive dyes (Ser-TPAs), i.e., in situ synergistic

Macrocyclic thermally activated delayed fluorescent (TADF) emitters have been demonstrated to realize high efficiency OLEDs, but the design concept was still confined to rigid 𝜋-conjugated structures. In this work, two macrocycle TADF emitters, Cy-BNFu and CyEn-BNFu, with flexible alkyl chain as linker and bulky aromatic hydrocarbon as wrapping units were designed and synthesized. The detailed photophysical

The unique electronic nature of the 1,2,4,5-tetrazine or s-tetrazine (tz) ring has sparked tremendous scientific interest over the last years. Tetrazines have found numerous applications, and their ability to coordinate to metal ions has opened the possibility of exploring their chemistry in both molecular systems and extended networks. The rich redox chemistry of s-tetrazines allows them to exchange

Exploiting the potential of curcuminoids (CCMoids) as molecular platforms, a new 3.53 nm extended system (pyACCMoid, 2) has been designed in two steps by reacting a CCMoid with amino-terminal groups (NH2-CCMoid, 1, of 1.79 nm lenght) with polycyclic aromatic hydrocarbon (PAH) aldehydes. CCMoid 2 contains pyrene units at both ends as anchoring groups to optimize its trapping in graphene nano-junctions

Ultraviolet nonlinear optical (UV NLO) materials have garnered significant interest for their prospective applications in advanced laser technologies. However, tailoring the desired structure in these materials remains a formidable challenge. Here, we propose a simple yet effective strategy for synthesizing rare-earth borates, KxNa3-xLa2B3O9 (x=23), by manipulating the A-site cations to induce structural

The variety of possible benzene isomers may provide a fundamental basis for understanding structural and reactivity patterns in organic chemistry. However, the vast majority of these isomers remain unsynthesized, while most of the experimentally known species are only moderately stable. Consequently, there is a high probability that the theoretically proposed isomers would also be barely metastable

Urea derivatives, polyureas, and poly(urea-urethanes) are materials of great interest. However, their current methods of synthesis involve toxic feedstocks - isocyanate and phosgene gas. There is significant interest in developing alternative methodologies for their synthesis from safer feedstocks. We report here new methods for the synthesis of urea derivatives, polyureas, and polyurea(urethane) using

The resurgence of interest in sodium-ion batteries (SIBs) is largely driven by their natural abundance and favorable cost, apart from their comparable electrochemical performance when compared with lithium-ion batteries (LIBs). The uneven geographic distribution of the raw materials required for LIBs has also contributed to this. The solid-state electrolyte (SSE) is typically one of the vital components

Cyclic polymers have applications across various fields, including material science, biomedicine, and inorganic chemistry. Cyclic polymers derived from alkyne monomers have expanded the application scope to include electronic materials and polyolefins. This review highlights recent advancements in the synthesis of cyclic polymers from both mono- and disubstituted alkynes. The aim is to provide a comprehensive

Solar-light driven reduction of CO2 to CH4 is a complex process involving multiple electron and proton transfer processes with various intermediates. Therefore, achieving high CH4 activity and selectivity remains a significant challenge. Covalent organic frameworks (COFs) represent an emerging class of photoactive semiconductors with molecular level structural tunability, modular band gaps, and high

Vitrimers are polymer networks with covalent bonds that undergo reversible exchange reactions and rearrange their topology as response to an external stimulus. The temperature-dependent change in viscoelastic properties is conveniently adjusted by selected catalysts. In these thermo-activated systems, the lack in spatial control can be overcome by using photolatent catalysts. Herein, we advance this

An unusual cascade C-H activation, vinylation and 6π-electrocyclization of 2-pyridyl aldimines with vinyl bromides /triflates is achieved by catalysis with a unique CCC pincer NHC-Ru(III) complex (Cat B) we explored. This reaction enables a rapid and diverse synthesis of polycyclic 4H-pyrido[1,2-a]pyrimidine derivatives in good to high yield mostly, and broad substrate scope. Mechanistic study suggests

Due to the intrinsic spatial orientation and structural novelty, Csp3-rich N-heterocycles have been recognized as an increasingly sought-after scaffolds as compared to the aromatic ring-based moieties, which obtained considerable recent attentions in drug discovery. Hence, we disclose a modular cobalt-catalyzed conformationally restricted alkylarylation strategy for the divergent access to Csp3-rich

Although there are few reduced dinitrogen complexes of scandium, this metal has revealed a new structural type in reductive dinitrogen chemistry by reduction of bis(pentamethylcyclopentadienyl) scandium halides under N2. Reduction of Cp*2ScI (Cp* = C5Me5) with potassium graphite (KC8) under dinitrogen generates the dark blue paramagnetic complex (Cp*2Sc)2(µ-η1:η1-N2), 1. This end-on bridging (N=N)2−

The cellular membrane transport of physiologically important cations and anions is omnipresent and regulates different physiological functions. Whereas a notable number of cation-anion transporters are being developed to transport salts across the membrane, developing an artificial cation-anion symporter with stimulus-responsive activities is an immense obstacle. Herein, for the first time, we report

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