The inductive effect is a central concept in chemistry and is often exemplified by the pKa values of acetic acid derivatives. The reduction in pKa is canonically attributed to the electron density of the carboxylate group being reduced through the inductive effect. However, wave functional theory calculations presented herein reveal that the charge density of the carboxylate group is not explained

The reaction chemistry of an unprecedented ‘inorganic cumulene’ - featuring a five-atom BNBNB chain - towards C=O (and related) multiple bonds is disclosed. In marked contrast to related all-carbon systems, the intrinsic polarity of the BNBNB chain (featuring electron-rich nitrogen and electron-deficient boron centres) enables metathesis chemistry with electrophilic heteroallenes such as CO2 and with

The recently discovered metagenomic urethanases UMG-SP1, UMG-SP2, and UMG-SP3 have emerged as promising tools to establish a bio-based recycling approach for polyurethane (PU) waste. These enzymes are capable of hydrolyzing urethane bonds in low molecular weight dicarbamates as well as in thermoplastic PU and the amide bond in polyamide employing a Ser-Sercis-Lys triad for catalysis, similar to members

The longest oligos that can be chemically synthesized are considered to be 200-mers. Here, we report direct synthesis of an 800-mer green fluorescent protein gene and a 1,728-mer Φ29 DNA polymerase gene on an automated synthesizer. Key innovations that enabled the breakthrough include conducting the synthesis on a smooth surface rather than within the pores of traditional supports, and the use of the

The development of catalytic technologies for sustainable energy conversion is a critical step toward addressing fossil fuel depletion and associated environmental challenges. High-efficiency catalysts are fundamental to advancing these technologies. Recently, field-effect facilitated catalytic processes have emerged as a promising approach in energy and environmental applications, including water

Polymer-metal nanocomposites are a fascinating class of materials that synergize the distinct properties of polymers and metals. Incorporating metal nanofillers into polymer matrices significantly enhances electrical conductivity, mechanical strength, and thermal stability through intricate chemical interactions. This review provides an in-depth understanding at current and emerging fabrication techniques

The search for efficient, earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) has identified unsaturated molybdenum disulfide (MoS₂) as a leading candidate. This review synthesis recent advancements in the engineering of MoS₂ to enhance its electrocatalytic properties. It focuses on strategies for designing an unsaturated electronic structure on metal catalytic centers and their

Proteins typically adopt a single fold to carry out their function, but metamorphic proteins, with multiple folding states, defy this norm. Deciphering the mechanism of conformational interconversion of metamorphic proteins is challenging. Herein, we employed nuclear magnetic resonance (NMR), circular dichroism (CD), and all-atom molecular dynamics (MD) simulations to elucidate the mechanism of fold

The interface between the perovskite layer and the electron transport layer is an extremely important factor that cannot be ignored in achieving high-performance perovskite photovoltaic technology. However, the void defects of the interface pose a serious challenge for high performance perovskite solar cells (PSCs). To address this, we report a polydentate ligand reinforced chelating strategy to strengthen

Non-centrosymmetric (NCS) compounds can exhibit many symmetry-dependent functional properties yet their rational structure design remains a great challenge. Herein, a strategy to introduce the F-centered octahedra to construct the peroveskite-type framework filled by the π-conjugated [B2O5]4− dimers is proposed to obtain NCS compounds. The first examples of antiperovskite or double antiperovskite borate

Oxygen vacancies in Ruddlesden−Popper (RP) perovskites (PV) [AO][ABO3]n play a pivotal role in engineering functional properties and thus understanding the relationship between oxygen-vacancy distribution and physical properties can open up new strategies for fine manipulation of structure-driven functionalities. However, the structural origin of preferential distribution for oxygen vacancies in RP

Developing dithienylethene (DTE)-based fluorescence switches triggered by biocompatible visible light has always been a long-term goal in view of their potential in numerous biological scenarios. However, their practical availability is severely limited by the short visible light (generally less than 500 nm) required for photocyclization, their inability to achieve red or near-infrared emission, and

Metal-organic frameworks (MOFs) can be prepared from oligomeric organic ligands to prepare materials referred to as oligoMOFs. Studies of oligoMOFs are relatively limited, with most existing reports focused on fundamental structure-property relationships. In this report, functional groups, such as terminal alkynes and pyridine groups, are installed on the tether between 1,4-benzene dicarboxylic acid

The benzene tetraanion-bridged rare earth inverse arene amidinate complexes [{Ln(κ1:η6-Piso)}2(μ-η6:η6-C6H6)] (2-Ln, Ln = Gd, Tb, Dy, Y; Piso = {(NDipp)2CtBu}, Dipp = C6H3iPr2-2,6) were prepared by the reduction of parent Ln(III) bis-amidinate halide precursors [Ln(Piso)2X] (Ln = Tb, Dy; X = Cl, I) or [Ln(Piso)2I] (Ln = Gd, Y) with 3 eq. KC8 in benzene, or by the reaction of the homoleptic Ln(II) complexes

Self-assembling cyclic peptide nanotubes are fascinating supramolecular systems with promising potential for various applications, such as drug delivery, transmembrane ionic channels, and artificial light-harvesting systems. In this study, we present novel pH-responsive nanotubes based on asymmetric cyclic peptide-polymer conjugates. The pH response is introduced by a tertiary amine-based polymer,

Chiral metal clusters, due to their intriguing optical properties and unique resemblance in size with biomolecules, have gained vast attention in recent times as potential candidates for application in bio-detection and therapy. While several strategies are reported for the synthesis of optically active clusters, a facile approach that enhances multitude of properties has remained a challenge. Herein

The synthesis, electrochemical, spectroelectrochemical, photophysical and light induced electron transfer reactions in two new anthanthrene quinodimethanes have been studied and analyzed in the context of dynamic electrochemistry. Their properties are dependent on the interconversion between folded and twisted forms, which are separated by a relatively small energy range, thus allowing to explore their

The shelf life of 2D MXenes in functional devices and colloidal dispersions is compromised due to oxidation in the aqueous system. Herein, a systematic investigation is carried out to explore the potential of various amino compounds as antioxidants for Ti3C2Tx MXenes. A range of basic, acidic, and neutral amino acids were examined for their effectiveness, where certain antioxidants failed to protect

Herein, we present a strategy to access a novel class of pH-responsive, dual-state emissive (DSE), highly fluorescent pyrrole-based chromophores via diformylation of dipyrroethenes (DPE) followed by condensation with various anilines derivatives. The DPE-based chromophores exhibit a large Stokes’ shift and maintain good fluorescent quantum yields. Remarkably, these chromophores demonstrate reversible

Hydrazine-assisted water splitting is a promising strategy for energy-efficient hydrogen production, yet challenges remain in developing effective catalysts that can concurrently catalyze both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) in acidic media. Herein, we report an effective bifunctional catalyst consisting of Rh clusters anchored on Co₃O₄ branched nanosheets

Graphdiyne (GDY) alone as photocatalyst is unsatisfactory because of low crystallinity, limited regulation of band gap, weak photogenerated charge separation, etc., and heterojunctioning with other materials is necessary to activate the photocatalytic activity of GDY. Through elaborate design, a diacetylene-rich linker (S2) was prepared and allowed to construct crystalline and structurally well-defined

Near-infrared (NIR) emitters with high two-photon absorption (2PA) cross-sections are of interest to enable in vivo imaging in the tissue transparency windows. This study explores the potential of DNA-stabilized silver nanoclusters (AgN-DNAs) as water-soluble two-photon absorbers. We investigate 2PA of four different atomically precise AgN-DNA species with far-red to NIR emission and varying nanocluster

Lithium metal batteries (LMBs) promise high-energy-density storage but face safety issues due to dendrite-induced lithium deposition, irreversible electrolyte consumption, and large volume changes, which hinder their practical applications. To address these issues, tuning lithium deposition by structuring a host for the lithium metal anode has been recognized as an efficient method. Herein, we report

Nanofluidics is the system of fluid transport limited to nano-confined space, including the transport of ions and molecules. The use of intelligent nanofluidics have shown great potential in energy conversion. However, ion transport is hindered by homogeneous membranes with uniform charge distribution and concentration polarization, which often leads to an undesirable power conversion performance.

Alkali activation was the common method to prepare commercial porous carbon. In a mixed alkali activation system, the role of individual alkali was generally assumed to be the same as in single alkali activation system, and only low corrosiveness of weak alkali was mostly emphasized. However, the intrinsic roles of individual alkali should be finely understanded and redefined to illuminate the activation

In this study, we theoretically examined the mechanism of aromaticity induced in closely stacked cofacial π-dimers of 4nπ antiaromatic molecules, which is called stacked-ring aromaticity, in terms of the effective number of π-electrons (Nπ) and Baird’s rule. High-precision quantum chemical calculations combined with a multi-configurational wavefunction analysis revealed that double-triplet [1(T1T1)]

Isoquinoline core is present in one of the largest subsets of bioactive natural products. The multifunctional isoquinoline core exerts diverse bioactivity, resulting in the development of numerous isoquinoline based drugs and molecules that are currently under clinical trials. We developed a new approach for phosphite-mediated alkyl migrations to C2 carbon for an overall ortho-C−H alkylation via N-alkylation

Sulfonium is an electrophilic and biocompatible group that is widely applied in synthetic chemistry on small molecules. However, there are few developments of peptide and protein-based sulfonium tools. We recently reported a sulfonium-mediated tryptophan crosslinking, and developed NleS+me2 (norleucine-demethylsulfonium) peptides as dimethyllysine mimics that crosslink site-specific methyllysine readers

The prevalence of naphthalene compounds in biologically active natural products, organic ligands and approved drugs has motivated the development of efficient strategies for their selective synthesis. C-H functionalization of naphthalene has been frequently used, but mainly focus on two-component reaction, while multiple-component C-H functionalization for the synthesis of naphthalene compounds has

The reaction between molybdenum(II) acetate and 5-aminoisophthalic acid (H2Iso-NH2) afforded [Mo12O12(μ2-O)12(Iso-NH2)12]12–, a novel molybdenum(V) metal–organic polyhedron (MOP) with a triangular antiprismatic shape stabilized by intramolecular N–H···O hydrogen bonds. The synthesis conditions, particularly the choice of solvent and reaction time, led to the precipitation of the Mo(V)-MOP in one of

De novo protein design is delivering new peptide and protein structures at a rapid pace. Many of these synthetic polypeptides form well-defined and hyperthermal-stable structures. Generally, however, less is known about the dynamic properties of the de novo designed structures. Here, we explore one aspect of dynamics in a series of de novo coiled-coil peptide assemblies: namely, peptide exchange within

It is an attractive but formidable challenge in the chemical recycling of polystyrene (PS) wastes to the value-added aromatic compounds due to the inertness of C-C bonds in polymer backbone. Here we develop a light-driven, copper-catalyzed protocol to achieve aerobic oxidation of various alkylarenes or real-life PS wastes to benzoic acid and oxidized styrene oligomers. The resulting oligomers can be

Large language models (LLMs) have emerged as powerful tools in chemistry, significantly impacting molecule design, property prediction, and synthesis optimization. This review highlights LLM capabilities in these domains and their potential to accelerate scientific discovery through automation. We also review LLM-based autonomous agents: LLMs with a broader set of tools to interact with their surrounding

We report the synthesis, structural characterization and magnetic properties of K3coronene, and demonstrate a computational screening workflow designed to accelerate the discovery of metal intercalated polycyclic aromatic hydrocarbon (PAH), a class of materials of interest following reports of superconductivity, but lacking demonstrated and understood characterised materials compositions. Coronene

Catalytic alkene isomerization is a powerful synthetic strategy for preparing valuable internal alkenes from simple feedstocks. The utility of olefin isomerization hinges on the ability to control both positional and stereoisomerism to access a single product among numerous potential isomers. Within base-metal catalysis, relatively little is known about how to modulate reactivity and selectivity with

Photoacids undergo an increase in acidity upon electronic excitation, enabling excited-state proton transfer (ESPT) reactions. A multitude of compounds that allow ESPT has been identified and integrated in numerous applications, as is outlined by reviewing the rich history of photoacid research reaching back more than 90 years. In particular, achievements together with ambitions and challenges are

The excessive accumulation of nitrate/nitrite (NOx-) in surface and groundwater has severely disrupted global nitrogen cycle and jeopardized public health. The electrochemical conversion of NOx- to ammonia (NH3) not only holds promise for ecofriendly NOx- removal, but also provides a green alternate to the energy-intensive Haber–Bosch process for NH3 production. Recently, in addition to electrocatalyst

The first carbocyclic gallylene [(ADC)2Ga(GaI2)] and bis-gallylene [(ADC)Ga]2 (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3) featuring a central C4Ga2 ring annulated between two 1,3-imidazole rings are prepared by KC8 reductions of [(ADC)GaI2]2. Treatment of [(ADC)Ga]2 with Fe2(CO)9 affords complex [(ADC)GaFe(CO)4]2 in which each Ga(I) atom serves as a two-electron donor. [(ADC)Ga]2 activates white phosphorus

Metal halide perovskites (MHPs) have been developed rapidly in light-emitting diodes (LEDs), laser, solar cells, photodetectors and other fields in recent years due to their excellent photoelectronic properties, which attract more researchers’ attention. Perovskite LEDs show great promise in the next generation of lighting and display technologies, and external quantum efficiency (EQE) values of polycrystalline

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

Non-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their Earth abundance combined with intriguing physical and chemical properties relevant for both fundamental studies and technological applications. Nevertheless, their synthesis is still primitive when compared to noble metals

Currently, there is no effective antiviral drugs nor vaccine for coronavirus disease 2019 (COVID-19)caused by acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Due to its high conservativeness andlow similarity with human genes, SARS-CoV-2 main protease (Mpro) is one of the most favorable drug targets.However, the current understanding of the molecular mechanism of Mpro inhibition is limited by

Despite the remarkable mechanical/optical/electrical properties, the inorganic particles and dynamic polymer assemblies encountered the difficulties in compatibility with structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare the inorganic nanocrystal-polymer assemblies. Experiencing

Biradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only few examples have been reported as active layer in organic field-effect transistors (OFETs) with charge mobility of around 10−3 cm2 V−1 s−1 due to a steric disadvantage of the mesityl group to kinetically stabilize