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

Some achiral cyanine dyes form well-ordered chiral assemblies exhibiting pronounced Circular Dichroism (CD) and Circularly Polarized Luminescence (CPL). Notably, achiral C8O3 cyanines self-assemble into tubular J-aggregates, which further organize into bundles displaying bisignate CD spectrum - hallmark of an exciton coupled system - and an unusual bisignated CPL. In contrast, the tubular aggregates

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

Systems incorporating the cis-Mo(O)2 motif catalyse a range of important thermal homogeneous and heterogeneous oxygen atom transfer (OAT) reactions spanning biological oxidations to platform chemical synthesis. Analogous light-driven processes could offer a more sustainable approach. The cis-Mo(O)2 complexes reported here photocatalyse OAT under visible light irradiation, and operate via a non-emissive

In this work, we designed and synthesized three spirobifluorene (SBF)-based hole-transporting materials (HTMs) by incorporating the di-4-tolylamino group at different positions of the SBF skeleton. These materials demonstrate excellent thermal stability with thermal decomposition temperatures (Td) up to 506 ºC and outstanding morphological stability with a glass transition temperature (Tg) exceeding

Controllable β-carbon elimination to extrude norbornene remains a long-standing challenge in palladium and norbornene chemistry. Herein, this manuscript described a switchable synthesis of biologically active C4-ethylaminoindole and C7-aminoindoline scaffolds by controlling the β-carbon elimination, utilizing aziridine as a C–H ethylamination reagent through a C-N bond cleavage reaction. Furthermore

S-adenosyl methionine (SAM)-dependent methyltransferases hold significant potential as tools for the biocatalytic synthesis of complex molecules due to their ability to methylate or alkylate substrates with high regio-, chemo-, and stereoselectivity. Recent advancements in enzyme-catalyzed S-methylation and S-alkylation of S-adenosyl homocysteine (SAH) using synthetic alkylation agents have expanded

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

Water radical cations play a pivotal role in various scientific and industrial fields due to their unique reactivity and capacity to drive complex chemical transformations. Here we explored the formation of quaternary ammonium cations through the direct oxidation reaction of aromatic amines, facilitated by water radical cations within water microdroplets. This process was monitored via in situ mass

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

Thiolate-protected metal nanoclusters (NCs) have been widely used in various electrocatalytic reactions, yet the dynamic evolution of metal NCs during electrocatalysis has been rarely explored and the activity origin remains largely ambiguous. Herein, using PtAu24(SCH3)18 NC as a prototype model, we combined advanced first-principles calculations and attenuated total reflection surface-enhanced infrared

Aqueous Zn-ion batteries are promising candidates for next-generation energy storage devices due to the advantages of high safety, low cost and good environmental friendliness. However, the uncontrollable dendrite growth and undesirable side reactions occurring on the Zn anode result in poor cycling stability. Herein, a Lewis base, triethanolamine, is used as an electrolyte additive to construct a

Highly efficient water splitting under visible light irradiation was achieved using Ir, Sb, and Al-codoped SrTiO3 of a single particulate metal oxide photocatalyst by a solid-state reaction followed by the flux treatment using SrCl2 and loading of a RhCrOx cocatalyst. The photocatalytic activity was improved by Al2O3 addition to the flux treatment, and doping of small amounts of Ir and Sb. It was notable

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

Chaotropic polyoxometalates (POMs) form robust host-guest complexes with γ-cyclodextrin (γ-CD), offering promising applications in catalysis, electrochemical energy storage, and nanotechnology. In this article, we provide the first computational insights on the supramolecular binding mechanisms using Density-Functional Theory and Classical Molecular Dynamics simulations. Focusing on the encapsulation

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

The application of silicon-based nanomaterials in fast-charging scenarios is hindered by volume expansion during lithiation and side reactions induced by surface effects. Constructing a robust encapsulation structure with high mechanical strength and conductivity is pivotal for optimizing the electrochemical performance of nanostructured silicon anodes. Herein, we propose a multifaceted hierarchical

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

This manuscript unveils the synthesis of 2H-thiazolo[4,5-d][1,2,3]triazole (ThTz), an unprecedented [5-5]-fused heteroaromatic system, and established a scalable synthetic procedure for producing large quantities of ThTz ring bearing a sulfone group on the thiazole ring. The sulfone moiety proves to be a versatile reactive tag, facilitating diverse transformations such as SNAr reactions, metal-catalyzed

The drug design principles are of great value in developing nanomedicines with favorable functionalities. Herein we propose a nanocarbon-enabled hybridization strategy to construct a pharmacologically cooperative therapeutic for improved cancer therapy in the light of the pharmacophore hybridization in medicinal chemistry and the synthetic principles of nanocarbons. An antioxidant defense pharmacological

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

Excited-state molecular dynamics simulations are crucial for understanding processes like photosynthesis, vision, and radiation damage. However, the computational complexity of quantum chemical calculations restricts their scope. Machine learning (ML) offers a solution by delivering high accuracy properties at lower computational costs. We present SpaiNN, an open-source Python software for ML-driven

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−

Conformational changes of non-covalent complexes are of fundamental importance to many chemical and biological processes. Yet, these low-energy structural changes are usually fast and difficult to monitor, which poses challenges in their detailed kinetic understanding. Described in this work is the kinetics and thermodynamics correlation of the conformational change of a model supramolecular system

Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [tBuOCO]WCC(CH3)3(THF)2 (1) to yield tungstacy-clopropene (3) and tungstacyclopentadiene (4) complexes. The ratio of 3 and 4 in the reaction mixture depends on the stoi-chiometry of the reaction. The maximum concentration of 3 occurs with one equiv of cyclooctyne and 4 is the exclusive product of the reaction above three equivalents

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

We report the synthesis of (TMA)AgBr2 (TMA = tetramethylammonium bromide) crystal comprising of inorganic anionic chains of -(AgBr2)∝-, stabilized by columnar stacks of organic TMA cations, with periodic arrangement of shorter and longer Ag(I)---Ag(I) bonds, though all Ag(I) ions are chemically equivalent. The presence of two chemically non-equivalent bridging Br ions is assigned to be the primarily

Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M–CAr bond forming an equilibria between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M–CAr bonds represents an unprecedented example of β-aryl elimination from a ketimide ligand in early

Technological enablers that use CO2 as a feedstock to create value-added chemicals, including ethanol, have gained widespread appeal. They offer a potential solution to climate change and promote the development of a circular economy. However, the conversion of CO2 to ethanol poses significant challenges, not only because CO2 is a thermodynamically stable and chemically inert molecule but also because

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