N-Heterocyclic carbene (NHC) organocatalysis has experienced significant advancements. Two distinct reaction pathways have been developed, ionic and radical, through Breslow intermediates (BIs) and Breslow enolates (BI-s), respectively. The ability to selectively generate these intermediates is crucial for optimizing reaction outcomes. In this paper we show that with mesoionic carbenes (MICs) it is

Facile one and two site reduction of hexachlorophosphazene using cyclic (alkyl)(amino)carbene substituents is shown to yield P-CAACMe-cyclo-(PNP(Cl)2NP(Cl)2N) 1 and P,P’-bis-CAACMe-cyclo-(PNPNP(Cl)2N) 2 (CAACMe=1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene). Compound 1 is characterized by its predominantly phosphorus centered HOMO, which results in typical phosphine-type nucleophilic

Radially π-conjugated macrocycles with mixed aromatic and quinonoid units are considered. As a function of including an increasing number of aromatic units into a ring-like nanohoop with quinonoid units, a transition occurs where the HOMO and LUMO levels cross, leading to a topological transition described for the first time. Such transitions have been seen before in ethynylene-linked oligoacene polymers

All-solid-state lithium-ion batteries (ASLIBs) are important and promising electric energy storage devices with high stabilities and energy densities. As burgeoning key materials in ASLIBs, rare earth (RE) halide solid-state electrolytes (SEs) have better overall electrochemical performance than do oxide and sulfide SEs. Technologies for the efficient preparation, mass production and recycling of RE

Organoalkoxysilanes (e.g. R–SiMe3-n(OR’)n, 1 ≤ n ≤ 3 with R=alkyl or aryl) have found various applications in synthetic chemistry and materials science because the silicon-bound alkoxy groups provide unique opportunities for further derivatization and transformations. Among the few catalytic strategies that allow the direct and intermolecular introduction of an alkoxysilyl unit onto an organic substrate

The selective oxidation and degradation of lignin are crucial for realizing its potential as a biofuel or petroleum substitute. Despite the importance of C–C bond cleavage for lignin valorization, this process is significantly challenging. Herein, we present plasmonic gold nanoparticles (Au NPs) as environmentally friendly and reusable photocatalysts for the chemoselective oxidation of the benzylic

Confocal microscopy using silicaphilic molecular probes is a promising approach to identify the ionic character of silica interfaces. Using ab initio and density functional theory we model the structural and electronic properties of the (2-(4-pyridyl)-5((4-(2-dimethyl-aminoethyl-aminocarbamoyl)-methoxy)phenyl)-oxazole (PDMPO) chromophore at different protonation states, in vacuum, and when next to

Despite significant progress in the B–H functionalization of carboranes, the development of cost-effective catalytic systems devoid of noble metals, coupled with mechanistic validation of regioselectivity control, remains a formidable challenge. Herein, we disclose an Ag salt-free, redox-neutral, and inexpensive ruthenium(II)-catalyzed protocol that enables exclusive B(4)–H acylmethylation of o-carboranes

Cysteine sulfenic acid (SOH) modifications are pivotal in redox signaling, yet establishing their causal biological roles remains challenging due to methodological limitations. Traditional approaches often lack precision or disrupt non-redox cysteine functions. This perspective highlights two innovative chemical biology strategies to address these challenges: (1) integrating bioorthogonal cleavage

Ammonia, as a carbon-free fuel and promising hydrogen carrier, has attracted significant attention in the context of a net-zero-emission scenario. Photocatalytic ammonia decomposition is a promising approach for hydrogen production, and much attention has been given to this area in recent years. This mini-review summarizes the latest research progress in photocatalytic ammonia decomposition for hydrogen

Selecting effective catalysts for the hydrogen evolution reaction (HER) among MXenes remains a complex challenge. While machine learning (ML) paired with density functional theory (DFT) can streamline this search, issues with training data quality, model accuracy, and descriptor selection limit its effectiveness. These hurdles often arise from incomplete understanding of the catalytic mechanisms. Here

Diabetes and its complications have drawn growing research attention due to their detrimental effects on human health. Although optical probes have been used to help understand many aspects of diabetes, the lung diseases caused by diabetes remain unclear and have rarely been explored. Herein, a tandem-reaction (TR) strategy is proposed based on the adjacent diol esterification-crosslinking reaction

Electrocatalysis provides a desirable approach for moving toward a sustainable energy future. Herein, a rapid and facile potential pulse method was implemented for a one-pot electrosynthesis of the amorphous Ni-Co-Fe-P (NCFP) electrocatalyst. The 2 mg cm−2 loadedelectrode displayed excellent trifunctional electrocatalytic activities toward the hydrogen evolution reaction (ηj=10HER = 102 mV), oxygen

Supramolecular chemistry empowers polymeric materials versatile beneficial features encompassing stimulus adaptation, e.g self-healing, to truly function in a biomimetic manner. To seek effective self-healing mechanism for current polymers with no trade-offs in other property perspectives still remains in disguise. Herein, we present a sustainable alternative of the conventional covalent elastomers

In deep learning methods, especially in the context of chemistry, there is an increasing urgency to uncover the hidden learning mechanisms often dubbed as “black box." In this work, we show that graph models built on computational chemical data behave similar to natural language processing (NLP) models built on text data. Crucially, we show that atom-embeddings, a.k.a atom-parsed graph neural activation

In this manuscript, we create a new hetero dyad consisting of two electron acceptors with nearly isoenergetic HOMO and LUMO levels, namely perylene diimide (PDI) and aza dioxa triangulenium (ADOTA). This dyad system displays an unusual and reversible excited state electron transfer process. Upon excitation, the dyad shows complete energy transfer from the locally excited PDI to the ADOTA moiety in

Controlling excited-state dynamics is crucial for achieving dual emissions of f ultralong room-temperature phosphorescence (URTP) and thermally activated delayed fluorescence (TADF), but remains challenging in the exploration of transition-metal compounds. Herein, we propose a new strategy to develop highly efficient TADF and URTP dual-emission materials by modulating URTP organic molecules through

The stretching vibration of hydroxyl groups, ν(OH), appears with a strong absorption in the 3 µm region of the infrared (IR) spectrum. In chiral molecular crystals, also vibrational circular dichroism (VCD) can be observed for this band, which is demonstrated by the example of two chiral alcohols crystallising with space groups P21 and P3121, respectively. Measurements demonstrate that the VCD bands

As the demand for deuterated compounds continues to rise in medicinal chemistry, various methods have been developed to incorporate deuterium atoms. Among these, achieving consecutive trans-dual deuteration remains a challenging task. We have designed a novel strategy to synthesize trans-dual deuterated cyclopropanes at adjacent carbon positions. This approach involves H/D exchange followed by a photocatalyzed

Co-crystals are composed of two or more chemically inequivalent molecular species, excluding solvents, generally in a stoichiometric ratio. Co-crystals are particularly important in pharmaceutical development, where a suitable co-crystal can significantly improve the physiochemical and pharmacokinetic properties of an active pharmaceutical ingredient. However, co-crystal discovery remains both practically

Three-dimensional (3D) cyanide hybrid organic-inorganic double perovskites (CHOIPs) have abundant electrical, optical, thermal, and magnetic properties due to their diverse chemical variability and structural flexibility, making them promising for applications in transducers, memories, and switch materials. However, the mechanical properties, crucial for practical application, have been overlooked

Melanin as a bio-optoelectronic material holds immense potential. However, understanding its exact molecular structure has been stalling for decades due to difficulties in experiments, which hinder uncovering its structure-property relationship. Conventional theoretical modeling is also limited due to the huge size of its chemical space, which results in millions of possible oligomer structures. Here

Stimuli-responsive lanthanide-based single-molecule magnets (Ln-SMMs) are attractive for their potential in information storage, sensors and molecular devices. However, challenges remain in synergistically tuning the magnetic and optical properties of Ln-SMMs at the same temperature. Herein, we report a mononuclear dysprosium complex containing anthracene units, namely [Dy(SeCN)2(NO3)(depma)2(4-hpy)2]

Cofacial porphyrin dimers have garnered extensive attention for their unique photophysical and catalytic properties, which strongly depend on structural configurations. However, precisely controlling key parameters, such as lateral and rotational displacements, interfacial distance, and stability, remains challenging. Herein, we present a novel strategy for engineering porphyrin dimer structures and

Excitation wavelength-dependent (Ex-De) chromophores, which exhibit changes in spectral composition with varying excitation wavelengths, have garnered significant interest. However, the pursuit of novel photoluminescence (PL) mechainsims and high luminescence quantum yields is facing huge challenges. Here, we discover that the introduction of a spinacine moiety to 2-(2-Hydroxy-5-methylphenyl)benzothiazole

Metal-organic frameworks (MOFs) are receiving growing interest as transformative materials for real-world atmospheric water harvesting applications. However, obtaining molecular-level details on how surface effects regulate MOF water uptake has proven to be elusive. Here, we present a novel methodology based on ambient pressure soft X-ray absorption spectroscopy (AP-NEXAFS), machine learning-assisted

G protein coupled receptors, particularly class A GPCRs are arguably the most important class of membrane receptors and preferred targets for drug development. Despite extensive research on how ligands modulate the receptor response, discovering new, highly specific ligands remains challeng- ing. However, finding residues outside the conserved microswitches that affect the active-inactive state equilibrium

Covalent organic framework (COF) is a promising material for oxygen catalysis. Herein, a novel highly stable conjugated two-dimensional Poly (benzimidazole porphyrin-cobalt) (PBIPorCo) with a large delocalization energy is synthesized by meso-5, 10, 15, 20-tetra (4-cyano-phenylporphyrin) cobalt (TCNPorCo) and 3,3'-diaminobenzidine (DAB). The decrease in energy between the HOMO and LUMO orbitals of

With the rapid increase in temperatures around the planet, the need to develop efficient means to reduce CO2 emissions has become one of the greatest challenges of the scientific community. Many different strategies are being studied worldwide, one of which consists of trapping the gas into porous materials, either for its short- or long-term capture and storage, or its re-use for the production of

Overcoming spin-forbidden radiation in chiral phosphors has attracted enormous attention because of their capacity in circularly polarized organic ultra-long room temperature phosphorescence (CP-OURTP). However, their developments have been hindered by the short lifetimes and low dissymmetry factors, which is attributed to the differing parity selection rules that govern the electric and magnetic dipole

Completely or partially ordered intermetallic compounds possess unique electronic structures and chemical bonding endowing them as an emergent class of catalytic materials for selective hydrogenation reactions. In this review, we focus on the structural and chemical aspects of the different classes of intermetallic compounds, followed by illustrative examples of the consequences of their structural/chemical

This study explores a novel N-heterocyclic carbene-mediated siloxane exchange mechanism, laying the foundation for designing covalent adaptable networks (CANs) with high temperature stability (>200 °C) for the dynamic covalent chem-istry. Small molecule siloxane compounds, obtained by hydrosilylation reactions, are used to demonstrate siloxane-exchange via a mechanism supported by density functional

Single-atomic Cu catalysts show promise for electrochemical CO2 reduction (CO2RR) to acetate, but their efficiency is limited by the difficulty in generating the CO intermediate needed for C–C coupling. While co-catalysts can enhance CO generation, weak interaction between co-catalytic and single-atom Cu sites hinders CO spillover, resulting in low acetate yield. Herein, we design atomic Cu–Ag pairs

This study presents a generic method to selectively enhance radiative pathways over non-radiative states by leveraging vibrational coupling between the host lattice and mid-gap states of doped transition metal ions. While previously demonstrated with Mn, this work successfully incorporates Ni2+ ions into CsPbCl3 perovskite nanocrystals (NCs), showcasing the method's versatility and tunability for radiative

Traditional aptasensors struggle to distinguish molecules with highly similar chemical structures due to the inherent flexibility of aptamers, which form 'nano-bushes' causing non-specific adsorption and reducing sensor specificity. To address this, we propose a novel strategy of anchoring aptamers at the single-molecule level onto atomic anchoring sites. We have designed a gold single-atom/titanium

Ullmann coupling has been one of the most important organic reactions for the formation of aryl–aryl bond, which is of great significance in medicinal chemistry, natural product synthesis, and optoelectronic material fabrication. However, the associated reaction mechanism has not been known with certainty and mostly relied on theoretical calculations, since the identification of reaction intermediates

Polymer-based organic room-temperature phosphorescent (ORTP) materials have advantages such as low cost, abundant resources and ease of processing, rendering them highly suitable for real-world applications. However, the trade-off between the phosphorescent quantum yield (phos.) and phosphorescent lifetime (phos.) highlights the challenge for the development of efficient ORTP materials. Here, a synergistic

Electrosynthesis of carbon monoxide (CO) from carbon dioxide (CO2) and water driven by renewable electricity represents a sustainable route to carbon upgrading, but the lack of cost-effective catalyst hinders its scaling-up. Here, we judiciously designed bimetallic Cu-In catalyst via in situ electroreduction of In-coated CuO nanowires. This facilely-prepared Cu-In catalyst delivers an excellent performance

Developing platinum-based electrocatalysts with high CO tolerance for methanol oxidation reaction (MOR) is crucial for the practical application of direct methanol fuel cells (DMFCs). Herein, we employed a straightforward one-step method to synthesize PtxCuy network nanowires (NWNs), which exhibit the advantages of structural stability and bimetallic ensembles. The synergistic effect of compressive

Layer manganese dioxide with special structure, low price and large theoretical specific capacitance/capacity is considered as a competitive candidate for various energy conversion and storage devices, such as supercapacitors, Li-ion, Na-ion, Zn-ion, etc. batteries. However, challenges such as low electronic/ionic conductivity, sluggish diffusion kinetics, and structural collapse during cycling are

Lithium metal batteries are regarded as promising energy storage devices due to their high theoretical capacity, low density, and low electrode potential. However, the high reactivity of lithium leads to side reactions with the electrolyte and dendritic growth which hinder their commercial application. In this study, a lithium metal anode material with a three-dimensional nanostructured interface was

The direct forge linkages between commercially available electrophiles are the powerful synthetic tools to the chemical bond construction. This strategy could eliminate the pre-synthesis of reactive organometallic reagents in couplings with electrophiles, thus providing the efficient, easily-handled and step-economical routes in organic synthesis. The reported approaches are mainly utilized in carbon-carbon

The present article reports on a new and efficient synthetic strategy towards tetracene-bipyridiniums. On the basis of extensive experimental analyses supported by calculations and DFT simulations, we report the first observation of a mixed valence complex formed in solution under standard conditions from an unconstrained bis-viologene derivative.

The formation of exposed active sites that have high activity and stability for oxygen evolution reaction (OER) catalysts is a significant opportunity for improving water electrolyzers. Low-index facets surface Ru can achieve both high activity and stability for OER. Here, we present a new catalyst design where low-index faceted Ru branches are grown off the corners of Pt nanocubes, forming open Ru

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

High-temperature X-ray detection holds promise potential in practical application with the development of industries. Organic-inorganic manganese-based halide (OIMH) scintillators have aroused a research upsurge due to their high X-ray attenuation ability, low preparation cost, outstanding photoluminescence performance, and flexible structures. However, the thermal quenching effects of OIMH materials

Spin conversion in molecular excited states is crucial for the development of next-generation optoelectronic devices. However, optimizing molecular structures for rapid spin conversion has relied on time-consuming experimental trial-and-error, which limits the elucidation of the structure-property relationships. Here, we report a Bayesian molecular optimization approach that accelerates virtual screening

Azobenzene (AZO) and its derivatives are of great importance in dyestuff and pharmaceutical industry, but their sustainable synthesis is seriously slower than expected due to the lack of high-performance catalysts. In this work, we reported a robust yet highly efficient catalyst of PdS mesoporous nanospheres (MNSs) with confined mesostructure and binary elemental composition that achieved sustainable

Water scarcity emerges as a critical global challenge, with the purity of aquatic ecosystems intimately linked to ammonium concentrations. The removal of ammonium ions (NH₄⁺) is vital for mitigating ammonium contamination and promoting the sustainability of nitrogenous resources. Capacitive deionization (CDI) utilizing organic electrodes offers a promising electrochemical solution through a unique

A potassium tert-butoxide (KOt-Bu)-mediated Mannich reaction between α-substituted-γ-lactams and N-silyl imines is reported. N-silyl imines are generated in situ from readily available aryl nitriles and directly combined with the lactams, without preformation of the lactam enolate, to afford the α-quaternary center-bearing Mannich bases in high yield and with high diastereoselectivity (24 examples)

The equilibrium dissociation constant (Kd) is a quantitative measure of the strength with which a drug binds to its receptor. Methods for determining Kd typically require a priori knowledge of protein concentration or mass. We report a simple dilution method for estimation of Kd using native mass spectrometry which can be applied to protein-ligand complexes involving proteins of unknown concentration

This perspective begins with the discovery of the Grignard reaction by a graduate student in the last years of the 19th century, before describing why it has remained largely unexplained for more than a century. From the summary of what has been achieved, focusing on the computational aspects, it is now clear that further studies of the chemistry of any chemical species that is highly sensitive to

Treatment of 2-(pyrazol-1-yl)-6-fluoropyridine with one equiv of the appropriate 4-substituted 1H-pyrazole in the presence of sodium hydride gives moderate yields of 2-(pyrazol-1-yl)-6-(4-methylpyrazol-1-yl)pyridine (LMe), 2-(pyrazol-1-yl)-6-(4-fluoropyrazol-1-yl)pyridine (LF), 2-(pyrazol-1-yl)-6-(4-chloropyrazol-1-yl)pyridine (LCl) and 2-(pyrazol-1-yl)-6-(4-bromopyrazol-1-yl)pyridine (LBr). Single

Prussian blue analogues (PBAs) are widely recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, many unqualified PBAs with unsatisfactory electrochemical performance are difficult to dispose of and pose a risk of environmental contamination. Additionally, the production process of layered oxides, another popular cathode material for SIBs, requires prolonged

A novel approach to the synthesis of the 2-thiabicyclo[2.1.1]hexane scaffold has been described. The method utilizes two highly reactive species: bicycle[1.1.0]butanes (BCBs) and thioketones. Their high reactivity enabled the formation of the desired product to occur under ambient conditions, without the need for catalysts, additives or light irradiation. To the best of our knowledge, this is the first

Understanding the interactions between metal-based nanoparticles and biological systems in complex environments (e.g., the human body, soils, and marine settings) remains challenging, especially at the single-cell and nanoscale levels. Capturing the dynamics of these interactions, such as metal distribution, nanoparticle growth, or degradation, in their native state (in vivo) is particularly difficult

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