Themed collection 2024 Chemical Science Covers

The comparison of homologous hydrogenases, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues that are remote from the active site may have a great influence on catalytic properties.

While chemistry has a role as the central science, other sciences are also central to solving the problems that lie ahead. To be more effective in this endeavor, we need to connect disciplines and break down the silos that artificially separate them.

Advances in bioorthogonal polyoxometalate (POM) chemistry will open exciting opportunities for the controlled use of stimuli-responsive POM-based organic–inorganic nanoassemblies in biomedical applications as well as catalysis and electronics.

This perspective focuses on the latest understanding of the folding-promotion mechanisms by chaperones and oxidoreductases and recent progress in the development of chemical mimics that possess activities comparable to enzymes.

We summarize the challenges to design and synthesize self-assembled molecules, discussing their synthetic routes and structural features in relationship to the efficiency of perovskite-based solar cells where they are applied as selective contacts.

The current amyloid hypothesis does not capture the full complexity of Aβ aggregation. Here we lay out a supersaturation framework to better understand the molecular mechanism of Alzheimer’s disease and to develop more effective treatment strategies.

Adamantane-type clusters exhibit a huge diversity of chemical compositions, structural details, and resulting properties.

Recent advances and present status of 3D-printed micro-batteries with respect to the connection between printable materials and printing techniques, as well as the rational design considerations are summarized.

Fluorescent probes for detecting complex environments in vivo play an important role in self-assembly in vitro.

This review highlights the design and synthesis of water-stable MOFs, as well as their applications in carbon capture.

This review covers the syntheses, functionalization strategies of hollow carbon-based materials, as well as their applications in electrocatalytic and thermocatalytic CO₂ conversion.

BenzoTag, a self-labeling protein developed using molecular evolution, enables wash-free labeling in live cells in seconds using low nanomolar dye concentrations.

The current–voltage characteristics of molecular junctions can be measured with a time resolution two orders of magnitude higher than previous methods, allowing detailed characterization of electronic states during mechanical modulation.

An electron-losing regulation strategy for stripping modulation by adding Oxolane (OL) additives is proposed. According to experimental results, new guidance for designing electrolyte additives is provided.

Phenylene urea, used as an aglet at the N-terminus, facilitates self-assembly. Simple dipeptides with phenylene urea assembled to form autofluorescent polygonal peptide tubes, while bis-urea pseudopeptides formed autofluorescent spherical vesicles.

The cephalosporin antibiotics cefiderocol, ceftazidime and cefepime undergo fragmentation on reaction with penicillin binding protein 3 from Pseudomonas aeruginosa.

Helically chiral MR-TADF compounds tBuPh-BN and DPA-tBuPh-BN show narrowband circularly polarized luminescence that translates into high-performance hyperfluorescent organic light-emitting diodes.

We present a supramolecular assembly of cucurbituril macrocycles and organomodified gold nanoparticles, referred to as “suprazyme”, with catalytic activity surpassing its components by over 50 times in a model oximation reaction.

In this work, molecular dynamics simulation with metadynamics is performed to understand the relationship between lanthanide ion solvation energetics and separation performance.

A fine-tuned reverse topological approach is developed for structure prediction and 94 823 precision-engineered metal–organic frameworks are designed.

We unveil a clear link between cation structural-disorder in the tetrahedral sites of fcc-structured superconducting A₃C₆₀ fullerides and their electronic properties as manifested by a reduction of the superconducting transition temperature, T_c.

Molecular solar thermal energy storage route using teralylenes with pyridine protonatable moieties for on-demand energy release achieved upon protonation with catalytic amounts of acid.

A hydrogen bonding cage effectively recognizes anions in water and catalyzes the oxidation of oxalate.

A bottom-up investigation strategy for eumelanin's structure–property relationship by a multidisciplinary approach, using 3D electron diffraction, solid-state NMR, density functional theory and electronic spectroscopy.

Highly efficient water splitting under visible light was achieved using Ir, Sb, and Al-codoped SrTiO₃ of a single particulate photocatalyst by a solid-state reaction followed by flux treatment using SrCl₂ and loading of a RhCrO_x cocatalyst.

Photocyclisation reactions offer a convenient and versatile method for constructing complex polycyclic scaffolds, particularly in the synthesis of natural products.

Symmetry-breaking approach exceeds the sensitivity of the vibrational Stark effect. Nitrile groups report on microscopic electric fields without interference from hydrogen-bonding interactions.

Computations were used to model the rearrangement of the barbaralyl cation, a structure that demonstrates nonclassical bridging, homoconjugation, fluxionality, non-statistical dynamic effects, post-transition state bifurcations, and tunneling!

Per-residue analysis of the thermodynamics of unfolding of β-hairpins provides insight into the non-covalent interactions between residues, and the individual contributions of residues and secondary structure type to the ΔH, ΔS, and ΔC_p of unfolding.

Naphthalenyl- and anthracenylpyridine cyclometalating ligands bind to Pt in different ways, which can be used to tune their emissive properties.

Mitochondrial-targeted protein degradation (mitoTPD) is explored using small-molecule degraders that leverage a mitochondria-localized protease. This approach restored mitochondrial morphology and shows potential for drug discovery.

Rearrangements of a bullvalene cage between constitutional isomers are directed by configurational isomerization of a pendant group through noncovalent interactions.

Population-weighted principal moments of inertia and exit vectors analyses of shapeshifting bullvalenes reveals the diversity in their 3D structures.

Cu(I) sites enhance their activity upon coordination with oxygen-donor ligands, as demonstrated by infrared photodissociation spectroscopy and ab initio calculations.

We zoomed in on the SARS-CoV-2 interaction layers in open and closed states, revealing a protein–solvent–glycan polarization network supporting the open state. Besides, we showed that the glycan shield maintains viral camouflage in both states.

Nucleic acids with hypermodified nucleosides perform stereoselective RNA/DNA-mediated peptide coupling, followed by thermal release of the peptide, leading to temperature-driven one-pot cycles with gradual homochiral L-peptide enrichment.

Featuring mostly nucleophilic but also electrophilic properties, phosphorus-bridged bicyclic germylenes require steric shielding to be protected from decomposition. The two nucleophilic sites, Ge and P, show competing reactivity.

Macrocyclic bis-diphosphenes, formally heavier derivatives of macrocyclic azobenzenes, are accessed for the first time.

Energy transfer barriers through affordable calculations. Density functional theory is shown to be a reliable tool to compute barriers between relatively large systems through the application of the classical formulation of the Marcus theory.

A new method for analyzing crystal structures of molecules distorted from their regular shape separates atom movements into symmetry modes so that molecular conformation of functional materials can be quantified and compared easily across databases.

Vacuum ultraviolet excitation of CO₂ clusters and concomitant energy transfer to naphthalene leads to ionization which provides an understanding of excited state chemistry relevant to astrochemistry.

High-throughput experimentation and computational chemistry were used to build machine learning models for Rh-catalyzed asymmetric olefin hydrogenation, identifying numerous factors affecting the accuracy of selectivity and reactivity predictions.

An aryne intermediate is generated upon mechanical dissociation of a benzocyclobutene mechanophore. Such force-generated reactive species could be used in materials and synthesis.

High-throughput calculations show 11 flow directions from *CO to *CHO on DACs. The catalyst disrupting the linear adsorption relationship is linked to multiple, not just one, flow direction.

Development of an innovative chalcogenide transfer vehicle for improving large scale aqueous quantum dot synthesis.

Machine learning potentials combined with enhanced sampling methods and grand-canonical Monte Carlo simulations allow for accurate modeling of CO₂ sorption into condensed-phase amines, highlighting the impact of proton transfer and solvent dynamics.

A promiscuous protein binder with redox activity efficiently promotes oxidative protein folding under condensed sub-millimolar conditions.

This study explores the mechanisms of photoactivation and radical formation during 3D laser printing using photoresists with a DETC photoinitiator. The role of DETC in high triplet states during radical polymerization is revealed.

Neat ITIC films are found to facilitate charge transfer, dissociation, and free carrier formation without the need for donor layers. This process, driven by V-type molecular stacking, significantly boosts organic photovoltaic efficiency.

X-ray absorption spectroscopy and variable temperature magnetometry show evidence of 4f-orbital mixing in Cp′₃Eu, which increases its magnetic susceptibility.

A methylated flufenamic acid gave two different polymorphs, mechanically deformable α form and fragile γ form. We successfully obtained the “intrinsically brittle” bent γ crystal by vapor-induced phase transition from the bent α crystal.

This work unlocks an opportunity to rapidly construct fused heterocyclic cations for efficient screening of single-molecular white-light-emitting materials and pure red-light-emitting materials.

Unraveling the interfacial structure on aqueous stepped TiO₂ surface by combing electrochemical scanning tunneling microscopy and machine learning accelerated molecular dynamics.

Sphere-shaped amorphous aggregates of Au₈ clusters entrapped within SDS nanoenvelopes are transformed into rhombic single nanocrystals upon simple sonication in solution, where the aggregation-induced emission (AIE) from Au₈ is notably enhanced.

A conformation engineering strategy is proposed to manipulate the crystal structure of electron deficient heteroarenes for superior n-type organic semiconductors with an electron mobility of 3.5 cm² V⁻¹ s⁻¹.

Covalent DFOB-DOTA dual chelator (‘D2’) binds ⁸⁹Zr (DFOB) and ¹⁷⁷Lu (DOTA) regio-selectively enabling ⁸⁹Zr–¹⁷⁷Lu pairing as a novel cancer-targeting theranostic.

Enantiopure [7]helicenes were utilized as molecular wrenches at the terminal K-regions of the conjugated pyrene nanoribbon to achieve a 99.9% conformational population of a single-handed helical ribbon with an end-to-end twist of 171°.

PYTA is demonstrated to rapidly and stably complex ²²⁵Ac, ¹⁷⁷Lu, ¹¹¹In, and ⁴⁴Sc, a “superfecta” of complementary but chemically distinct radiometals for targeted theranostic applications.

This work presents a direct site-selective oxygen–sulfur substitution method that enables transforming polyoxometalates [XW₁₂O₄₀]⁴⁻ (X = Si, Ge) to Keggin-type polyoxothiometalates [XW₁₂O₂₈S₁₂]⁴⁻ using sulfurizing reagents in an organic solvent.

Multi-cavity discrete coordination cages (MCDCC) are prepared by mixing Pd(II) with designer bis- and tris-monodentate ligands in a 5 : 4 : 4 ratio. Two trinuclear sub-frameworks are conjoined in the molecular architecture of the ensuing MCDCC.

A novel peptidic bispecific antibody (pBsAb) is developed by integrating EGFR-binding cyclic peptide with an anti-SIRP-α antibody, promotes cancer cells recognition, suppresses "don't eat me" signal, and enhances phagocytosis and tumour infiltration.

[Ni(bpy)₃]²⁺ soft landed on surfaces dissociates spontaneously. Codeposition of stable anions with cations enables preservation of the structure of [Ni(bpy)₃]²⁺.

A water-soluble, cell-permeable, turn-on Mn²⁺ sensor visualizes Mn²⁺ dynamics live and provides an estimate for endogenous labile Mn²⁺ in a living mammalian cell.

We introduce planarity breaking as a new design strategy for controlled supramolecular polymerization.

Fast room-temperature phosphorescence with high quantum yields up to 38% in solution from metal-free organic 1,2-diketones is reported, along with the mechanism and molecular design principles governing the fast phosphorescence.

Advanced vacuum temperature-programmed desorption up to 1600 °C can be used for precise quantification and chemical speciation of nitrogen species in perovskite-type oxides at the bulk level, complementing the surface-sensitive XPS techniques.

Carbon–carbon (C–C) bond formation is a cornerstone of synthetic chemistry, relying on routes such as transition-metal mediated cross-coupling for the introduction of new carbon-based functionality.

AIxFuse learns to fuse pharmacophores to generate potential dual-target drugs through collaborative learning by Monte Carlo tree search and machine learning.

The high nuclearity cubane-assembled Mn-oxo clusters serve as effective precursors for the preparation of monodispersed Mn₃O₄ nanocrystals through the colloidal chemistry approach.