Themed collection 2024 ChemSci Pick of the Week Collection
Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis
O2 is an attractive oxidant but it is also kinetically inert which limits its use in synthetic transformations. Metal–ligand cooperativity is a promising biomimetic strategy to activate O2 for oxidative reactivity and catalysis.
Chem. Sci., 2024,15, 16409-16423
https://doi.org/10.1039/D4SC03896G
Opportunities and challenges for plastic depolymerization by biomimetic catalysis
This perspective highlights the challenges and opportunities in achieving sustainable plastic recycling under mild conditions by imitating the active sites and the substrate-binding clefts of enzymes.
Chem. Sci., 2024,15, 6200-6217
https://doi.org/10.1039/D4SC00070F
Revisiting poly(vinyl chloride) reactivity in the context of chemical recycling
An overview of PVC functionalization through the lens of chemical recycling.
Chem. Sci., 2024,15, 5802-5813
https://doi.org/10.1039/D3SC06758K
Hybrid and composite materials of organic crystals
Combining organic crystals and polymers results in a new class of all-organic, lightweight, flexible materials with unprecedented mechanical robustness, resilience, and diversity in combination with other functional materials.
Chem. Sci., 2024,15, 2684-2696
https://doi.org/10.1039/D3SC06469G
Chiral ionic organic single-crystal and its exfoliated two-dimensional nanosheets with enhanced enantioseparation
Chiral ionic organic single-crystal (CIOC) were prepared for the first time via ionic self-assembly using organic anions and cations. Interestingly, the CIOC can be ultrasonically exfoliated to 2D nanosheets and exhibit enhanced enantioseparation.
Chem. Sci., 2024, Advance Article
https://doi.org/10.1039/D4SC04990J
Exploring efficient and air-stable d2 Re(V) alkylidyne catalysts: toward room temperature alkyne metathesis
We report the first non-d0 Re(V) alkylidyne complex capable of effecting alkyne metathesis at room temperature, featuring air/moisture stability, broad functional group compatibility, and scalable synthesis.
Chem. Sci., 2024, Advance Article
https://doi.org/10.1039/D4SC05369A
Automated electrosynthesis reaction mining with multimodal large language models (MLLMs)
Leveraging multimodal large language models (MLLMs) to process multimodal data inputs and complex inter-modality data dependencies for automated (electro)chemical data mining from scientific literature.
Chem. Sci., 2024, Advance Article
https://doi.org/10.1039/D4SC04630G
Acid-sensitive photoswitches: towards catalytic on-demand release of stored light energy
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.
Chem. Sci., 2024,15, 16034-16039
https://doi.org/10.1039/D4SC04973J
Conjugated polymers of an oxa[5]helicene-derived polycyclic heteroaromatic: tailoring energy levels and compatibility for high-performance perovskite solar cells
Alternating copolymerization of a helical polycyclic heteroaromatic with another conjugated unit possessing different electronic characteristics tuned the energy levels and the compatibility with organic salts.
Chem. Sci., 2024,15, 15263-15273
https://doi.org/10.1039/D4SC04244A
π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes
Naphthalenyl- and anthracenylpyridine cyclometalating ligands bind to Pt in different ways, which can be used to tune their emissive properties.
Chem. Sci., 2024,15, 14644-14650
https://doi.org/10.1039/D4SC04799K
Direct evidence for ligand-enhanced activity of Cu(I) sites
Cu(I) sites enhance their activity upon coordination with oxygen-donor ligands, as demonstrated by infrared photodissociation spectroscopy and ab initio calculations.
Chem. Sci., 2024,15, 14635-14643
https://doi.org/10.1039/D4SC04582C
Computational insights into aqueous speciation of metal-oxide nanoclusters: an in-depth study of the Keggin phosphomolybdate
Herein, we present a new computational methodology that unlocks the prediction of the complex multi-species multi-equilibria processes involved in the formation of complex metal-oxo nanoclusters.
Chem. Sci., 2024,15, 14218-14227
https://doi.org/10.1039/D4SC03282A
In situ electrosynthesis of quinone-based redox-active molecules coupling with high-purity hydrogen production
The asymmetric electrolysis cell concept was introduced to simultaneously produce quinone-based redox-active molecules and high-purity hydrogen gas.
Chem. Sci., 2024,15, 13185-13190
https://doi.org/10.1039/D4SC03033H
Two- and three-photon processes during photopolymerization in 3D laser printing
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.
Chem. Sci., 2024,15, 12695-12709
https://doi.org/10.1039/D4SC03527E
Exploring the influence of H-bonding and ligand constraints on thiolate ligated non-heme iron mediated dioxygen activation
The kinetics study herein experimentally demonstrates that an inner-sphere ET mechanism is involved in the conversion of triplet O2 into a powerful oxidant by an RS–Fe complex. Hydrogen-bond donors are shown to destabilize the transition-state.
Chem. Sci., 2024,15, 12710-12720
https://doi.org/10.1039/D4SC02787F
Dynamically blocking leakage current in molecular tunneling junctions
Incorporating mixed flexible-rigid backbones into molecular junctions can dynamically block tunneling currents and enhance rectification.
Chem. Sci., 2024,15, 12721-12731
https://doi.org/10.1039/D4SC02829E
4f-Orbital mixing increases the magnetic susceptibility of Cp′3Eu
X-ray absorption spectroscopy and variable temperature magnetometry show evidence of 4f-orbital mixing in Cp′3Eu, which increases its magnetic susceptibility.
Chem. Sci., 2024,15, 12667-12675
https://doi.org/10.1039/D4SC01300J
Synthesis of polyoxothiometalates through site-selective post-editing sulfurization of polyoxometalates
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.
Chem. Sci., 2024,15, 11267-11271
https://doi.org/10.1039/D4SC02912G
A general graph neural network based implicit solvation model for organic molecules in water
Novel approach combining graph neural network and the physically motivated functional form of an implicit solvent model enables the description of solvation effects with the accuracy of explicit solvent simulations at a fraction of the time.
Chem. Sci., 2024,15, 10794-10802
https://doi.org/10.1039/D4SC02432J
Nitrogen monoxide and calix[4]pyrrolato aluminate: structural constraint enabled NO dimerization
The dimerization of nitrogen monoxide (NO) is highly relevant in biochemical and environmental redox processes. Here, it is shown how structral constraint and element-ligand cooperativity can steer this reaction.
Chem. Sci., 2024,15, 10803-10809
https://doi.org/10.1039/D4SC02378A
Site-selective S-gem-difluoroallylation of unprotected peptides with 3,3-difluoroallyl sulfonium salts
Bench-stable 3,3-difluoroallyl sulfonium salts proved to be versatile fluoroalkylating reagents for site-selective S-gem-difluoroallylation of cysteine residues in unprotected peptides. The newly added functional groups are poised for ligation.
Chem. Sci., 2024,15, 10002-10009
https://doi.org/10.1039/D4SC02681K
Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion
Neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion with an [M3+–(C6H6)4−–M3+] core electronic structure were synthesized and characterized. They behave as a four-electron reductant to reduce unsaturated substrates.
Chem. Sci., 2024,15, 8740-8749
https://doi.org/10.1039/D4SC02491E
β-Terrecyclene synthase constructs the quadrane backbone in terrecyclic acid biosynthesis
The construction of a quadrane scaffold by β-terrecyclene synthase via Coates' route is demonstrated through mutagenesis and isotopically sensitive branching studies. Subsequent enzymatic modifications convert β-terrecyclene into terrecyclic acid.
Chem. Sci., 2024,15, 8750-8755
https://doi.org/10.1039/D4SC01208A
Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification
A tricyclononene and tricyclononadiene monomer library is studied experimentally and computationally to deepen understanding of structure propagation rate relationships in ROMP. A novel poly(tricyclononadiene) post-ROMP functionalization is explored.
Chem. Sci., 2024,15, 8334-8345
https://doi.org/10.1039/D4SC01986E
A high-resolution structural characterization and physicochemical study of how a peptoid binds to an oncoprotein MDM2
How a peptoid binds to a protein was revealed by a co-crystal structure and systematic physicochemical studies.
Chem. Sci., 2024,15, 7051-7060
https://doi.org/10.1039/D4SC01540A
Thermoswitchable catalysis to inhibit and promote plastic flow in vitrimers
We show that weaker acid catalysis has profound effects on the dynamicity of vinylogous urethane based polymer networks. Moreover, the dynamicity could be adjusted by changing electronic and steric parameters in the catalytic environment.
Chem. Sci., 2024,15, 7061-7071
https://doi.org/10.1039/D4SC00417E
Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene
A bent azide intermediate is key to form 1-azido-1′-nitrenoferrocene from 1,1′-diazidoferrocene, as shown with UV-pump–mid-IR-probe transient absorption spectroscopy and density functional theoryTD-DFT calculations including spin–orbit coupling.
Chem. Sci., 2024,15, 6707-6715
https://doi.org/10.1039/D4SC00883A
High-throughput single-cell mass spectrometry enables metabolic network analysis by resolving phospholipid CC isomers
A high-throughput single-cell MS platform that can perform both lipid profiling and unsaturated lipid CC location isomer resolution analysis was developed, which can be effectively used for in-depth structural lipid metabolism network analysis.
Chem. Sci., 2024,15, 6314-6320
https://doi.org/10.1039/D3SC06573A
Streamlining the automated discovery of porous organic cages
Efficiently merging low-cost high-throughput screening and characterisation, automated data analysis, computational modelling, and cagey – a custom database analysis tool, enhances large-scale data curation and accelerates discovery of organic cages.
Chem. Sci., 2024,15, 6331-6348
https://doi.org/10.1039/D3SC06133G
Electronic isomerism in a heterometallic nickel–iron–sulfur cluster models substrate binding and cyanide inhibition of carbon monoxide dehydrogenase
A protein-based model of carbon monoxide dehydrogenase displays distinct X-ray absorption, EPR, and vibrational signatures upon CO and CN− binding that support ligand-dependent electronic rearrangement throughout the nickel–iron–sulfur core.
Chem. Sci., 2024,15, 5916-5928
https://doi.org/10.1039/D4SC00023D
Oxidation-induced ambiphilicity triggers N–N bond formation and dinitrogen release in octahedral terminal molybdenum(V) nitrido complexes
N–N bond formation in octahedral, terminal d1 Mo(V) nitridos to give μ-dinitrogen complexes requires one eletron oxidation with 0.5 equivalents of oxidant to open a kinetically feasible ambiphilic nitrido coupling pathway.
Chem. Sci., 2024,15, 5152-5162
https://doi.org/10.1039/D4SC00090K
Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset
Simulations reveal that both charge and exciton delocalisation can significantly improve the efficiency of charge generation in organic photovoltaics and explain the failure of classical hopping approaches.
Chem. Sci., 2024,15, 4779-4789
https://doi.org/10.1039/D3SC05409H
A covalent organic framework as a dual-active-center cathode for a high-performance aqueous zinc-ion battery
We designed a covalent organic framework (TA-PTO-COF) as a dual-active-center cathode. This work presents a promising organic cathode material for a high-performance aqueous zinc-ion battery.
Chem. Sci., 2024,15, 4341-4348
https://doi.org/10.1039/D3SC07013A
Photoswitchable imines: aryliminopyrazoles quantitatively convert to long-lived Z-isomers with visible light
Simple structural modifications significantly boost the photochromic performance of imine-based photoswitches. This work lays a foundation for exploring new motifs in light-addressable dynamic combinatorial chemistry.
Chem. Sci., 2024,15, 3872-3878
https://doi.org/10.1039/D3SC05841G
Iron(IV) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N2
Silylation of iron-alkyl-dinitrogen complexes gives high-spin iron(IV) products that also have an iron(II) resonance structure. The stability and reactivity of these compounds depends on the alkyl group, with insertion and homolysis observed.
Chem. Sci., 2024,15, 3485-3494
https://doi.org/10.1039/D3SC05939A
Busting the myth of spontaneous formation of H2O2 at the air–water interface: contributions of the liquid–solid interface and dissolved oxygen exposed
The air–water interface is not the site for H2O2(aq) formation; instead, it takes place at the solid–water interface.
Chem. Sci., 2024,15, 3093-3103
https://doi.org/10.1039/D3SC06534K
PoseBusters: AI-based docking methods fail to generate physically valid poses or generalise to novel sequences
PoseBusters assesses molecular poses using steric and energetic criteria. We find that classical protein-ligand docking tools currently still outperform deep learning-based methods.
Chem. Sci., 2024,15, 3130-3139
https://doi.org/10.1039/D3SC04185A
A scalable synthesis of adjuvanting antigen depots based on metal–organic frameworks
ZIF-8 vaccine enhances the humoral immune response through sustained antigen exposure to the immune system whilst zinc adjuvants the vaccine via inducing T cell activation.
Chem. Sci., 2024,15, 2731-2744
https://doi.org/10.1039/D3SC06734C
Alternatives to fluorinated binders: recyclable copolyester/carbonate electrolytes for high-capacity solid composite cathodes
A series of poly(ester-b-carbonate) electrolytes are prepared by a one-pot procedure and structure–property relationships are observed. The polymer was used as a composite cathode binder with excellent discharge capacity and capacity retention.
Chem. Sci., 2024,15, 2371-2379
https://doi.org/10.1039/D3SC05105F
Designing solvent systems using self-evolving solubility databases and graph neural networks
Our self-evolving graph neural networks for predicting solubilities reconciled different magnitudes of errors and uncertainties of experimental and computational databases, maximizing the database size and the model’s prediction accuracy.
Chem. Sci., 2024,15, 923-939
https://doi.org/10.1039/D3SC03468B
About this collection
In 2018, the Chemical Science Editorial Team launched ‘ChemSci Pick of the Week’ as a means to select and promote our favourite articles from the week and share them with the wider chemical community. This on-going web collection showcases all ChemSci Picks from 2024, which are highlighted on our journal social media pages via the #ChemSciPicks hashtag.