Themed collection 2023 Chemical Science HOT Article Collection

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 critical task of activating and cleaving inert C–C bonds during plastic upcycling and recycling holds substantial importance.

This perspective focuses on strategies to manipulate and optimize three key determinants of metal-based molecular photosensitizers – the absorption profile, the excited-state redox potentials, and the excited-state lifetime.

We describe our efforts to develop a decatungstate (DT)-catalyzed C–H ¹⁸F- and ¹⁹F-fluorination reaction, and the discovery and exploitation of electrostatic effects in DT catalysis for the synthesis of radiotracers for PET imaging.

We provide an overview of coordination cage catalysis, highlighting how mechanistic understanding can help address the challenges in this area leading to new opportunities in non-covalent reactivity.

Advances in molecular electronic ferroelectrics are summarized. In addition, electronic pyroelectrics using electron transfer is introduced as a promising alternative in the development of polarization switching materials.

The quest for generating novel chemistry knowledge is critical in scientific advancement, and machine learning (ML) has emerged as an asset in this pursuit.

This perspective highlights recent advances and challenges in transition-metal (oxy)nitrides, which are promising photocatalysts for overall water splitting, and discusses opportunities to upgrade the solar-to-hydrogen energy conversion efficiency.

Using core/shell based perovskite materials is a promising strategy to stabilize perovskite nanocrystal phases and passivate the surface, in order to improve both the stability and the optical properties of the material and in turn of light emitting diodes.

Targeted protein degradation strategies employing proteins as binders for degradation targets.

Hydride transfer (HT) is a fundamental step in a wide range of reaction pathways, including those mediated by dihydropyridinates (DHP⁻s).

By drawing inspiration from photoredox catalysis, the field of radical-mediated alkane functionalization has made remarkable advancements recently to address the challenges of today and future.

This perspective article highlights redox catalysis of organic molecules via photoinduced electron transfer, which is well exploited for the important photoredox reactions including hydrogen evolution, water oxidation and synthetic applications.

The activity of Ni–Mo catalysts for the hydrogen evolution reaction originates from the interfaces of alloy–oxide or alloy–hydroxide, in which the oxide or hydroxide promotes water dissociation and the alloy accelerates hydrogen combination.

Synchrotron radiation enables probing a wide range of length scales operando, hence being a powerful tool in battery research. Challenges ahead involve cell design (especially for multi-modal approaches) and protocols for automated data analysis.

By taking inspiration from the structures and reactivities of its past, organolanthanide chemistry has managed to reinvent itself for the challenges of today and the future.

Organo-functionalisation of polyoxometalates with peptide moieties is an effective approach to obtain diverse arrays of functional hybrid materials, where each component influences the resulting change, surface chemistry, polarity, and redox properties.

This review article highlights the diverse ways in which recent developments in the areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

We discuss the current state-of-the-art in exploiting fluorescence-based techniques for analysing polymer systems and soft matter materials, as well as provide an outlook on future opportunities and challenges.

This review comprehensively summarizes the key features of existing liquid electrolyte formulations for Si and Li metal anodes and proposes design rules for advanced liquid electrolyte chemistry.

The combination of molecular imprinting approaches and nanomaterials has recently emerged in new approaches for the imprinting of nanomaterials. This review summarizes the latest studies and the potential implications and applications of this field.

This review covers recent progress in tyrosine-selective cleavage, functionalization, and conjugation of peptides and proteins. Key applications of Tyr modification are highlighted, demonstrating its great potential for chemistry and biology.

This work reviewed recent advances in the design, fabrication, and responsiveness of permeable polymersomes, and their diverse applications in the fields of biomimetic nanoreactors, artificial cells and organelles, as well as nanomedicine were highlighted.

This review provides a multidisciplinary overview of the challenges and opportunities for dynamic covalent chemistry-based macromolecules towards the design of new, sustainable, and recyclable materials for a circular economy.

A primer that covers the discovery and validation process for novel aptamers and highlights recent applications of aptamers in biosensing and cell separations.

This review explores the benefits of flow chemistry and dispels the notion that it is a mysterious “black box”, demonstrating how it can push the boundaries of organic synthesis through the understanding of its governing principles.

This work reviewed the new progress of conductive hydrogels in the application of tissue repair and provided a useful reference for further preparation of safer and more efficient conductive hydrogels for tissue engineering.

This review provides the recent progress in the application of inorganic-based biomaterials for rapid hemostasis and wound healing, including preparation methods, material systems, intrinsic mechanisms and biofunctions.

Harnessing knowledge from crystal structures yields a model that can predict a variety of chemistry-relevant outcomes.

¹⁹F NMR analysis of ion-pairing and reaction kinetics shows that TBAT can act as a genuine surrogate for TBAF, as well as a reservoir for rapidly-reversible release of traces of it, to effect both direct (k_d) and dissociative (k_F) fluoride transfer.

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.

Photo-induced electrochemiluminescence imaging of single cells is reported using an infrared light stimulus.

The all-trans dyad can function as a molecular ruler but complications arise from the cis-configuration.

New methods allow the very smooth synthesis of highly pure MUC5AC glycopeptides containing 20 GalNAc units on 10 tandem repeats within a week.

A series of heptamethine–oxonol dyes featuring different heterocyclic end groups were designed with the aim to explore structure–property relationships in π-extended coupled polymethines.

We report upconversion for a rigid tetracene dimer that yields 20× that of a monomer model. This is due to a 30× relative enhancement in TTA, indicating participation by intramolecular multiexciton states, including the ⁵TT, in productive channels.

Chemists heavily rely on visual cues for routine tasks. Here, we introduce a computer vision system to automatically monitor and control diverse workup processes based on visual aspects, advancing toward autonomous operations.

This work demonstrates a novel strategy to address the notorious ACQ of non-AIE type fluorophores in an aqueous medium through deep insights into the structural effects leading to anti-ACQ properties, which could benefit the potential applications.

0D hybrid indium halide exhibits near-unity PLQY and negligible self-absorption realizing multiple cutting-edge optoelectronic applications in high-performance white LED, X-ray scintillation and reversible fluorescent probe toward tribromomethane.

Fine-tuned GPT-3 shows robust performance for the prediction of electronic and functional properties for organic molecules, with resilience to information loss and noise.

Two synthesized Gd₆Cu₂₄ clusters—Gd₆Cu₂₄-IM and Gd₆Cu₂₄-AC—exhibit excellent electrocatalytic water oxidation activity in an aqueous solution of a weak acid (pH = 6) and had turnover frequencies of 319 and 169 s⁻¹ at 1.70 V, respectively.

Atomistic simulations explain recent experimental findings of dielectric polarization suppression in confined water, revealing it originates in an anti-ferroelectric order driven by spontaneous antiparallel alignment of water dipoles at surfaces.

One-electron oxidation of a chloranil dianion (CA²⁻) to its radical form (CA˙⁻) disrupts the local solvation structure formed by ethanol in acetonitrile, resulting in a large entropy change and a large Seebeck coefficient of CA^2−/˙⁻ thermocells.

Ketones are ubiquitous motifs in the realm of pharmaceuticals and natural products.

Simple iron salts are able to photocatalyze the diazidation, dichlorination, and fluorochlorination of alkenes via the merger of ligand-to-metal charge transfer (LMCT) and either radical ligand transfer (RLT) or fluorine atom transfer (FAT).

A nonenzymatic reaction converting pyruvate to phosphoenolpyruvate (PEP) is shown to proceed through carboxylate phosphorylation, suggesting that only a single phosphorylation mechanism was needed to initiate metabolic networks.

Directional Mn dopant migration (outward/inward) was achieved by inserting a CdZnS “atomic trap” with a small size mismatch with dopants in core/multi-shell QDs. A larger initial substitutional site allows for active trapping and dopant migration.

Anionic forms of a macrocyclic cyclophane were crystallized by treating the neutral hydrocarbon with alkali metals (Li, Na and K). The di-anions show decreased bond-length alternation, consistent with global aromaticity, whereas the anti-aromatic tetra-anion has a low-symmetry geometry.

The homologation of boronic acids with diazoalkanes obtained by photochemical decomposition of N-tosylhydrazones leads to substituted benzylboronates, previously unavailable under thermal conditions. Batch and continuous flow reactions are described.

Intramolecular phosphine-stabilized tetra-coordinated Ge(IV) di-cations are established. Dispersed charges lead to Si–H activation initially at the P-site, which ultimately migrates to the Ge-site due to geometric constraint empowered Lewis acidity.

Non-linear threshold analysis enabled discovery of a highly soluble (1.3 M) bipyrimidine anolyte. Stable cycling in a full flow battery cell for 75 cycles.

Excited state evolution of the rhodium(III) complex [Rh(III)(phen)₂(NH₃)₂]²⁺ (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states.

Substituted pyridazinediones (PDs) enable reversible and tuneable cysteine modification with exemplification on peptides, proteins and hydrogels.

The development of a one-pot method to tune the primary chain dispersity in polymer networks and the notable effect of primary chain dispersity on gel degradation.

We report a holistic study of the isolation, structure elucidation, total syntheses, and biological evaluation of three unprecedented sesterterpenoids, orientanoids A–C (1–3).

We report the discovery of an ortho regioselective oxidative halodeboronation of N-aryl amides and ureas with wide-ranging applications in pharmaceuticals, materials science, and synthetic organic chemistry.

Net-clipping is a strategy for the topological prediction of MOFs built with reduced-symmetry linkers. It is based on the deconstruction of nets by clipping half of the connectivity in tetrahedral, hexagonal, cubic or hexagonal prismatic nodes.

Anisotropic thermal diffusivity correlates with the intermolecular interactions in two cocrystals with varying halogen acceptor abilities, which also influenced the superelastic and ferroelastic behaviour.

A melamine-based glucoside, MG-C11, has the ability to form a dynamic hydrogen-bonding network between detergent molecules, responsible for the markedly enhanced efficacy for GPCR stabilization compared to LMNG and previously developed TTG-C11.

Herein, we report the dicarbofunctionalization of enol silyl ethers via an Fe-catalyzed decoupled cross-coupling of (fluoro)alkyl halides, and enol silyl ethers.

Small molecule degraders and stabilizers of squalene synthase based on the same scaffold are reported, which respectively accelerate or block its natural degradation.

We develop a platform for recyclable polyurethane-based thermosets fabricated by photopolymerization. Tunable mechanical properties and 3D printing are demonstrated, with mild acid-catalyzed degradation enabled by hemiacetal linkages.

Minimal models of cages are used to map the accessible cage topologies based on building block properties.

We show that radical migration in a heme peroxidase can be controlled and directed to a rationally designed site through simply removing an oxygen atom form the protein structure.

A long range π-conjugation has been realized by the designed π–π interactions in phenanthrene/phenanthrene-based molecular crystals, forming the “transannular effect”, which can be amplified by high pressure and induce novel piezoluminescence.

In this work, we describe the engineering of a microbial platform to produce six different C₄ chemicals at near quantitative yields using a combination of metabolic engineering and directed evolution.

A novel method termed cell surface engineering coupling biomembrane fusion based on metal organic layers was developed for dynamic membrane proteome profiling.

M₆L₁₂ nanospheres, with isolated gold sites fixed on the windows, were utilized as an example to prove that the cage windows present a confinement effect for substrate pre-organization and transition state stabilization leading to high rates.

Structural distortion of the secondary coordination sphere driven by the incorporation of an alkali metal in Ce³⁺ imidophosphorane complexes tunes the Ce^3+/4+ oxidation potential.

A general design strategy for photo-triggered release of acyl radicals was developed. With an acetyl radical donor, we showed the potential of acyl radicals to precisely modulate cell redox homeostasis, to promote NSC differentiation, and to improve the cognitive abilities of early AD mice.