Themed collection 2020 Chemical Science HOT Article Collection

Near-infrared fluorescent molecular probes with improved imaging depth and optimized biodistribution have been reviewed, showing great potential for diagnosis of nephro-urological diseases.

Hydrogen atom transfer from metal hydrides to alkenes appears to underlie widely used catalytic methods – the mechanistic implications are fascinating.

This perspective provides insight into recent electro-organic methods and general trends in this field, and opens up prospects for future viewpoints.

This minireview highlights the recent advances in small molecule activation and catalytic applications of homonuclear dimetallenes, dimetallynes and interconnected bismetallylenes of heavier group 14 elements.

Nickel-catalyzed three-component alkene difunctionalization has rapidly emerged as a powerful tool for forging multiple C–C bonds in a single step.

Materials discovery is a crucial yet experimentally slow and wasteful process. We discuss how discovery can be accelerated by focusing on making predictions that are synthetically realisable.

Adding an external electric field to reactions driven by quantum mechanical tunneling brings a whole new dimension to the idea of switch chemistry.

Complexes of a highly Lewis acidic Mg cation and the full series of Ph–X (X = F, Cl, Br, I) have been structurally characterized. The Mg⋯X–Ph angle decreases with halogen size on account of the growing halogen σ-hole.

Surface enhancement effects in the sensing of anions at redox-active molecular films are investigated in detail and rationalised based on a consideration of the dielectric binding microenvironment.

Peptide sequence can be used to control the self-assembly and structures of nanoscale molybdenum blue polyoxometalate (POM) wheel-shaped clusters.

Herein, we report a new tandem diaza-Cope rearrangement polymerization synthesizing enantiopure polymers with defect-free C–C bond formation. Furthermore, these polymers can be applied as high-performance turn-on Zn²⁺ sensors.

One-pot synthesis of aza[4]helicenes is accomplished through two successive C–H activation/cyclizations, which exhibit on/off fluorescence switching through reversible transformation between helical and planar conformations.

Herein, we report the first room temperature switchable Fe(III) molecular spin crossover (SCO) tunnel junction.

We investigated the mechanism of the magnetic field effect (MFE) on the emission of a luminescent radical doped into host crystals. It was revealed that the spin sublevel population of radical dimers in the ground states is the key that governs the MFE.

A mechanochemistry based approach is proposed to detect and map stress history during dynamic processes.

Machine learning using one class classification on a database of existing co-crystals enables the identification of co-formers which are likely to form stable co-crystals, resulting in the synthesis of two co-crystals of polyaromatic hydrocarbons.

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(II) complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂.

NoSpherA2 brings quantum crystallography to routine structure determination and to the analysis of chemical properties for any class of materials.

Li₃InP₂ exhibits a polyanionic framework of corner-sharing InP₄ tetrahedra and DFT computations reveal the stability trend for indium in the tetragonal structure compared to the orthorhombic structure of the lighter homologues.

A hypoxia-tolerant photosensitizer FBC-based nanoplatform with strong NIR absorbance and ultra-high stability was facilely prepared for PDT of deep tumors.

Single site OH → F substitution at the termini of maltotetraose leads to significantly improved hydrolytic stability towards α-amylase and α-glucosidase relative to the natural compound.

Synthetic polymers consume green light as fuel for intramolecular crosslinking, yielding non-equilibrium single chain nanoparticles that can be light-stabilised, kinetically and chemically trapped, or else unfold in the absence of light fuel.

A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(I) coordination network, giving drastically different host–guest recognition behaviours.

The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated.

An extensive application of cobalt-catalyzed Mukaiyama-type cyclization of γ-hydroxy olefins and a late-stage Stille-type reaction enabled syntheses of four diastereomers of amphirionin-2 to establish its absolute configuration.

A di(o-tolyl)borylgold complex added to CO/N double bond to form Au–C and B–O/N bonds. DFT calculations revealed a two-step mechanism consisting of the coordination of O/N atom to B atom followed by nucleophilic migration of Au atom.

A chemo-enzymatic site-specific fluorination strategy is employed to obtain glyco-nanoparticles with tuneable selectivity towards galectins.

Unusual solute to solvent induced chirality in ROA comes from specific conformer equilibria in the ground and the excited states.

In this work, a series of photochemical reactions were performed on isotopically labelled substrates to explore the validity of Hammond's postulate for the excited state.

An extremely long-lived localised singlet diradical with π-single bonding character is found in a macrocyclic structure that retards the radical–radical coupling reaction by the “stretch and solvent-dynamic effects”.

Chemoselective deamination of adenine in the presence of N⁶-methyladenine using nitrite enables single-nucleotide resolution sequencing of N⁶-adenine methylation sites in DNA and RNA.

Biomimetic cascade hydrogen bonds promote covalent capture of a nucleophile by polarizing the electrophilic reaction site, while suppressing non-productive acid–base chemistry as the competing reaction pathway.

Downstream to alkene hydrosilylation, the opening of the cyclopropane ring in benzyl-substituted VCPs is interlinked with an S_EAr of the aryl group.

Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats.

The application of Electrospray and Electrosonic Spray Ionization Mass Spectrometry (ESI-MS and ESSI-MS) to study accelerated reaction kinetics in droplets is examined using numerical models, new experimental data, and prior literature.

Metal free click reactions used to glycosylate ubiquitin and its mutant A28C afforded two protein scaffolds with high affinity for Burkholderia ambifaria lectin (BambL).

A new mitochondrial uncoupler that forms membrane permeable dimers through interactions of remote acidic and anion receptor groups.

With total scattering methods and stacking fault simulations, we observe previously predicted random local layer offsets in a COF, which are typically disguised by the apparent crystallographic symmetry but strongly influence properties.

A fullerene-based Lewis-basic macrocyclic ligand underwent complexation with alkali-metal ions in 1 : 1 and 1 : 2 fashions, resulting in considerable perturbation to absorption properties as well as the potential surface inside the cage.

An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects.

Catalytically competent titanium-hydrides are reactive and difficult to isolate. We use EPR spectroscopy to define the electronic and geometrical structures as well as dynamics of an open-shell Ti-H active in syndiospecific olefin polymerization.

[Cp*Fe(CO)₂]⁺ facilitates the α-deprotonation of unsaturated C–C bond for propargylic and allylic C–H functionalization. Mechanistic studies reveal insights into the superior performance of the electron-rich and hindered ligand on iron.

Upon light irradiation, multimerized self-assembled caged Two-in-One siRNA nanoparticles (Multi-Chol-siRNA) were collapsed to release trapped siRNAs for multiple RNAi-induced gene silencing activity.

DNA-compatible C(sp³)–H activation reactions of aliphatic carboxylic acids, amides, and ketones were developed for efficient access to DEL synthesis.

Ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold were prepared to evaluate the influence of the central organic linker on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds.

By integrating algebraic topology and deep learning, we provide a reliable ranking of binding affinities, binding site analysis, and fragment decomposition for 137 SARS-CoV-2 main protease inhibitors.

Computational studies reveal near-IR emitting nanohoops and the effect of strain on donor and acceptor units used in conjugated polymers.

The NLRP3 inflammasome regulates production of the pro-inflammatory cytokines interleukin-1β (IL-1β) and IL-18, and contributes to inflammation exacerbating disease.

Calculated conductance through Au_n–S–Bridge–S–Au_n constructs are compared to experimental magnetic exchange coupling parameters in Tp^Cum,MeZn(SQ–Bridge–NN) complexes, where SQ = semiquinone radical and NN = nitronylnitroxide radical.

Covalently grafting C₆₀ molecules onto black phosphorus (BP) nanosheets improves their tumor inhibition rate from 36.6% to 88.2%.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.

A metallic single-molecule magnet was synthesised demonstrating simultaneous metallic conduction and excellent SMM properties at the same temperature range for the first time, with potential applications in molecule-based quantum spintronics.

Photo-oxygenation of β-amyloid (Aβ) has been considered an efficient way to inhibit Aβ aggregation in Alzheimer's disease (AD). We present the first example of Aβ-responsive photodynamic therapy to treatment of AD by using PKNPs self-assemblies.

A combined experimental and theoretical study on the mechanism of the C–F bond activation of C₆F₆ with [Ni(NHC)₂] is provided.

(PBP)Ir pincer complexes containing a boryl-iridium linkage reversibly bind ethylene as an ethylidene bridging B and Ir.

Concise syntheses of spiroviolene and spirograterpene A have been achieved from a common intermediate, indicating a structure revision of one is necessary along with implications for its biosynthesis.

A metal–organic framework/polymer derived catalyst containing single-atom nickel species shows good performance for electroreduction of CO₂ to CO.

In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement for the preparation of a variety of quaternary trifluoromethyl α-ε-amino acids in high yields with excellent enantioselectivities.

A new MCTS variant with a reinforcement learning value network and solvent prediction model proposes shorter synthesis routes with greener solvents.

Visualizing dynamic change in the number of protons during electroreduction of protons in attoliter volume zero-mode waveguides.

Room temperature Rh-catalysed tetradehydro-Diels–Alder reaction via an unusual Rh-stabilised allene.

Force spectroscopy was used to measure the adhesion of Leishmania to synthetic mimics of galectins on the sand fly midgut.

The molecular mechanism of the proteolysis reaction catalyzed by SARS-CoV-2 M^pro, one of the enzymes essential for the replication process of the virus responsible for the COVID-19 pandemic, is described using computational QM/MM methods.

Protecting molecular structures from disclosure against external parties is of great relevance for industrial and private associations, such as pharmaceutical companies.

Foldameric local surface mimetics (LSMs) detect spots at protein surfaces and are promising building blocks in a fragment-centric design of xenobiotic structures and protein–protein interaction inhibitors.

We show that a [Er–Ce–Er] molecular trinuclear coordination compound is a promising platform to implement the three-qubit quantum error correction code protecting against pure dephasing, the most important error in magnetic molecules.

The developed DNA bipedal walker represents improved sensitivity, kinetics and walking steps for intracellular fluorescence imaging of base-excision repairing.

Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation.

A three-step, modular and divergent sequence accessing challenging spirocyclic pyrrolidines has been developed, featuring a novel reductive spirocyclization cascade.

A chiral N,N′-dioxide/Fe(OTf)₂ complex catalyzed enantioselective [1,3] O-to-C rearrangement of racemic alkyl vinyl ethers was described.