Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals
Hydrogen atom transfer from metal hydrides to alkenes appears to underlie widely used catalytic methods – the mechanistic implications are fascinating.
Electro-organic synthesis – a 21st century technique
This perspective provides insight into recent electro-organic methods and general trends in this field, and opens up prospects for future viewpoints.
Near-infrared fluorescent molecular probes for imaging and diagnosis of nephro-urological diseases
Near-infrared fluorescent molecular probes with improved imaging depth and optimized biodistribution have been reviewed, showing great potential for diagnosis of nephro-urological diseases.
Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis
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.
Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes
Nickel-catalyzed three-component alkene difunctionalization has rapidly emerged as a powerful tool for forging multiple C–C bonds in a single step.
Can we predict materials that can be synthesised?
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.
A protecting group strategy to access stable lacunary polyoxomolybdates for introducing multinuclear metal clusters
A “protecting group strategy” for unstable lacunary polyoxomolybdates enabled successful synthesis of two types of tetranuclear manganese clusters.
A ground-state-dominated magnetic field effect on the luminescence of stable organic radicals
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.
Enhanced voltammetric anion sensing at halogen and hydrogen bonding ferrocenyl SAMs
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.
Magnesium–halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex
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.
Peptide sequence mediated self-assembly of molybdenum blue nanowheel superstructures
Peptide sequence can be used to control the self-assembly and structures of nanoscale molybdenum blue polyoxometalate (POM) wheel-shaped clusters.
Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn2+ sensors
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.
Molecular engineering enabling reversible transformation between helical and planar conformations by cyclization of alkynes
One-pot synthesis of azahelicenes is accomplished through two successive C–H activation/cyclizations, which exhibit on/off fluorescence switching through reversible transformation between helical and planar conformations.
A critical analysis of electrospray techniques for the determination of accelerated rates and mechanisms of chemical reactions in droplets
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.
Fast reversible isomerization of merocyanine as a tool to quantify stress history in elastomers
A mechanochemistry based approach is proposed to detect and map stress history during dynamic processes.
One class classification as a practical approach for accelerating π–π co-crystal discovery
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.
Total synthesis and complete configurational assignment of amphirionin-2
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.
Fucosylated ubiquitin and orthogonally glycosylated mutant A28C: conceptually new ligands for Burkholderia ambifaria lectin (BambL)
Metal free click reactions used to glycosylate ubiquitin and its mutant A28C afforded two protein scaffolds with high affinity for Burkholderia ambifaria lectin (BambL).
Aryl urea substituted fatty acids: a new class of protonophoric mitochondrial uncoupler that utilises a synthetic anion transporter
A new mitochondrial uncoupler that forms membrane permeable dimers through interactions of remote acidic and anion receptor groups.
Total scattering reveals the hidden stacking disorder in a 2D covalent organic framework
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.
Accurate crystal structures and chemical properties from NoSpherA2
NoSpherA2 brings quantum crystallography to routine structure determination and to the analysis of chemical properties for any class of materials.
An ultra-stable bio-inspired bacteriochlorin analogue for hypoxia-tolerant photodynamic therapy
A hypoxia-tolerant photosensitizer FBC-based nanoplatform with strong NIR absorbance and ultra-high stability was facilely prepared for PDT of deep tumors.
Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states
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.
Enhancing glycan stability via site-selective fluorination: modulating substrate orientation by molecular design
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.
Supertetrahedral polyanionic network in the first lithium phosphidoindate Li3InP2 – structural similarity to Li2SiP2 and Li2GeP2 and dissimilarity to Li3AlP2 and Li3GaP2
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.
On-surface isostructural transformation from a hydrogen-bonded network to a coordination network for tuning the pore size and guest recognition
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.
Reversible carbon–boron bond formation at platinum centers through σ-BH complexes
A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(II) complex [Pt(ItBuiPr′)(ItBuiPr)][BArF], 1, with tricoordinated boranes HBR2.
Cation recognition on a fullerene-based macrocycle
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.
Hyperpositive non-linear effects: enantiodivergence and modelling
An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects.
Structure and dynamics of catalytically competent but labile paramagnetic metal-hydrides: the Ti(III)-H in homogeneous olefin polymerization
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.
Room temperature conductance switching in a molecular iron(III) spin crossover junction
Herein, we report the first room temperature switchable Fe(III) molecular spin crossover (SCO) tunnel junction.
Nucleophilic reactivity of the gold atom in a diarylborylgold(I) complex toward polar multiple bonds
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.
Born–Oppenheimer approximation in optical cavities: from success to breakdown
The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated.
On Raman optical activity sign-switching between the ground and excited states leading to an unusual resonance ROA induced chirality
Unusual solute to solvent induced chirality in ROA comes from specific conformer equilibria in the ground and the excited states.
Iron-catalyzed α-C–H functionalization of π-bonds: cross-dehydrogenative coupling and mechanistic insights
[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.
Multimerized self-assembled caged two-in-one siRNA nanoparticles for photomodulation of RNAi-induced gene silencing
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.
Merging C(sp3)–H activation with DNA-encoding
DNA-compatible C(sp3)–H activation reactions of aliphatic carboxylic acids, amides, and ketones were developed for efficient access to DEL synthesis.
Introducing affinity and selectivity into galectin-targeting nanoparticles with fluorinated glycan ligands
A chemo-enzymatic site-specific fluorination strategy is employed to obtain glyco-nanoparticles with tuneable selectivity towards galectins.
Bis[pyrrolyl Ru(II)] triads: a new class of photosensitizers for metal–organic photodynamic therapy
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.
Unveiling the molecular mechanism of SARS-CoV-2 main protease inhibition from 137 crystal structures using algebraic topology and deep learning
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.
Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study
Computational studies reveal near-IR emitting nanohoops and the effect of strain on donor and acceptor units used in conjugated polymers.
Impact of the macrocyclic structure and dynamic solvent effect on the reactivity of a localised singlet diradicaloid with π-single bonding character
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”.
Single-nucleotide resolution of N6-adenine methylation sites in DNA and RNA by nitrite sequencing
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.
Is there a photochemical Hammond postulate?
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.
Selective inhibition of the K+ efflux sensitive NLRP3 pathway by Cl− channel modulation
The NLRP3 inflammasome regulates production of the pro-inflammatory cytokines interleukin-1β (IL-1β) and IL-18, and contributes to inflammation exacerbating disease.
Biomimetic hydrogen-bonding cascade for chemical activation: telling a nucleophile from a base
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.
Intramolecular Friedel–Crafts alkylation with a silylium-ion-activated cyclopropyl group: formation of tricyclic ring systems from benzyl-substituted vinylcyclopropanes and hydrosilanes
Downstream to alkene hydrosilylation, the opening of the cyclopropane ring in benzyl-substituted VCPs is interlinked with an SEAr of the aryl group.
Structural basis for recognition of bacterial cell wall teichoic acid by pseudo-symmetric SH3b-like repeats of a viral peptidoglycan hydrolase
Combining genetic, biochemical and computational approaches, we elucidated the molecular mechanisms underlying the recognition of Listeria wall teichoic acid by bacteriophage-encoded SH3b repeats.
Transferrable property relationships between magnetic exchange coupling and molecular conductance
Calculated conductance through Aun–S–Bridge–S–Aun constructs are compared to experimental magnetic exchange coupling parameters in TpCum,MeZn(SQ–Bridge–NN) complexes, where SQ = semiquinone radical and NN = nitronylnitroxide radical.
Enhancing the photodynamic therapy efficacy of black phosphorus nanosheets by covalently grafting fullerene C60
Covalently grafting C60 molecules onto black phosphorus (BP) nanosheets improves their tumor inhibition rate from 36.6% to 88.2%.
‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads
Supramolecular synthons are exploited to synthesize –OH functionalized sp3-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.
Simultaneous manifestation of metallic conductivity and single-molecule magnetism in a layered molecule-based compound
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.
Target-driven supramolecular self-assembly for selective amyloid-β photooxygenation against Alzheimer's disease
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.
Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene
A combined experimental and theoretical study on the mechanism of the C–F bond activation of C6F6 with [Ni(NHC)2] is provided.
Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene
(PBP)Ir pincer complexes containing a boryl-iridium linkage reversibly bind ethylene as an ethylidene bridging B and Ir.
Total syntheses of spiroviolene and spirograterpene A: a structural reassignment with biosynthetic implications
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 for electrocatalysis
A metal–organic framework/polymer derived catalyst containing single-atom nickel species shows good performance for electroreduction of CO2 to CO.
Catalytic asymmetric synthesis of quaternary trifluoromethyl α- to ε-amino acid derivatives via umpolung allylation/2-aza-Cope rearrangement
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.
Towards efficient discovery of green synthetic pathways with Monte Carlo tree search and reinforcement learning
A new MCTS variant with a reinforcement learning value network and solvent prediction model proposes shorter synthesis routes with greener solvents.
Acid–base chemistry at the single ion limit
Visualizing dynamic change in the number of protons during electroreduction of protons in attoliter volume zero-mode waveguides.
Rhodium-catalysed tetradehydro-Diels–Alder reactions of enediynes via a rhodium-stabilized cyclic allene
Room temperature Rh-catalysed tetradehydro-Diels–Alder reaction via an unusual Rh-stabilised allene.
Glycan–glycan interactions determine Leishmania attachment to the midgut of permissive sand fly vectors
Force spectroscopy was used to measure the adhesion of Leishmania to synthetic mimics of galectins on the sand fly midgut.
Revealing the molecular mechanisms of proteolysis of SARS-CoV-2 Mpro by QM/MM computational methods
The molecular mechanism of the proteolysis reaction catalyzed by SARS-CoV-2 Mpro, 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.
Neuraldecipher – reverse-engineering extended-connectivity fingerprints (ECFPs) to their molecular structures
Protecting molecular structures from disclosure against external parties is of great relevance for industrial and private associations, such as pharmaceutical companies.
Proteomimetic surface fragments distinguish targets by function
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.
A heterometallic [LnLn′Ln] lanthanide complex as a qubit with embedded quantum error correction
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.
A bipedal DNA nanowalker fueled by catalytic assembly for imaging of base-excision repairing in living cells
The developed DNA bipedal walker represents improved sensitivity, kinetics and walking steps for intracellular fluorescence imaging of base-excision repairing.
Surface hydration for antifouling and bio-adhesion
Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation.
A modular and divergent approach to spirocyclic pyrrolidines
A three-step, modular and divergent sequence accessing challenging spirocyclic pyrrolidines has been developed, featuring a novel reductive spirocyclization cascade.
Chiral Fe(II) complex catalyzed enantioselective [1,3] O-to-C rearrangement of alkyl vinyl ethers and synthesis of chromanols and beyond
A chiral N,N′-dioxide/Fe(OTf)2 complex catalyzed enantioselective [1,3] O-to-C rearrangement of racemic alkyl vinyl ethers was described.
About this collection
This on-going web collection showcases all of the HOT Chemical Science articles published in 2020, as recommended by referees. Congratulations to all of the authors whose articles are featured.