New avenues for C–B bond formation via radical intermediates
Efficient radical routes to important alkyl and aryl boronic esters have been developed over the past few years. Such reactions are complementary to existing transition-metal catalysed cross coupling processes.
A review of biomass materials for advanced lithium–sulfur batteries
This review summarizes recent progress of biomass-derived materials in Li–S batteries. These materials are promising due to their advantages including strong physical and chemical adsorption, high abundance, low cost, and environmental friendliness.
Reductive radical-polar crossover: traditional electrophiles in modern radical reactions
The concept of reductive radical-polar crossover (RRPCO) reactions has recently emerged as a valuable and powerful tool to overcome limitations of both radical and traditional polar chemistry.
Visual kinetic analysis
Naked-eye comparison of reaction profiles is a powerful tool to extract mechanistic information – FAQ, video tutorial and templated examples included.
RNA Imaging in Living Mouse Enabled by in Vivo Hybridization Chain Reaction Circuit with Tripartite DNA Probe
LiMg(IO3)3: an excellent SHG material designed by single-site aliovalent substitution
An excellent SHG iodate, LiMg(IO3)3, has been obtained via the aliovalent substitution of defect-containing MIV sites with ordered Mg2+.
A rare earth hydride supported ruthenium catalyst for the hydrogenation of N-heterocycles: boosting the activity via a new hydrogen transfer path and controlling the stereoselectivity
A novel Ru/YH3 catalyst with excellent performance in terms of activity and stereoselectivity for hydrogenation of N-heterocycles is developed.
Single-molecule dynamic DNA junctions for engineering robust molecular switches
Highly robust DNA molecule switches were engineered by utilizing single-molecule dynamic three-way junctions.
Preferential binding of unsaturated hydrocarbons in aryl-bisimidazolium·cucurbituril complexes furbishes evidence for small-molecule π–π interactions
Restricting the internal cavity size of cucurbituril with auxiliary guests sets up an intermolecular interaction chamber for hydrocarbons, which provides insights into dispersion, arene–hydrocarbon interactions, and desolvation effects.
Development of a hydrolysis-based small-molecule hydrogen selenide (H2Se) donor
Hydrolysis-based H2Se donors provide new chemical tools for investigating biological H2Se.
Synthesis of bicyclo[3.1.0]hexanes by (3 + 2) annulation of cyclopropenes with aminocyclopropanes
(3 + 2) annulation of cyclopropenes and aminocyclopropanes under mild photoredox conditions leading to bicyclo[3.1.0]hexanes with high diastereoselectivity for fluorinated derivatives.
Dissociation path competition of radiolysis ionization-induced molecule damage under electron beam illumination
Molecule damage under TEM electron beam illumination is studied using a systematical ab initio method. Three main dissociation paths are revealed which explains the experimentally observed mass spectra of the dissociation fragments of the C2H6O2+.
α-D-Gal-cyclophellitol cyclosulfamidate is a Michaelis complex analog that stabilizes therapeutic lysosomal α-galactosidase A in Fabry disease
α-D-Gal-cyclophellitol cyclosulfamidate is a new class of neutral, conformationally-constrained competitive glycosidase inhibitor that stabilizes α-gal A and prevents its degradation both in vitro and in cellulo by mimicry of the Michaelis complex conformation.
Computational design of syntheses leading to compound libraries or isotopically labelled targets
Network-search routines over large graphs of retrosynthetic scenarios are adapted to multi-target design operating on one common search graph enabling design of syntheses of compound libraries or isotopically labelled targets.
Facile triflic acid-catalyzed α-1,2-cis-thio glycosylations: scope and application to the synthesis of S-linked oligosaccharides, glycolipids, sublancin glycopeptides, and TN/TF antigens
Studies of S-linked glycoconjugates have attracted growing interest because of their enhanced chemical stability and enzymatic resistance over O-glycoside counterparts.
Merging hypervalent iodine and sulfoximine chemistry: a new electrophilic trifluoromethylation reagent
Two prominent trifluoromethylation reagent classes join forces in a bench stable hypervalent iodosulfoximine CF3 transfer agent. We report its synthesis, properties and reactivity, opening up new possibilities in trifluoromethylation chemistry.
A hybrid blue perovskite@metal–organic gel (MOG) nanocomposite: simultaneous improvement of luminescence and stability
Weakly blue emitting EAPbBr3 NCs transformed into a highly intense blue material after embedding inside metal–organic gel (MOG) matrix. The nanocomposite showing outstanding stability in water and under UV light for longer period of time.
Electronic structures of bent lanthanide(III) complexes with two N-donor ligands
Halide abstraction chemistry is performed on a series of trigonal lanthanide(III) complexes to provide bent complexes that contain only two N-donor ligands.
Surface enhanced dynamic nuclear polarization solid-state NMR spectroscopy sheds light on Brønsted–Lewis acid synergy during the zeolite catalyzed methanol-to-hydrocarbon process
Surface-enhanced dynamic nuclear polarization solid-state NMR spectroscopy has been applied to identify the role of surface-carbene species and elucidating Brønsted–Lewis acid synergy during the zeolite-catalyzed methanol-to-hydrocarbon process.
A light-responsive, self-immolative linker for controlled drug delivery via peptide- and protein-drug conjugates
Photoirradiation of the PC4AP linker generates an active intermediate that reacts intramolecularly with a primary amine on the carrier peptide/protein, leading to rapid release of the drug without generating any toxic side products.
Efficient occlusion of oil droplets within calcite crystals
Remarkably efficient occlusion of 250–500 nm oil droplets within single calcite crystals is achieved using anionic amphiphilic diblock copolymer emulsifiers.
Living β-selective cyclopolymerization using Ru dithiolate catalysts
Herein, we demonstrate the first example of living β-selective CP by rational engineering of the steric factor on monomer or catalyst structures, along with a mechanistic investigation by in situ kinetic studies using 1H NMR spectroscopy.
Enantioselective total synthesis of the unnatural enantiomer of quinine
A practical enantioselective total synthesis of the unnatural (+)-quinine and (−)-9-epi-quinine enantiomers, which are important organocatalysts, is reported.
Design, synthesis and application of a new type of bifunctional Le-Phos in highly enantioselective γ-addition reactions of N-centered nucleophiles to allenoates
A novel class of bifunctional cyclic phosphine catalysts (Le-Phos) is reported, which showed good performances in enantioselective γ-addition reactions of N-centered nucleophiles and allenoates under mild conditions.
Development of a DUB-selective fluorogenic substrate
Developing USP16-selective ubiquitin-based reagents to study USP16 and its related biology.
The molecular mechanisms of light adaption in light-harvesting complexes of purple bacteria revealed by a multiscale modeling
The spectral tuning of LH2 antenna complexes arises from H-bonding, acetyl torsion, and inter-chromophore couplings.
Anion carriers as potential treatments for cystic fibrosis: transport in cystic fibrosis cells, and additivity to channel-targeting drugs
Synthetic anion transporters are active in cystic fibrosis cells, and are additive to clinically-approved drugs, suggesting new combination therapies for this lethal genetic condition.
Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction
An N2-bridged ditungsten complex is presented that undergoes N2-splitting or hydrogen evolution upon protonation depending on the acid and reaction conditions. Spectroscopic, kinetic and computational results emphasize the impact of hydrogen bonding on the reaction selectivity.
Synergistic catalysis on Fe–Nx sites and Fe nanoparticles for efficient synthesis of quinolines and quinazolinones via oxidative coupling of amines and aldehydes
A heterogeneous nanocomposite of Fe–Fe3C nanoparticles and Fe–Nx sites on N-doped porous carbon allows for efficient synthesis of quinolines and quinazolinones via oxidative coupling of amines and aldehydes in aq. solution using H2O2 as the oxidant.
On the unsuspected role of multivalent metal ions on the charge storage of a metal oxide electrode in mild aqueous electrolytes
The hidden role of hexaaquo metal ion complexes in the proton-coupled electron charge storage at a metal oxide electrode.
Photoefficient 2nd generation molecular motors responsive to visible light
A new series of visible light-driven artificial rotary molecular motors is presented including the most red-shifted example to date.
Configuration determination by residual dipolar couplings: accessing the full conformational space by molecular dynamics with tensorial constraints
The use of tensorial orientational constraints for NMR-derived residual dipolar couplings (RDCs) in molecular dynamics simulations brings detailed structural models of flexible molecules in solution in reach.
Tip-enhanced Raman spectroscopy for structural analysis of two-dimensional covalent monolayers synthesized on water and on Au (111)
Two-dimensional covalent monolayers synthesized at an air/water interface were structurally analyzed by tip-enhanced Raman spectroscopy (TERS). Finally, on-metal surface synthesis of a 2D polymer was demonstrated under ambient conditions.
Catalytic, transannular carbonyl-olefin metathesis reactions
Transannular carbonyl-olefin metathesis reactions complement existing procedures for related ring-closing, ring-opening, and intermolecular carbonyl-olefin metathesis. This enables molecular editing of steroid-derived frameworks.
Enzyme-mediated dynamic combinatorial chemistry allows out-of-equilibrium template-directed synthesis of macrocyclic oligosaccharides
Artificial templates can control out-of-equilibrium self-assembly in an enzyme-mediated dynamic system of cyclodextrins, even allowing access to products not selected in Nature.
Selective catecholamine detection in living cells by a copper-mediated oxidative bond cleavage
A copper-mediated oxidative bond cleavage induced by catecholamines is developed into a turn-on fluorescent probe for imaging of the neurotransmitter in living cells.
Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks
We report three electrically conductive metal–organic frameworks (MOFs) based on a tetrathiafulvalene linker and La3+.
Discovery of selective, antimetastatic and anti-cancer stem cell metallohelices via post-assembly modification
A remarkable array of mechanistic and pharmacological behaviours is discovered via click derivatisation of asymmetric, optically pure helicate-like compounds.
Orthogonal functionalization of alternating polyesters: selective patterning of (AB)n sequences
A series of AB alternating polyesters are orthogonally patterned to install two different functionalities at regular intervals along the backbone and with high precision.
Electronic coherence lifetimes of the Fenna–Matthews–Olson complex and light harvesting complex II
The study of coherence between excitonic states in naturally occurring photosynthetic systems offers tantalizing prospects for uncovering mechanisms of efficient energy transport.
A general synthesis of dendralenes
The first broad spectrum dendralene synthesis permits the widest structural and substituent variation and promotes applications in step economic synthesis.
Low dimensional representations along intrinsic reaction coordinates and molecular dynamics trajectories using interatomic distance matrices
Principal Component Analysis on a series of molecular geometries (e.g., a reaction coordinate or trajectory) provides maximum structural variance in the fewest dimensions, and so can offer an objective, comprehensible depiction of the transformation.
A Cu–Pd single-atom alloy catalyst for highly efficient NO reduction
Highly active and selective NO reduction was achieved at low temperatures using a minimum amount of noble metal Pd.
Engineering multilayer chemical networks
History and layer design as new features in dynamic multilayer networks.
A symbiotic hetero-nanocomposite that stabilizes unprecedented CaCl2-type TiO2 for enhanced solar-driven hydrogen evolution reaction
We report a symbiotic hetero-nanocomposite that stabilizes unprecedented CaCl2-type TiO2 for enhanced solar-driven hydrogen evolution reaction.
Catalyst shuttling enabled by a thermoresponsive polymeric ligand: facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium
A thermoresponsive polymeric Pd-complex was synthesized, enabling highly efficient cross-couplings and continuous catalyst-recycling flow reactions with ultralow Pd usages.
Electron density learning of non-covalent systems
Machine learning model of the electron densities for analyzing non-covalent interaction patterns in peptides.
Metallohelices that kill Gram-negative pathogens using intracellular antimicrobial peptide pathways
Iron-based self-assembled optically pure compounds mimic the mechanisms of small peptides, according to biophysical, genomic, transcriptomic and other analyses.
Controlling magnetism of Au133(TBBT)52 nanoclusters at single electron level and implication for nonmetal to metal transition
The [Au133(SR)52]q nanocluster is discovered to possess one spin per particle when q = 0, but no unpaired electron when q = +1.
Ligand-controlled diastereodivergent, enantio- and regioselective copper-catalyzed hydroxyalkylboration of 1,3-dienes with ketones
A ligand-controlled diastereodivergent copper-catalyzed borylative coupling between 1,3-dienes and ketones enables the enantioselective synthesis of densely functionalized tertiary homoallylic alcohols.
Chaperone-like chiral cages for catalyzing enantio-selective supramolecular polymerization
Chiral organic cages can assist enantio-selective supramolecular polymerization through a catalyzed assembly (catassembly) strategy, like chaperones assist the assembly of biomolecules.
Magnesium hydride alkene insertion and catalytic hydrosilylation
The β-diketiminato magnesium hydride, [(BDI)MgH]]2, reacts with alkenes and catalyses their hydrosilylation with PhSiH3.
Efficient in vivo synthesis of lasso peptide pseudomycoidin proceeds in the absence of both the leader and the leader peptidase
Post translational modifications can help maintain the threaded lasso topology of pseudomycoidin.
Influence of the distal guanidine group on the rate and selectivity of O2 reduction by iron porphyrin
The O2 reduction reaction (ORR) catalysed by iron porphyrins with covalently attached pendant guanidine groups is reported.
A proof-reading mechanism for non-proteinogenic amino acid incorporation into glycopeptide antibiotics
A complex interplay of non-ribosomal peptide synthetase domains works together with trans-acting enzymes to ensure effective GPA biosynthesis.
Design of non-ionic carbon superbases: second generation carbodiphosphoranes
The edge-cutting design, synthesis and characterization of the so far strongest non-ionic carbon superbases is presented.
Accelerated robotic discovery of type II porous liquids
High-throughput automation was used to streamline the synthesis, characterisation, and solubility testing, of new Type II porous liquids, accelerating their discovery.
The ubiquitous cross-coupling catalyst system ‘Pd(OAc)2’/2PPh3 forms a unique dinuclear PdI complex: an important entry point into catalytically competent cyclic Pd3 clusters
Pd3-type clusters generated from Pd(OAc)2/nPPh3, formed via a dinuclear Pd(I) species, exhibit high activity in Suzuki–Miyaura cross-coupling.
A quantitative uncertainty metric controls error in neural network-driven chemical discovery
A predictive approach for driving down machine learning model errors is introduced and demonstrated across discovery for inorganic and organic chemistry.
Steric and electronic control of an ultrafast isomerization
Synthetic control and the influence of steric and electronic factors on the ultrafast (picosecond) isomerization of penta-coordinate ruthenium dithietene complexes (Ru((CF3)2C2S2)(CO)(L)2, where L = a monodentate phosphine ligand) is reported.
In situ real-time tracing of hierarchical targeting nanostructures in drug resistant tumors using diffuse fluorescence tomography
Nanoparticles that respond to specific endogenous or exogenous stimuli in tumor tissues are actively being developed to address multidrug resistance owing to multiple advantages, including a prolonged circulation time, enhanced permeability and retention effect, and superior cellular uptake.
Observation of osmotically driven, highly controllable and reconfigurable oil/water phase separation
Osmotically driven, highly controllable and reconfigurable water–oil phase separation was achieved for the first time using ionic liquid systems.
Taming conformational heterogeneity in and with vibrational circular dichroism spectroscopy
Genetic fitting algorithm accounting for the uncertainty in computed energies allows a significantly more reliable assignment of stereochemistry and conformational heterogeneity of chiral compounds using vibrational circular dichroism.
Anthracene-based mechanophores for compression-activated fluorescence in polymeric networks
The recent attention given to functionalities that respond to mechanical force has led to a deeper understanding of force transduction and mechanical wear in polymeric materials.
Relayed hyperpolarization from para-hydrogen improves the NMR detectability of alcohols
NMR signal strength improvements delivered through hyperpolarisation via para-hydrogen enable the facile detection of alcohols.
Pore-size dominated electrochemical properties of covalent triazine frameworks as anode materials for K-ion batteries
Pore-size dominated K-ion storage behaviour in covalent triazine frameworks.
A generalized deep learning approach for local structure identification in molecular simulations
We demonstrate a PointNet-based deep learning approach to classify local structure in molecular simulations, learning features directly from atomic coordinates.
Electrochemical C–H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source
The well-known [(TAML)Fe(OH2)]− complex undergoes proton-coupled oxidation to an Fe-oxo species that supports electrochemical C–H oxidation and alcohol dehydrogenation.
Insights from 125Te and 57Fe nuclear resonance vibrational spectroscopy: a [4Fe–4Te] cluster from two points of view
Can sulfur-to-tellurium exchange serve as a method to understand iron–sulfur clusters of enzymatic systems?
A natural solution to photoprotection and isolation of the potent polyene antibiotic, marinomycin A
Perfect partners for photoprotection: orally ingestible sporopollenin confers striking photoprotection to the powerful, polyene antibiotic, marinomycin A, as well as enabling its selective extraction.
About this collection
This on-going web collection showcases all of the HOT Chemical Science articles published in 2019, as recommended by referees. Congratulations to all of the authors whose articles are featured.