Themed collection 2019 Chemical Science HOT Article Collection
Metal–organic framework gels and monoliths
This perspective links the synthesis of MOF Gels to the formation of MOF-monoliths and their resultant properties and application.
Current advances in tin cluster chemistry
Clusters containing tin atoms show a huge variety of molecular structures, chemical as well as physical properties.
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.
Influenza as a molecular walker
The neuraminidase on the surface of influenza viruses make the virus a receptor-cleaving molecular walker, similar to molecular spiders.
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.
Expanding medicinal chemistry into 3D space: metallofragments as 3D scaffolds for fragment-based drug discovery
Fragment-based drug discovery (FBDD) using 3-dimensional metallofragments is a new strategy for the identification of bioactive molecules.
The importance of nanoscale confinement to electrocatalytic performance
Nanoparticles mimicking the three-dimensional architecture of enzymes where the reaction occurs down a channel isolated from bulk solution, referred here as nanozymes, were used to explore the impact of nano-confinement on electrocatalytic reactions.
Uncommon structural and bonding properties in Ag16B4O10
Ag16B4O10, obtained via hydrothermal synthesis, displays an unprecedented bonding scheme, hosting excess electrons localized pairwise in cluster-like silver subunits.
Single-molecule nanopore sensing of actin dynamics and drug binding
Nanopipettes were used for real-time investigation into actin dynamics and drug binding at single-molecule resolution, showing promise for a better understanding of the mechanism of protein–protein interactions and drug discovery.
Conformational control of Pd2L4 assemblies with unsymmetrical ligands
Steric and geometric constraints were used to design unsymmetrical ditopic ligands that form single Pd2L4 cage isomers with high fidelity.
A photo-regulated aptamer sensor for spatiotemporally controlled monitoring of ATP in the mitochondria of living cells
A photo-regulated ATP sensor coupled with cationic DQAsomes is developed for spatiotemporally controlled imaging of ATP in the mitochondria of living cells.
Chiral cis-iron(II) complexes with metal- and ligand-centered chirality for highly regio- and enantioselective alkylation of N-heteroaromatics
A cis-β FeII complex having metal- and ligand-centered chirality catalyzes highly regio- and enantioselective alkylation of indoles (at the N1, C2, or C3 position), pyrroles and anilines with α,β-unsaturated 2-acyl imidazoles (48 examples, up to 99% ee).
A complete picture of protein unfolding and refolding in surfactants
The time-resolved study reveals several transition states during SDS-induced unfolding of the protein, as well as under refolding of the protein by the nonionic surfactant C12E8.
CsAlB3O6F: a beryllium-free deep-ultraviolet nonlinear optical material with enhanced thermal stability
A new potential deep-ultraviolet nonlinear optical material CsAlB3O6F was designed by a rational selection of fundamental structural units. This material does not require toxic raw materials and can be grown in an open system.
Manipulating molecules with strong coupling: harvesting triplet excitons in organic exciton microcavities
Exciton-polaritons are quasiparticles with mixed photon and exciton character with the potential to modify chemical properties of materials. Here, they are used to provide dark, high-spin triplet-pair states a new pathway to emit light.
Chelation with a twist: a bifunctional chelator to enable room temperature radiolabeling and targeted PET imaging with scandium-44
The small-cavity, bifunctional chelator picaga coordinates Sc-44 at room temperature and enables PET imaging of an in vivo tumor target.
Biosynthesis of plant tetrahydroisoquinoline alkaloids through an imine reductase route
An artificial approach has been developed for efficient biosynthesis of plant tetrahydroisoquinoline alkaloids from dihydroisoquinoline precursors.
Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals
Ptychographic X-ray computed tomography visualizes the effects crystallography and solution composition have on occlusion motif and occlusion density of crystalline nanocomposites.
Programmable dynamic covalent nanoparticle building blocks with complementary reactivity
A toolkit of two complementary dynamic covalent nanoparticles enables programmable and reversible nanoparticle functionalization and construction of adaptive binary assemblies.
Enantioselective synthesis of P-chiral tertiary phosphine oxides with an ethynyl group via Cu(I)-catalyzed azide–alkyne cycloaddition
Highly enantioselective CuAAC reactions for the synthesis of versatile P-chiral phosphorus synthons featuring a versatile ethynyl group were developed.
Accurate cancer cell identification and microRNA silencing induced therapy using tailored DNA tetrahedron nanostructures
DNA tetrahedron nanostructures (DTNSs) were prepared to improve the accuracy of cancer diagnosis through real-time monitoring and imaging three intracellular miRNAs, as well as to realize cancer therapy induced by miRNA silencing.
Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt(II) porphyrin–porphyrin dyad
Asymmetrical Pacman dinuclear Co bisporphyrin shows significantly improved activity and selectivity for catalytic reduction of O2 to water in comparison with corresponding mononuclear Co porphyrins and symmetrical dinuclear Co bisporphyrins.
Covalent bonds in positron dihalides
We report a computational study on homo- and heteronuclear e+[X−Y−] compounds formed by two halide anions (X−, Y− = F−, Cl−, Br−) and one positron.
Ruthenium based antimicrobial theranostics – using nanoscopy to identify therapeutic targets and resistance mechanisms in Staphylococcus aureus
A detailed study on the uptake and antimicrobial activity of a RuII theranostic complex with wild-type S. aureus, MRSA, and other mutants has identified the specific resistance mechanisms that Gram-positive bacteria display against this lead.
RNA imaging in living mice enabled by an in vivo hybridization chain reaction circuit with a tripartite DNA probe
Using an in vivo hybridization chain reaction with a tripartite DNA probe to image RNA in living mice may open the door for intracellular RNA imaging in living mammalian animals, implying its potential for tumor biology studies and theranostics.
Aqueous microdroplets containing only ketones or aldehydes undergo Dakin and Baeyer–Villiger reactions
The Dakin and Baeyer–Villiger (BV) oxidation reactions require addition of peroxides as oxidants and an acid or a base as a catalyst.
A quantitative assessment of the dynamic modification of lipid–DNA probes on live cell membranes
A comprehensive and quantitative study of the dynamic process of lipid–DNA conjugate modification onto cell membranes.
A pencil-and-paper method for elucidating halide double perovskite band structures
Explaining most known double perovskite electronic structures and predicting new ones using Linear Combination of Atomic Orbitals analysis.
Interconversion and reactivity of manganese silyl, silylene, and silene complexes
Interconversions between manganese silylene and silene complexes are reported, including those involving the first spectroscopically observed silene complexes with an SiH substituent, and their involvement in ethylene hydrosilylation is discussed.
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+.
Ratiometric fluorescence imaging of Golgi H2O2 reveals a correlation between Golgi oxidative stress and hypertension
Based on a novel Golgi-targeting phenylsulfonamide group, a two-photon (TP) fluorescent probe, Np-Golgi, was developed for in situ H2O2 ratiometric imaging in living systems.
Precise modulation of molecular weight distribution for structural engineering
Modulating MWD through precise blending of discrete macromolecules provides a model platform for highlighting the importance of chain length heterogeneity.
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+.
Identifying high-performance catalytic conditions for carbon dioxide reduction to dimethoxymethane by multivariate modelling
An efficient algorithmic workflow was developed to optimize seven process parameters of a homogeneous catalytic system with minimal experimental effort.
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.
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 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.
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.
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.
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 DUB-selective fluorogenic substrate
Developing USP16-selective ubiquitin-based reagents to study USP16 and its related biology.
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.
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.
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.
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.
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.
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 general synthesis of dendralenes
The first broad spectrum dendralene synthesis permits the widest structural and substituent variation and promotes applications in step economic synthesis.
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.
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.
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.
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.
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.
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.
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.
Electron density learning of non-covalent systems
Machine learning model of the electron densities for analyzing non-covalent interaction patterns in peptides.
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.
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.
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.
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.
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.