Visual kinetic analysis
Naked-eye comparison of reaction profiles is a powerful tool to extract mechanistic information – FAQ, video tutorial and templated examples included.
A novel mass spectrometry-cleavable, phosphate-based enrichable and multi-targeting protein cross-linker
A thiochromenone antibiotic derived from Pseudomonas quinolone signal selectively targets the Gram-negative pathogen Moraxella catarrhalis
Potent and selective in vitro and in vivo antiproliferative effects of metal–organic trefoil knots
A set of metal–organic trefoil knots (M-TKs) generated by metal-templated self-assembly of a simple pair of chelating ligands were well tolerated in vitro by non-cancer cells but were significantly more potent than cisplatin in both human cancer cells––including those resistant to cisplatin––and in zebrafish embryos.
Combination of gallium(III) with acetate for combating antibiotic resistant Pseudomonas aeruginosa
Combination of Ga(III) with acetate greatly enhances the antimicrobial activity of Ga(III) against P. aeruginosa, and shows promise to combat the crisis of antimicrobial resistance.
Ionic liquid cations as methylation agent for extremely weak chalcogenido metalate nucleophiles
Imidazolium-based ionic liquids served to selectively methylate terminal chalcogenide ligands of chalcogenidometalate clusters [Sn10S16O4(SMe)4]4−, [Mn4Sn4Se13(SeMe)4]6−, and [Hg6Te10(TeMe)2]6−.
Synthesis of glycopolymers with specificity for bacterial strains via bacteria-guided polymerization
Glycopolymers with specificity to template strain of E. coli were synthesised by the bacteria-sugar monomer-aptation-polymerization.
Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator
Platinadithiolene nanosheet synthesized by interfacial transmetallation is a possible candidate of a 2D topological insulator at room temperature and an effective catalyst for the electrochemical HER.
Enantioseparation by crystallization using magnetic substrates
Enantiospecific crystallization of the three amino acids asparagine (Asn), glutamic acid hydrochloride (Glu·HCl) and threonine (Thr), induced by ferromagnetic (FM) substrates, is reported.
Brønsted acid catalysis – the effect of 3,3′-substituents on the structural space and the stabilization of imine/phosphoric acid complexes
Advanced NMR and theoretical studies reveal detailed insights into monomeric and dimeric structures plus deviating experimental and theoretical E/Z-populations.
Using coligands to gain mechanistic insight into iridium complexes hyperpolarized with para-hydrogen
Hyperpolarised iridium carboxyimine complexes yield diagnostic signals whilst undergoing ligand exchange processes rationalised by NMR and DFT.
Atomic Resolution Map of the Soluble Amyloid Beta Assembly Toxic Surfaces
Quo vadis niobium? Divergent coordination behavior of early-transition metals towards MOF-5
Despite its prevalence, cation exchange is not the only immobilization pathway for foreign cations in the epochal MOF-5 metal–organic framework.
Theoretical design of a technetium-like alloy and its catalytic properties
Based on the concept of density of states (DOS) engineering, we theoretically designed a pseudo-Tc material (Mo–Ru alloy) and investigated its electronic structure, phase stability and catalytic activity by using density functional theory.
Synergetic interaction between neighboring platinum and ruthenium monomers boosts CO oxidation
The synergetic effect between neighboring Pt and Ru monomers supported on N vacancy-rich g-C3N4 promotes the catalytic CO oxidation.
Photoelectric effect accelerated electrochemical corrosion and nanoimprint processes on gallium arsenide wafers
Here we report photoelectric-effect-enhanced interfacial charge transfer reactions.
Highly regioselective complexation of tungsten with Eu@C82/Eu@C84: interplay between endohedral and exohedral metallic units induced by electron transfer
Interplay between inner and outer metallic units induced by charge transfer is observed in tungsten complexes of Eu@C2(5)-C82 and Eu@C2(13)-C84.
The antioxidant activity of polysulfides: it's radical!
Sulfurized olefins (polysulfides) containing four (or more) sulfur atoms react efficiently with peroxyl radicals by homolytic substitution, accounting for their primary antioxidant activity.
NosL is a dedicated copper chaperone for assembly of the CuZ center of nitrous oxide reductase
The Cu(I)-binding protein NosL functions specifically as an assembly factor for the unique CuZ centre of nitrous oxide reductase (N2OR).
Synthesis and characterization of an unnatural boron and nitrogen-containing tryptophan analogue and its incorporation into proteins
A boron and nitrogen containing unnatural analogue of tryptophan is synthesized and incorporated into proteins.
Triperyleno[3,3,3]propellane triimides: achieving a new generation of quasi-D3h symmetric nanostructures in organic electronics
A novel propellane rylene imide is synthesized. It serves as a versatile building block for quasi-D3h symmetric nanostructures.
Mapping binary copolymer property space with neural networks
We map the property space of binary copolymers to understand how copolymerisation can be used to tune the optoelectronic properties of polymers.
A sulfonium tethered peptide ligand rapidly and selectively modifies protein cysteine in vicinity
A unique peptide stabilization method provides a tethered sulfonium that can rapidly and selectively modify protein cysteine in close vicinity.
Diketopyrrolopyrrole-based fluorescence probes for the imaging of lysosomal Zn2+ and identification of prostate cancer in human tissue
Diketopyrrolopyrrole-based fluorescent probes have been developed for the detection of low pH and Zn2+ in an AND logic fashion. They can discriminate between cancerous and healthy prostate tissue.
Synthesis of sterically hindered 4,5-diarylphenanthrenes via acid-catalyzed bisannulation of benzenediacetaldehydes with alkynes
Acid-catalyzed bisannulation of benzenediacetaldehydes with alkynes provided a rapid access to sterically hindered 4,5-diarylphenanthrenes and multisubstituted phenanthrenes regioselectively.
Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fluorescence
Alkali metal complexes of an enantiopure iminophosphonamide bearing chiral centers at both nitrogen atoms are described. They show bright phosphorescence and thermally activated delayed fluorescence (TADF).
One metal is enough: a nickel complex reduces nitrate anions to nitrogen gas
A nickel complex was found to be capable of stepwise reducing nitrate to dinitrogen gas using carbon monoxide as the reaction partner.
A rhodium catalyzed cycloisomerization and tandem Diels–Alder reaction for facile access to diverse bicyclic and tricyclic heterocycles
A rhodium catalyzed cycloisomerization of 1,6-allenenes successfully prepared six-membered ring exocyclic 1,3-dienes. Further tandem Diels–Alder reaction with various dienophiles provided diverse bicyclic and tricyclic heterocycles. This methodology is characterised by complete atom and step economy, low catalyst loading, and excellent chemo-, regio-, and diastereoselectivity.
Chiral diversification through the assembly of achiral phenylacetylene macrocycles with a two-fold bridge
Multiple chiral molecules were generated through the assembly and double-bridging of achiral phenylacetylene macrocycles.
The full dynamics of energy relaxation in large organic molecules: from photo-excitation to solvent heating
In some molecular systems, such as nucleobases, polyenes or sunscreens, substantial amounts of photo-excitation energy are dissipated on a sub-picosecond time scale. Where does this energy go or among which degrees of freedom it is being distributed at such early times?
Photon upconversion utilizing energy beyond the band gap of crystalline silicon with a hybrid TES-ADT/PbS quantum dots system
Photon upconversion with an excitation of energy below the band gap of crystalline silicon was demonstrated with a hybrid system consisting of molecules based on a thiophene conjugated acene (i.e., TES-ADT) and lead sulphide (PbS) quantum dots.
Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium
A general and practical method to directly convert phenols into primary anilines with cheap and easy-to-handle hydrazine as the amine and hydride sources catalyzed by Pd/C.
Breaking the 1,2-HOPO barrier with a cyclen backbone for more efficient sensitization of Eu(III) luminescence and unprecedented two-photon excitation properties
Breaking the barrier of 1,2 HOPO complexes with extremely emissive Eu-Cy-HOPO (overall quantum yield −30.2%) that displays two photon properties.
Direct observation of prion protein oligomer formation reveals an aggregation mechanism with multiple conformationally distinct species
The aggregation of the prion protein (PrP) plays a key role in the development of prion diseases.
Helical orbitals and circular currents in linear carbon wires
Disubstituted odd-carbon cumulenes are linear carbon wires with helical π-orbitals, which results in circular current around the wire.
Photoinitiated carbonyl-metathesis: deoxygenative reductive olefination of aromatic aldehydes via photoredox catalysis
Carbonyl–carbonyl olefination, known as McMurry reaction, represents a powerful strategy for the construction of olefins.
Aqueous acid-based synthesis of lead-free tin halide perovskites with near-unity photoluminescence quantum efficiency
Aqueous acid-based synthesis of lead-free tin halide perovskites with near-unity photoluminescence quantum efficiency and high chemical yield is described.
Deep neural network learning of complex binary sorption equilibria from molecular simulation data
We employed deep neural networks (NNs) as an efficient and intelligent surrogate of molecular simulations for complex sorption equilibria using probabilistic modeling.
Construction of a cross-layer linked G-octamer via conformational control: a stable G-quadruplex in H-bond competitive solvents
A discrete and well-defined G-octamer system has been established through conformational design of monomers. The crystal structures of G-octamers were obtained for the first time. The covalent linked G-quadruplex exhibited significantly improved stability in both methanol and DMSO.
Anisotropic strain release in a thermosalient crystal: correlation between the microscopic orientation of molecular rearrangements and the macroscopic mechanical motion
We report the salient effect of the crystal of gold complex that bridges the gap between macroscopic mechanical movements (i.e., jump) and microscopic changes of the crystal structure.
Highly selective palladium-catalyzed one-pot, five-fold B–H/C–H cross coupling of monocarboranes with alkenes
Palladium-catalyzed five-fold B–H/C–H cross coupling of monocarboranes with alkenes enables the synthesis of selectively penta-functionalized boron clusters.
Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl
The first insertion reaction of CO with a molecular complex of the heavy p-block elements is reported (principal quantum number > 4).
Constructing new metal–organic frameworks with complicated ligands from “One-Pot” in situ reactions
A “One-Pot” strategy has been developed to construct new metal–organic frameworks with complicated ligands from simple precursors by integrating organic and coordination chemistry.
A catalytic protein–proteomimetic complex: using aromatic oligoamide foldamers as activators of RNase S
An aromatic oligoamide foldamer acts as an α-helix mimetic and binds to the RNase S-protein resulting in restoration of its catalytic function.
Controlling a burn: outer-sphere gating of hydroxylamine oxidation by a distal base in cytochrome P460
One amino acid makes the difference between a metalloenzyme and a metalloprotein in two otherwise effectively identical cytochrome P460s.
Thorium- and uranium-azide reductions: a transient dithorium-nitride versus isolable diuranium-nitrides
Evidence for a transient, highly reactive ThNTh nitride is presented, in contrast to uranium analogues that are stable and isolable. Surprisingly, computational studies reveal a σ > π energy ordering for all these bridging nitride bonds, a phenomenon for actinides only observed before in terminal uranium nitrides and uranyl.
Dithiane-directed Rh(III)-catalyzed amidation of unactivated C(sp3)–H bonds
A Rh(III) catalysed dithiane directed C(sp3)–H amidation for the synthesis of usefully protected β-aminoaldehyde derivatives is described.
Revising the measurement process in the variational quantum eigensolver: is it possible to reduce the number of separately measured operators?
We have introduced two approaches to reduce the number of separately measured terms in molecular Hamiltonians within the Variational Quantum Eigensolver (VQE) technique for solving the electronic structure problem.
Facile synthesis of AIEgens with wide color tunability for cellular imaging and therapy
Facile synthesis and bio-applications of a series of AIEgens with widely tunable emissions ranging from violet to near-infrared are reported.
A chemical reaction controlled by light-activated molecular switches based on hetero-cyclopentanediyls
Biradicals were applied as molecular switches to control chemical reactions that involve the activation of small molecules. The mechanism was studied by experimental and computational methods.
A dinuclear ruthenium(II) phototherapeutic that targets duplex and quadruplex DNA
A previously reported dinuclear DNA imaging probe has been converted into a phototherapeutic through the incorporation of RuII(TAP)2 fragments (TAP = 1,4,5,8-3 tetraazaphenanthrene).
ppm Pd-catalyzed, Cu-free Sonogashira couplings in water using commercially available catalyst precursors
A new catalyst that derives from commercially available precursors for copper-free, Pd-catalyzed Sonogashira reactions at the sustainable ppm level of precious metal palladium under mild aqueous micellar conditions has been developed.
Catalytic asymmetric allylation of aldehydes with alkenes through allylic C(sp3)–H functionalization mediated by organophotoredox and chiral chromium hybrid catalysis
We have developed a catalytic asymmetric nucleophilic allylation of aldehydes using simple alkenes as pronucleophiles without relying on stoichiometric metals.
Nickel-catalyzed anti-Markovnikov hydroarylation of alkenes
We have developed a nickel-catalyzed anti-Markovnikov hydroarylation of alkenes using aryl halides as coupling partners.
Catalytic radical difluoromethoxylation of arenes and heteroarenes
The first visible light photocatalytic generation and utilization of the OCF2H radical for direct (hetero)aryl C–H difluoromethoxylation at room temperature.
Hydroxyl-mediated ethanol selectivity of CO2 hydrogenation
This paper describes the promotional effect of hydroxyl groups over RhFeLi/TiO2 catalysts for the ethanol synthesis via CO2 hydrogenation.
Stereoselective synthesis of alkyl-, aryl-, vinyl- and alkynyl-substituted Z-enamides and enol ethers
Highly stereoselective synthesis of Z-enamides and enol ethers at room temperature via an umpolung/cross coupling strategy applicable to drugs and natural products.
Acyclic 1,2-dimagnesioethanes/-ethene derived from magnesium(I) compounds: multipurpose reagents for organometallic synthesis
The sometimes redox reversible 1,2-additions of magnesium(I) dimers across several alkenes and one alkyne yield 1,2-dimagnesioethanes and a 1,2-dimagnesioethene. Treatment of these with bulky amido metal halide precursors affords novel products via three reactivity modes.
Enantioselective intramolecular C–H amination of aliphatic azides by dual ruthenium and phosphine catalysis
By combining a chiral-at-metal ruthenium catalyst with catalytic amounts of tris(p-fluorophenyl)phosphine (both 1 mol%), the challenging catalytic enantioselective ring-closing C(sp3)-H amination of unactivated aliphatic azides has been achieved with high enantioselectivities.
An Al-doped SrTiO3 photocatalyst maintaining sunlight-driven overall water splitting activity for over 1000 h of constant illumination
The development of robust and efficient water splitting photocatalysts overcomes a long-standing barrier to sustainable large-scale solar hydrogen evolution systems.
Dinuclear manganese alkoxide complexes as catalysts for C–N bond cleavage of simple tertiary N,N-dialkylamides to give esters
Amide bonds are stable due to the resonance between the nitrogen lone pair and the carbonyl moiety, and therefore the chemical transformation of amides, especially tertiary amides, involving C–N bond fission is considered one of the most difficult organic reactions, unavoidably requiring harsh reaction conditions and strong acids or bases.
Cooperativity basis for small-molecule stabilization of protein–protein interactions
A cooperativity framework to describe and interpret small-molecule stabilization of protein–protein interactions (PPI) is presented, which allows elucidating structure–activity relationships regarding cooperativity and intrinsic affinity.
Insights into mechanochemical reactions at the molecular level: simulated indentations of aspirin and meloxicam crystals
Working towards a fundamental description of mechanochemical reactions through the use of classical molecular dynamics simulations. Capturing the transfer of molecules between two non-volatile molecular crystals during mechanochemical events.
From nano-balls to nano-bowls
Depending on the reaction conditions, either guest or host truncation is observed upon self-assembly of [Cp*Fe(η5-P5)], [(CpCr)2(η5-As5)] and copper halides.
Structure revision of cryptosporioptides and determination of the genetic basis for dimeric xanthone biosynthesis in fungi
Three novel dimeric xanthones, cryptosporioptides A–C were isolated from Cryptosporiopsis sp. 8999 and their structures elucidated.
Through-space charge transfer hexaarylbenzene dendrimers with thermally activated delayed fluorescence and aggregation-induced emission for efficient solution-processed OLEDs
Through-space charge transfer hexaarylbenzene dendrimers containing circularly-arrayed electron donors and acceptors exhibit thermally activated delayed fluorescence and aggregation-induced emission effects, giving EQE of 14.2% for solution-processed OLEDs.
A molecular picture of surface interactions of organic compounds on prevalent indoor surfaces: limonene adsorption on SiO2
Integration of experiment, theory and modeling to understand the interaction type and kinetics of limonene on silica surfaces.
Influence of intramolecular secondary sphere hydrogen-bonding interactions on cytochrome c oxidase inspired low-spin heme–peroxo–copper complexes
Structural/electronic influence of metalloenzyme-inspired synthetic heme–peroxo–copper models containing intramolecular hydrogen bonding interactions.
Achieving efficient and robust catalytic reforming on dual-sites of Cu species
This paper describes how Cu+ species act as electrophilic sites to facilitate the adsorption and activation of formate and restrict the Ostwald ripening of Cu species, leading to an efficient and robust steam reforming of bio-DME.
Heterolytic bond activation at gold: evidence for gold(III) H–B, H–Si complexes, H–H and H–C cleavage
Gold(III) forms spectroscopically detectable H–B and H–Si σ-complexes; experiments and DFT calculations demonstrate heterolytic H–Si, H–H and H–C bond cleavage.
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.