Research

This list contains the 50 most recently published research articles, including advance online publication articles that have not yet been published in a journal issue.

Showing: 1–25 of 50

AOP
  1. Placing and shaping liposomes with reconfigurable DNA nanocages

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    Controlling liposome shape, arrangement and dynamics is important for biophysical studies and synthetic biology applications. Now, using a family of reconfigurable DNA nanocages as templates, spherical, tubular, toroidal and helical liposomes with predefined geometry have been produced. DNA-guided membrane fusion and bending is also demonstrated.

    See also: News and Views by Stefan Howorka

  2. CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis AOP

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    Previous methods to transform unsaturated substrates into carbonyl-containing products have generally relied on the use of hazardous carbon monoxide and tailor-made catalysts for each nucleophile employed. Now, shuttle catalysis can be used to perform a CO- and HCl-free transfer hydrochlorocarbonylation to access acid chlorides that can be transformed in situ into virtually any carbonyl-containing product.

  3. Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates AOP

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    Both click chemistry and polymer synthesis require reliable transformations with high selectivity, efficiency and fidelity. Now, bifluoride salts can be used as powerful catalysts for the sufur(VI) fluoride exchange (SuFEx) click reaction and they are applied to the synthesis of polysulfates and polysulfonates in a practical and scalable manner.

  4. Total synthesis of (–)-tubingensin B enabled by the strategic use of an aryne cyclization AOP

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    The total synthesis of tubingensin B — an indole diterpenoid that bears a daunting chemical structure — has now been achieved. The design and evolution of this succinct total synthesis underscores the utility of long-avoided aryne intermediates for the introduction of structural motifs that have conventionally been viewed as challenging.

  5. Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation AOP

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    With recent and improved understanding of how nuclear and electronic degrees of freedom can interact with each other comes the opportunity to directly control electronic processes. Now it has been shown that ultrafast vibrational excitation can direct light-induced intramolecular electron transfer along a specific path.

  6. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst AOP

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    It is still a great challenge to synthesize value-added products with two or more carbons directly from CO2. Now, a bifunctional catalyst composed of reducible metal oxides (In2O3) and zeolites (HZSM-5) is prepared and yields high selectivity to gasoline-range hydrocarbons (78.6%) with a high octane number directly from CO2 hydrogenation.

  7. Structural snapshots of concerted double E–H bond activation at a transition metal centre AOP

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    X-ray and neutron diffraction studies, in conjunction with quantum chemical techniques, have been used to define a new oxidative bond activation pathway that involves simultaneous activation of both bonds of a β-diketiminate-stabilized GaH2 unit at a single metal centre.

  8. Catalytic asymmetric trifluoromethylthiolation via enantioselective [2,3]-sigmatropic rearrangement of sulfonium ylides AOP

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    The asymmetric Doyle-Kirmse reaction using chiral Rh(II)- or Cu(I)-catalysts provides SCF3-containing compounds in highly efficient and enantioselective manner. The reaction proceeds through enantioselective formation of sulfonium ylide from a diazoester and allyl- or propargyl trifluoromethyl sulfide, followed by concerted [2,3]-sigmatropic rearrangement with the transfer of chirality from sulfur to carbon.

  9. Complete protein–protein association kinetics in atomic detail revealed by molecular dynamics simulations and Markov modelling AOP

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    Uncovering the microscopic details of protein–protein association via direct molecular dynamics (MD) simulations has been prevented by the excessive lifetimes of associated states. Now, association and dissociation for the barnase–barstar complex has been studied by adaptive high-throughput MD simulations and Markov modelling, revealing intermediate structures, energetics and kinetics on microseconds-to-hours timescales.

  10. Coherent singlet fission activated by symmetry breaking AOP

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    Singlet fission — converting a singlet exciton to two triplet excitons — may be useful for improving photovoltaic efficiency. Ultrafast spectroscopic measurements and quantum chemical calculations have now uncovered aspects of the process critical to it occurring efficiently, including the role of intermolecular vibrations and symmetry breaking, and the location of a conical intersection on the excited-state potential energy surface.

  11. A reductive aminase from Aspergillus oryzae AOP

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    An enzyme (AspRedAm) capable of coupling carbonyls with a variety of amines in a reductive amination has now been discovered. Kinetic studies revealed that the enzyme catalysed both the imine formation step, as well as the reduction step. Structure and mutagenesis studies have highlighted essential catalytic residues and preparative scale examples have demonstrated total turnover numbers up to 32,000.

  12. Enantioselective, intermolecular benzylic C–H amination catalysed by an engineered iron-haem enzyme

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    The intermolecular amination of C–H bonds is an enabling transformation for the synthesis of nitrogen-containing molecules; however, developing catalysts for this class of reactions is very challenging. Now, an iron-based enzyme for this reaction has been engineered, demonstrating that a protein can confer a difficult new function upon an otherwise unreactive base metal.

    See also: News and Views by Rudi Fasan

  13. Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity

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    The oxidative prowess of cytochrome P450s has been suggested to stem from the electron-donating axial ligand. Now, a selenocysteine-ligated P450 compound I has been trapped and characterized providing an avenue to examine this hypothesis. Measurements reveal that the selenolate-ligated compound I cleaves C–H bonds more rapidly than the wild-type equivalent.

    See also: News and Views by Rudi Fasan

  14. Cytosolic antibody delivery by lipid-sensitive endosomolytic peptide AOP

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    The trapping of antibodies in endosomes often limits their use for intracellular targeting. Now, a single amino acid substitution on a spider-venom peptide has been shown to attenuate the cell membrane lytic activity and enables the selective rupturing of endosomal membranes. The peptide can be used to facilitate the escape of antibodies from endosomes into the cytosol.

  15. Salinomycin kills cancer stem cells by sequestering iron in lysosomes AOP

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    Cancer stem cells are typically refractory to conventional treatments. Now, an unprecedented mechanism has been discovered by which salinomycin and derivatives can sequester iron in lysosomes leading to cytoplasmic iron depletion and the subsequent production of reactive oxygen species that are lethal to the cell. This discovery of the importance of iron in cancer stem cell maintenance provides an opportunity for developing new therapeutics.

  16. Incipient class II mixed valency in a plutonium solid-state compound AOP

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    Unlike in the d block, intervalence charge transfer is rare in the 5f block owing to localized valence electrons and poor overlap between metal and ligand orbitals. Delocalization of 5f electrons has now been observed in a Pu(III)/Pu(IV)–pyridinedicarboxylate solid-state compound. It occurs through metal-to-ligand charge transfer with both plutonium centres.

  17. Anionic silicate organic frameworks constructed from hexacoordinate silicon centres AOP

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    Hexacoordinate silicon is seen often in molecular compounds, but very rarely in crystalline silicate materials. Now, reversible Si–O chemistry has been used to assemble octahedral dianionic SiO6 building units and anthracene derivatives into crystalline, microporous silicate organic frameworks that share characteristics of both covalent organic frameworks and inorganic zeolites.

  18. Synthesis and materialization of a reaction–diffusion French flag pattern AOP

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    A DNA-based reaction network has now been developed that creates a French flag pattern with immobile and sharp borders from a shallow initial concentration gradient. The output pattern can be used to control the macroscopic organization of DNA-decorated particles thereby inducing a French flag pattern of colloidal aggregation.

  19. Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions AOP

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    The field of high-valent uranium chemistry has been dominated by the linear uranyl moiety [UO2]2+ and its imido analogues. A family of tetrakis(imido)uranate dianions has now been developed that displays four uranium–nitrogen multiple bonds. Their geometry is dictated by cation coordination and steric factors rather than electronic ones.

  20. Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

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    Reports of superconductivity in KxPicene spurred interest in alkali-intercalated polyaromatic hydrocarbon (PAH) compounds, but their compositions and structures have remained unclear. Now crystalline K2Pentacene and K2Picene — neither of which are superconducting — have been prepared by mild synthesis. Structural analysis shows that the cation sites arise within the molecular layers from reorientation of the PAHs within a herringbone packing.

    See also: Article by Yasuhiro Takabayashi et al., News and Views by Roser Valentí et al.

  21. π-electron S = ½ quantum spin-liquid state in an ionic polyaromatic hydrocarbon

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    Cooperative electronic properties that arise purely from carbon π-electrons can lead to unconventional superconductivity and quantum magnetism. New packing architectures have now been established in two caesium-intercalated polyaromatic hydrocarbons, CsPhenanthrene and Cs2Phenanthrene, both strongly correlated multi-orbital Mott insulators. The frustrated magnetic topology in CsPhenanthrene also renders it a spin-½ quantum spin liquid candidate.

    See also: Article by F. Denis Romero et al., News and Views by Roser Valentí et al.

  22. Transition-metal-free chemo- and regioselective vinylation of azaallyls AOP

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    Cross coupling under transition-metal-free conditions is an attractive and economic alternative to traditional transition metal-catalysed methods. Metal-free coupling of azaallyls has now been demonstrated with vinyl bromide electrophiles, delivering allylic amines in excellent yields. Moreover, mechanistic evidence supports dual reaction pathways triggered by azaallyl anions and radicals.

  23. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6 AOP

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    The assembly–disassembly–organization–reassembly (ADOR) process has recently enabled the synthesis of unusual — and sometimes previously inaccessible — inorganic materials. Further insight into its complex mechanism has now been gained that explains the unexpected formation and structure of such a zeolite.