Nanoscale materials articles within Nature Chemistry

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  • News & Views |

    The first two examples of zigzag carbon nanobelts have been reported. These compounds have been elusive targets for synthetic chemists for 35 years, but strategic structural modifications and mastering challenging multi-step syntheses finally brought success.

    • Birgit Esser
    •  & Mathias Hermann
  • Article |

    Stimuli-responsive control of drug activation can mitigate issues caused by poor drug selectivity. Now, it has been shown that mechanical force—induced by ultrasound—can be used to activate drugs in three different systems. This approach has enabled the activation of antibiotics or a cytotoxic anticancer agent from synthetic polymers, polyaptamers and nanoparticle assemblies.

    • Shuaidong Huo
    • , Pengkun Zhao
    •  & Andreas Herrmann
  • Article |

    A six-helix bundle DNA structure called meta-DNA has now been assembled and shown to possess some structural properties similar to those of single-stranded DNA. Two meta-DNAs containing complementary ‘meta-base pairs’ are shown to form double helices. Meta-DNA building blocks are also used to construct a series of DNA architectures and to perform a hierarchical strand-displacement reaction.

    • Guangbao Yao
    • , Fei Zhang
    •  & Hao Yan
  • News & Views |

    A series of mesoscale supramolecular hexagonal grids have been constructed in solution through stepwise intra- then intermolecular coordination-driven self-assembly, and characterized with atomic resolution by scanning tunnelling microscopy and spectroscopy.

    • Ruoning Li
    •  & Yongfeng Wang
  • Article |

    The photoinduced dimerization of a prochiral anthracenecarboxylic acid occurs in an enantioselective fashion when the molecules are adsorbed on helical metal nanostructures. This enantiopreference arises mostly from the helicity of the silver and copper substrates—prepared using shear forces during the deposition process—and may also be influenced by chiroplasmonic effects.

    • Xueqin Wei
    • , Junjun Liu
    •  & Zhifeng Huang
  • Article |

    Metal-mediated self-assembly in solution typically leads to small two- and three-dimensional architectures on scales smaller than 10 nm, but now a series of large, discrete, two-dimensional supramolecular hexagonal grids have been prepared through a combination of intra- and intermolecular coordination interactions. These 20-nm-wide grids have been imaged at submolecular resolution using scanning tunnelling microscopy.

    • Zhe Zhang
    • , Yiming Li
    •  & Xiaopeng Li
  • News & Views |

    A balance between order and disorder provides living materials with just the right amount of disorder needed to sustain life. This feature is currently not found in synthetic materials. Now, a route to the production of composite membranes that are simultaneously stiff and reconfigurable upon contact has been developed.

    • Ankit Jain
    •  & Rein V. Ulijn
  • Article |

    Controlling single-molecule magnets (SMMs) with ultrashort laser pulses could be key to future data storage devices, however, the photophysics of SMMs is complex. Now, using a monomer model system, it has been shown that optical excitation of Mn(iii)-SMMs leads to a modulation of the Jahn–Teller distortion, which is important for its magnetic anisotropy.

    • Florian Liedy
    • , Julien Eng
    •  & J. Olof Johansson
  • Article |

    The deposition of noble metals onto two-dimensional transition metal dichalcogenides is crucial for practical applications, including in catalysis and sensing, yet this process has remained difficult to control. Now, gold and silver have been shown to grow on colloidal transition metal dichalcogenide nanosheets into either atomically thin layers or nanoparticles whose sizes and morphologies depend on the relative strengths of the interfacial noble metal–chalcogen bonds.

    • Yifan Sun
    • , Yuanxi Wang
    •  & Raymond E. Schaak
  • Article |

    Quantum dots functionalized with energy-accepting dyes hold promise for converting low-energy photons into higher-energy visible light for bioimaging, catalysis and solar energy harvesting. Now, it has been shown that non-toxic silicon quantum dots can be used in these systems; the transfer of spin-triplet excitons to molecules at their surface has been observed.

    • Pan Xia
    • , Emily K. Raulerson
    •  & Sean T. Roberts
  • Article |

    A solution-processing step has been used to prepare quantum-well structures that comprise a thin layer of perovskite sandwiched between two layers of conjugated oligothiophene derivatives. The band gap of the resulting 2D hybrid perovskites can be fine-tuned by functionalizing the organic component, which also improves the stability of the system.

    • Yao Gao
    • , Enzheng Shi
    •  & Letian Dou
  • Article |

    Tuning the selectivity for [2+2] photocycloadditions remains challenging. Now, triplet–triplet energy transfer from CdSe quantum dots enables the homo- and heterocouplings of 4-vinylbenzoic acid derivatives via [2+2] photocycloaddition. Preorganization of substrates on the quantum dots reverses intrinsic stereoelectronic preferences to yield cyclobutane products with unprecedented diastereo- and regioselectivity.

    • Yishu Jiang
    • , Chen Wang
    •  & Emily A. Weiss
  • News & Views |

    Frank–Kasper phases are topologically close-packed structures typically found in ordered mixtures of ‘hard particles’ such as metallic alloys. Now, a shape amphiphile has been shown to self-assemble into a Frank–Kasper Z phase, which had so far remained elusive in soft materials.

    • Abhiram Reddy
    •  & Gregory M. Grason
  • Article |

    The Z phase, one of three fundamental Frank–Kasper phases—topologically close-packed structures commonly found in metal alloys—is associated with a relatively large volume ratio between its constituents. This means it is typically not formed in single-component soft materials. Now, a shape amphiphile has been shown to self-assemble in a variety of unconventional structures, including the Z phase.

    • Zebin Su
    • , Chih-Hao Hsu
    •  & Stephen Z. D. Cheng
  • Article |

    Polyacetylene is an ideal system to probe to gain a better understanding of the nature of charge transport in conducting polymers. Now, individual atomically precise polyacetylene chains have been synthesized on a copper surface and characterized using a range of techniques, revealing a doping-induced semiconductor-to-metal transition.

    • Shiyong Wang
    • , Qiang Sun
    •  & Wei Xu
  • News & Views |

    Precipitation processes enable the fast preparation of a variety of inorganic materials, although typically with little control over their morphology. Now, their one-, two- or three-dimensional growth has been promoted simply by tuning the electrolytic dissociation of the reactants and the supersaturation of the solution.

    • Mihui Park
    • , Gi-Hyeok Lee
    •  & Yong-Mook Kang
  • Article |

    Precipitation enables the straightforward production of a variety of inorganic materials, but the rapid reaction rates involved typically make controlling their morphologies difficult. Now, the growth of either one-, two- or three-dimensional materials has been promoted by tuning of the reactants’ electrolytic dissociation and solution supersaturation, without the need for capping agents and templates.

    • Wei-Hong Lai
    • , Yun-Xiao Wang
    •  & Shi-Xue Dou
  • Article |

    In native photosystem II (PSII), multi-chromophore antennas surround the reaction centre, capturing light and triggering the quantized (four-flashes) photo-oxidation of water to oxygen. The PSII ‘quantasome’ is the most efficient photo-electrolyser built so far. An artificial quantasome has now been developed; it is specifically designed for oxygen evolution by self-assembling light-harvesting-perylene bisimides with a ruthenium polyoxometalate water-oxidation catalyst.

    • Marcella Bonchio
    • , Zois Syrgiannis
    •  & Maurizio Prato
  • Article |

    MoS2 single layers spontaneously undergo a slow oxygen substitution reaction under ambient conditions giving rise to solid-solution-type 2D molybdenum oxy-sulfide crystals. The oxygen substitution sites of the 2D MoS2xOx crystals act as efficient single-atom catalytic centres for the hydrogen evolution reaction.

    • János Pető
    • , Tamás Ollár
    •  & Levente Tapasztó
  • Article |

    Aryl functionalization of carbon nanotubes generates sp3 defects capable of quantum light emission. A multiplicity of possible binding configurations, however, leads to spectrally diverse emission bands. Now, it is shown that the structural symmetry of zigzag nanotubes and a high chemical selectivity for ortho configurations results in defect-state emission from a single narrow band.

    • Avishek Saha
    • , Brendan J. Gifford
    •  & Stephen K. Doorn
  • Article |

    Surface engineering is an attractive route to tune the processability, stability and functionalities of 2D materials, but typically introduces defects in the resulting structures. Now, the issue has been circumvented through pre-synthetic functionalization instead; an isoreticular family of robust layered coordination polymers has been mechanically exfoliated to give functionalized crystalline magnetic monolayers.

    • J. López-Cabrelles
    • , S. Mañas-Valero
    •  & E. Coronado
  • Article |

    As of yet, no clear structure–performance descriptors have been developed to tune the catalytic activity of zeolitic methanol-to-olefin catalysts. Now it has been shown that introducing Lewis acidity into Brønsted acidic zeolites boosts their performance. Although Brønsted acidity is found to define propylene selectivity, Lewis acidity is responsible for prolonging lifetime.

    • Irina Yarulina
    • , Kristof De Wispelaere
    •  & Jorge Gascon
  • News & Views |

    Sodium chloride phases with unconventional non-1:1 stoichiometries are known to exist under high-pressure conditions. Now, Na2Cl and Na3Cl two-dimensional crystals have been obtained under ambient conditions, on graphene surfaces, from dilute solutions.

    • Artem R. Oganov
  • News & Views |

    The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

    • Bert M. Weckhuysen
  • Article |

    The common form of salt has a 1:1 ratio of Na+ and Cl; however, species that deviate from this can be found under extreme conditions, such as high pressure. Now, as a result of cation–π interactions that promote ion–surface adsorption, Na2Cl and Na3Cl have been observed as two-dimensional crystals on graphene at ambient conditions.

    • Guosheng Shi
    • , Liang Chen
    •  & Haiping Fang
  • Article |

    Multi-electron redox reactions are kinetically sluggish; however, plasmonic nanoparticles have shown promise as multi-electron reduction catalysts. Now, the principles that govern the harvesting of multiple electron–hole pairs from plasmonically excited gold nanoparticle photocatalysts are elucidated, providing a general foundation for the plasmonic catalysis of challenging multi-electron, multi-proton chemistry, such as N2 fixation and CO2 reduction.

    • Youngsoo Kim
    • , Jeremy G. Smith
    •  & Prashant K. Jain
  • Article |

    Living systems rely on externally tuneable and stimuli-responsive conformational changes of proteins and protein assemblies for a wide range of essential functions. A combination of experimental and computational analyses has now enabled the fabrication of a rationally designed, synthetic, stimuli-responsive protein assembly through modulation of its free-energy landscape.

    • Robert Alberstein
    • , Yuta Suzuki
    •  & F. Akif Tezcan
  • Article |

    The phase in which a crystal exists can have a direct influence over its properties; however, it is usually difficult to control during synthesis. Now it has been shown that micrometre-sized metallic 1T′-MoS2- and 1T′-MoSe2-layered crystals can be prepared in high phase purity on a large scale, and that they display promising electrocatalytic activity towards the hydrogen evolution reaction.

    • Yifu Yu
    • , Gwang-Hyeon Nam
    •  & Hua Zhang
  • Article |

    Nanocatalysts can undergo various dynamic phenomena that affect their activity, such as restructuring and spillover. Now, using spatially and temporally resolved imaging of individual catalytic reactions, cooperative communication between different sites within single palladium- and gold-based nanocatalysts, and between different nanocatalysts, has been observed during three distinct catalytic reactions.

    • Ningmu Zou
    • , Xiaochun Zhou
    •  & Peng Chen
  • Article |

    Heterometallic nanomaterials in unusual crystal phases that are impossible to form in the bulk state can show interesting physical and chemical properties. Here, crystal-phase heterostructured 4H/fcc Au nanowires are used as seeds to epitaxially grow a variety of binary and ternary hybrid noble metal nanostructures on the phase boundary.

    • Qipeng Lu
    • , An-Liang Wang
    •  & Hua Zhang
  • Article |

    Complex interfacial supramolecular architectures promise unique physical and chemical properties, but are challenging to make. Now, it has been shown that a simple organic precursor can undergo a convergent multi-step on-surface transformation to give more complex building blocks that assemble into a semi-regular Archimedean tessellation with long-range order.

    • Yi-Qi Zhang
    • , Mateusz Paszkiewicz
    •  & Florian Klappenberger
  • Article |

    A renewed interest in C–H bond activation has developed on account of the recent increased availability of shale gas. Now, using a combination of surface science, microscopy, theory and nanoparticle studies, the ability of coke-resistant Pt/Cu single-atom alloys to efficiently activate C–H bonds in alkanes has been demonstrated under realistic catalytic conditions.

    • Matthew D. Marcinkowski
    • , Matthew T. Darby
    •  & E. Charles H. Sykes
  • Article |

    A practical realization of selective IR-driven reaction-rate control has been hampered by competing processes leading to sample heating. Now, the acceleration of a bimolecular ground-state reaction in solution using the IR excitation of a vibration connected to the reaction coordinate is demonstrated. The behaviour is monitored and understood using a combination of femtosecond IR-pump IR-probe spectroscopy and theoretical calculations.

    • Till Stensitzki
    • , Yang Yang
    •  & Karsten Heyne
  • Article |

    The ability to merge the photophysical properties of semiconductor quantum dots with those of well-understood and inexpensive molecular chromophores is important for the development of various emerging photonic and optoelectronic technologies. Now, 1-pyrenecarboxylic acid-functionalized CdSe quantum dots have been shown to undergo thermally activated delayed photoluminescence and display tunable photophysical properties.

    • Cédric Mongin
    • , Pavel Moroz
    •  & Felix N. Castellano
  • Article |

    Photosynthesis uses sunlight to oxidize or reduce reaction centres multiple times and prepare them for multiple-electron-transfer reactions. Now, it has been shown that a molecular proxy for a multiple-electron-transfer electrocatalyst can be oxidized twice by dye molecules when both are anchored to a mesoporous TiO2 thin film and excited with low-intensity visible light.

    • Hsiang-Yun Chen
    •  & Shane Ardo
  • News & Views |

    Non-covalent interactions can organize planar molecules into two-dimensional arrays. It has now been shown that such arrays can be combined at the solid–liquid interface into bilayered heterostructures.

    • Manfred Buck
  • News & Views |

    Building materials with clusters instead of atoms promises unconventional properties, but those 'superatomic solids' are often too fragile to manipulate. Now, intercalating a guest within an ionic layered solid made of fullerenes and metal chalcogenide clusters greatly alters its conductivity and optical properties without disrupting its crystalline structure.

    • Shiv N. Khanna
    •  & Arthur C. Reber
  • News & Views |

    DNA double helical structures are supramolecular assemblies that are typically held together by classical Watson–Crick pairing. Now, nucleotide chelation of silver ions supports an extended silver–DNA hybrid duplex featuring an uninterrupted silver array.

    • Pascal Auffinger
    •  & Eric Ennifar
  • Article |

    Intercalation — a cornerstone of materials science with wide-ranging applications — has now been demonstrated in a superatomic crystal. A redox-active tetracyanoethylene guest was inserted into the lattice of a material consisting of alternate layers of {Co6Te8} clusters and C60 fullerenes, leading to a single-crystal-to-single-crystal transformation that significantly modulates the material's optical and electrical transport properties.

    • Evan S. O'Brien
    • , M. Tuan Trinh
    •  & Xavier Roy
  • Article |

    Supramolecular heterostructures have been formed by the sequential deposition of two molecular layers with different symmetries and lattice constants — one consisting of carboxylic acid, the other of cyanuric acid and melamine — on a hexagonal boron nitride substrate. Characterization by atomic force microscopy and molecular dynamics simulations shows epitaxial arrangements between the layers.

    • Vladimir V. Korolkov
    • , Matteo Baldoni
    •  & Peter H. Beton
  • Article |

    Octameric complexes of serine are long known for their special properties, such as their enhanced stability and preference for homochirality. Yet, there is no consensus on their structures. Now, experimental data on the serine octamer–dichloride complex is presented that supports a highly symmetrical, highly stable structure.

    • Jongcheol Seo
    • , Stephan Warnke
    •  & Gert von Helden
  • Article |

    A metallo–DNA hybrid nanowire composed only of silver-mediated base pairs has been prepared and its crystal structure resolved by X-ray diffraction. The nanowire, which is 2 nm wide and whose length reaches the μm to mm scale, holds silver ions into uninterrupted one-dimensional arrays along the DNA helical axis.

    • Jiro Kondo
    • , Yoshinari Tada
    •  & Yoshiyuki Tanaka
  • Article |

    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.

    • Zhao Zhang
    • , Yang Yang
    •  & Chenxiang Lin
  • Article |

    Converting oxygen-rich biomass into fuels requires the removal of oxygen groups through hydrodeoxygenation. MoS2 monolayer sheets decorated with isolated Co atoms bound to sulfur vacancies in the basal plane have now been synthesized that exhibit superior catalytic activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene when compared to conventionally prepared materials.

    • Guoliang Liu
    • , Alex W. Robertson
    •  & Shik Chi Edman Tsang
  • Article |

    Di- and tripeptide building blocks in which the C-terminus has been converted into an aldehyde are shown to form dynamic chemical networks through imine condensation followed by the formation of cyclic N,N-acetals. The networks exhibit multi-phase growth of prion-like assemblies that template the formation of chain-length-specific peptide-like oligomers.

    • Chenrui Chen
    • , Junjun Tan
    •  & David G. Lynn
  • Article |

    Simple peptides are shown to assemble into well-defined amyloid phases with paracrystalline surfaces that can catalyse reactions in an enantioselective manner. Modifying individual amino acids in the building blocks enables the structure of the assembled aggregates, and the reactions that they can catalyse, to be controlled predictably.

    • Tolulope O. Omosun
    • , Ming-Chien Hsieh
    •  & David G. Lynn
  • News & Views |

    The process of electronic energy transfer between molecules has long fascinated chemists. Femtosecond spectroscopy measurements of a series of molecular dimers now reveal signals that arise from non-Born–Oppenheimer coupling, suggesting a new mechanism to enhance energy transfer.

    • Daniel B. Turner
  • Article |

    Synthetic heterodimers provide a platform to demonstrate molecular design principles of vibronic coupling. Now, it has been shown that quantum beating caused by vibronic coupling can be controlled by packing a structurally flexible heterodimer on single-walled carbon nanotubes. This quantum beating requires a vibration to be resonant with the energy gap between excited states and structural rigidity.

    • Lili Wang
    • , Graham B. Griffin
    •  & Gregory S. Engel