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A chemically powered unidirectional rotary molecular motor based on a palladium redox cycle
Control of motion at the molecular level is an integral requirement for the development of future nanoscale machinery. Now, governed by the fundamental reactivity principles of organometallic chemistry, a biaryl rotor is shown to exhibit 360° unidirectional rotary motion driven by the conversion of two simple fuels.
- Beatrice S. L. Collins
- , Jos C. M. Kistemaker
- & Ben L. Feringa
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Quasicrystallinity expressed in two-dimensional coordination networks
Quasicrystalline materials exhibit long-range order but no translational periodicity. Now, a random tiling quasicrystal has been fabricated on a Au(111) surface by coordination interactions between europium centres and linear dicarbonitrile linkers under stoichiometry control. The 2D metal–organic network exhibits the simultaneous presence of four-, five- and six-fold vertices and dodecagonal symmetry.
- José I. Urgel
- , David Écija
- & Johannes V. Barth
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Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry
Few-layer black phosphorus (BP) is a promising semiconductor, but it is highly reactive and susceptible to ambient degradation. Covalent functionalization with aryl radicals has now been shown to significantly improve the stability of exfoliated BP, as well as the performance of BP-based electronic devices through a controllable p-type doping effect.
- Christopher R. Ryder
- , Joshua D. Wood
- & Mark C. Hersam
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Dissipative self-assembly of vesicular nanoreactors
Dissipative self-assembly processes are energetically uphill and require the continuous consumption of energy. Now, by using ATP as a chemical fuel, the dissipative self-assembly of vesicles has been demonstrated. These transiently formed supramolecular assemblies are able to sustain a chemical reaction and it is shown that the yield depends on the lifetime of the vesicles.
- Subhabrata Maiti
- , Ilaria Fortunati
- & Leonard J. Prins
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News & Views |
Polyphony in B flat
Early theories suggested the possibility of atomically thin boron layers, but electron-deficient boron favours multicentre bonds and assembles into various polymorphs, making the synthesis of such layers challenging. Now, in two independent experiments, the deposition of atomic boron has offered this long-sought material on a silver platter.
- Zhuhua Zhang
- , Evgeni S. Penev
- & Boris I. Yakobson
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Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions
The influence of the thermodynamic driving force for photoinduced electron-transfer between single-walled carbon nanotubes and fullerene derivatives has been investigated. The Marcus inverted region and small reorganization energies were observed for this model organic heterojunction. Small reorganization energies aid in minimizing energy losses for solar conversion to electricity or fuels.
- Rachelle Ihly
- , Kevin S. Mistry
- & Jeffrey L. Blackburn
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Chemical polyglycosylation and nanolitre detection enables single-molecule recapitulation of bacterial sugar export
Capsular polysaccharides are a protective layer enveloping pathogenic bacteria. Understanding their export could guide the design of therapeutics that render bacteria vulnerable to attack by the immune system or other therapeutic agents. Now, a synthetic strategy of polyglycosylation has been developed to obtain defined capsular polysaccharide fragments. Subsequent nanolitre detection enables their export to be studied at the single-molecule level.
- Lingbing Kong
- , Andrew Almond
- & Benjamin G. Davis
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An autonomous molecular assembler for programmable chemical synthesis
Molecular machines that assemble polymers in a programmed sequence are fundamental to life. Now, synthetic machinery built from DNA has been used to execute a molecular program that produces peptides, or olefin oligomers, with a defined sequence. The oligomeric product is linked to a double-stranded DNA product that records the sequence of reactions that were executed.
- Wenjing Meng
- , Richard A. Muscat
- & Andrew J. Turberfield
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Molecular rectifier composed of DNA with high rectification ratio enabled by intercalation
Understanding the correlation between structure and charge transport properties of a DNA-based single molecule device is crucial to the creation of nanoscale functional devices. Now, a DNA-based molecular rectifier with a high rectification ratio has been constructed by site-specific intercalation of small molecules (coralyne) into native double-stranded DNA.
- Cunlan Guo
- , Kun Wang
- & Bingqian Xu
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Experimental realization of two-dimensional boron sheets
A variety of two-dimensional materials have been reported in the past few years, yet single-element systems—such as graphene and black phosphorus—have remained rare. 2D allotropes of boron have long been predicted and recently investigated. Two boron sheets have now been grown on a Ag(111) surface by molecule beam epitaxy that exhibit significant chemical stability against oxidation.
- Baojie Feng
- , Jin Zhang
- & Kehui Wu
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News & Views |
Mismatched lattices patched up
Controlling interfaces between transition-metal oxides and dissimilar structures is crucial for practical applications, yet has remained a quandary. Now, a coherent interface that bridges a perovskite and a fluorite structure has been formed using judiciously chosen metal cations.
- Kenneth R. Poeppelmeier
- & James M. Rondinelli
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Self-assembly of size-controlled liposomes on DNA nanotemplates
Precise control of vesicle size is highly desirable both for basic biochemical research and biomedical applications. Now, monodispersed sub-100-nm vesicles with predefined sizes have been produced using a method based on membrane self-assembly within a DNA-nanostructure guide.
- Yang Yang
- , Jing Wang
- & Chenxiang Lin
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Controlled growth of high-density CdS and CdSe nanorod arrays on selective facets of two-dimensional semiconductor nanoplates
Controlling the morphology and composition of hybrid nanostructures is desirable for applications, but it has proven challenging to precisely combine different nucleation sites and growth modes. Now, three types of hierarchical 1D/2D nanostructures have been prepared by selectively growing semiconductor nanorod arrays (CdS or CdSe) on the different facets of hexagonal nanoplates.
- Xue-Jun Wu
- , Junze Chen
- & Hua Zhang
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Synthesis of a distinct water dimer inside fullerene C70
Endohedral C70 fullerenes containing either one or two water molecules have now been prepared using a molecular-surgery approach. The structure of H2O@C70 was determined by single-crystal X-ray analysis, revealing the encapsulated water molecule to be in an off-centre position. In (H2O)2@C70, the two water molecules form a discrete dimer held together with a single hydrogen bond.
- Rui Zhang
- , Michihisa Murata
- & Yasujiro Murata
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Reprogramming the assembly of unmodified DNA with a small molecule
Cyanuric acid, a small molecule with three thymine-like faces, reprogrammes the assembly of unmodified poly(adenine) into long fibres with a unique internal structure. The association of adenine and cyanuric acid units into a hexameric rosette motif brings together poly(adenine) triplexes with subsequent cooperative polymerization.
- Nicole Avakyan
- , Andrea A. Greschner
- & Hanadi F. Sleiman
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Interface control by chemical and dimensional matching in an oxide heterostructure
The behaviour of heterostructures, crucial in nanodevices, largely depends on interfacial phenomena. These have proven difficult to control when the different materials adopt distinct crystal structures. Now, a coherent interface between perovskite and fluorite has been achieved that relies in particular on the coordination flexibility of judiciously chosen metal cations.
- Marita O'Sullivan
- , Joke Hadermann
- & Matthew J. Rosseinsky
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Reversible Bergman cyclization by atomic manipulation
The Bergman cyclization is a fascinating rearrangement reaction with implications beyond organic chemistry. It has now been shown that a reversible Bergman cyclization reaction in a single molecule sitting on an ultrathin NaCl film can be triggered and directly imaged using atomic force microscopy. The interconverted diradical and diyne products are shown to have distinct chemical and physical properties.
- Bruno Schuler
- , Shadi Fatayer
- & Leo Gross
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Controlled partial interpenetration in metal–organic frameworks
Interpenetration of metal–organic frameworks (MOFs) is a common phenomenon, in which a structure consists of two or more identical, entangled sub-lattices. Now, MOFs with variable, fractional degrees of occupancy of one of two sub-lattices have been prepared. The extent of interpenetration can be controlled either during synthesis or by autocatenation, a framework rearrangement process.
- Alan Ferguson
- , Lujia Liu
- & Shane G. Telfer
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Transfer of molecular recognition information from DNA nanostructures to gold nanoparticles
DNA nanostructures are typically used as molecular scaffolds. Now, it has been shown that they can also act as reusable templates for ‘molecular printing’ of DNA strands onto gold nanoparticles. The products inherit the recognition elements of the parent template: number, orientation and sequence asymmetry of DNA strands. This converts isotropic nanoparticles into complex building blocks.
- Thomas G. W. Edwardson
- , Kai Lin Lau
- & Hanadi F. Sleiman
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News & Views |
Molecules bearing robotic arms
Mass production at the nanoscale requires molecular machines that can control, with high fidelity, the spatial orientation of other reactive species. The demonstration of a synthetic system in which a molecular robotic arm can be used to manipulate the position of a chemical cargo is a significant step towards achieving this goal.
- Ivan Aprahamian
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Pick-up, transport and release of a molecular cargo using a small-molecule robotic arm
Factory assembly lines often feature robots that pick up, reposition and connect components in a programmed manner. Now, it has been shown that a molecular machine is able to pick up a cargo, reposition it, set it down and release it at a site approximately 2 nm away from the starting position.
- Salma Kassem
- , Alan T. L. Lee
- & Jordi Solà
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News & Views |
Sweet fullerenes vanquish viruses
Fullerene-based dendritic structures coated with 120 sugars can be made in high yields in a relatively short sequence of reactions. The mannosylated compound is shown to inhibit Ebola infection in cells more efficiently than monofullerene-based glycoclusters.
- Sébastien Vidal
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Incorporation of well-dispersed sub-5-nm graphitic pencil nanodots into ordered mesoporous frameworks
Doping mesoporous materials is an attractive way to tune their properties, but typically disrupts the host materials’ structures. Ultrasmall graphitic pencil nanodots have now been prepared, doped with heteroatoms, and inserted in a well-dispersed manner within the ordered structure of mesoporous materials including TiO2, carbon and silica, by a co-assembly approach.
- Biao Kong
- , Jing Tang
- & Dongyuan Zhao
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Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy
Singlet fission, a spin-allowed conversion of a spin-singlet state into a pair of spin-triplet excitons, may be useful for the development of next-generation photovoltaics. Ultrafast coherence measurements now show that vibrational motions play a critical role in fission as they facilitate the mixing of triplet-pair states with singlet excitons.
- Artem A. Bakulin
- , Sarah E. Morgan
- & Akshay Rao
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News & Views |
One rule for the electron-rich...
A vast number of possible isomers exist for each fullerene, yet few are observed experimentally. Neutral fullerenes typically minimize adjacent pentagons, but charged ones often tolerate them. Now, a simple model taking into account structural strain and π electronic aspects predicts the asymmetric relative stabilities of charged isomers.
- Patrick Fowler
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Cage connectivity and frontier π orbitals govern the relative stability of charged fullerene isomers
The stability of charged fullerenes is not as well understood as that of their neutral counterparts, with, for example, more frequent violations of the isolated-pentagon and pentagon-adjacency penalty rules. Now, a simple model based on the concepts of cage connectivity and frontier π orbitals predicts the relative stability of cationic and anionic fullerene isomers.
- Yang Wang
- , Sergio Díaz-Tendero
- & Fernando Martín
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Unidirectional rotary motion in achiral molecular motors
Avoiding equal probability for clockwise and anticlockwise rotation is essential for the function of molecular motors, and both biological and synthetic systems take advantage of chirality to control the rotary direction. Now it has been shown, by integrating two rotor moieties in a symmetric meso motor design, that light-driven unidirectional rotary motion can be achieved in an achiral system.
- Jos C. M. Kistemaker
- , Peter Štacko
- & Ben L. Feringa
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Co-assembly, spatiotemporal control and morphogenesis of a hybrid protein–peptide system
Amphiphilic-peptide-driven opening of elastin-like protein molecules triggers the self-assembly of a multilayered membrane. This dynamic system can undergo morphogenesis into hierarchically ordered tubular structures that can be used to create complex scaffolds for tissue engineering.
- Karla E. Inostroza-Brito
- , Estelle Collin
- & Alvaro Mata
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Shaping quaternary assemblies of water-soluble non-peptide helical foldamers by sequence manipulation
The self-assembly of short amphiphilic α-helicomimetic foldamers bearing proteinaceous side-chains can be controlled by manipulating the side-chain sequence. This enables the foldamers to be programmed to form either discrete helical bundles containing isolated cavities, or pH-responsive water-filled channels with controllable pore diameters.
- Gavin W. Collie
- , Karolina Pulka-Ziach
- & Gilles Guichard
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News & Views |
Nanocrystals by design
Nanocrystals with precisely defined structures offer promise as components of advanced materials yet they are challenging to create. Now, a nanocrystal made up of seven cadmium and twelve chloride ions has been synthesized via a biotemplating approach that uses a de novo designed protein.
- Li Shang
- & Gerd Ulrich Nienhaus
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Efficient green methanol synthesis from glycerol
Impure glycerol is obtained as a significant by-product of biodiesel production. Now it is shown that this crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low pressure process.
- Muhammad H. Haider
- , Nicholas F. Dummer
- & Graham J. Hutchings
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A cascade reaction network mimicking the basic functional steps of adaptive immune response
A cascade reaction network has been created that can function in a manner that is superficially similar to the most basic steps of the vertebrate adaptive immune response. This reaction network uses DNA and enzymes as simple artificial analogues of the components of the acquired immune system.
- Da Han
- , Cuichen Wu
- & Weihong Tan
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Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides
Perovskite materials show great promise for solar cell devices, owing in particular to their high power conversion efficiency. Now, the addition of butylphosphonic acid 4-ammonium cations during a one-step process has been shown to improve both the efficiency and moisture stability of perovskite photovoltaics, through the formation of hydrogen-bonding crosslinks between neighbouring grains.
- Xiong Li
- , M. Ibrahim Dar
- & Michael Grätzel
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Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids
Graphene possesses numerous interesting properties yet the preparation of pristine sheets has remained challenging, hindering practical applications. Now, a rapid, highly efficient step has been devised that uses microwave irradiation in oligomeric ionic liquids to exfoliate graphite into pristine ‘single layer’ sheets (<1 nm thick). A concentrated dispersion of the resulting material behaves as a physical gel.
- Michio Matsumoto
- , Yusuke Saito
- & Takuzo Aida
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Light-controlled self-assembly of non-photoresponsive nanoparticles
Controlling the self-assembly of nanoparticles using light has been demonstrated in many systems where the particle surfaces are functionalized with photoswitchable ligands. Now, it has been shown that the light-controlled self-assembly of non-photoresponsive nanoparticles can be achieved in a quantitative and reversible fashion by placing them in a photoresponsive medium.
- Pintu K. Kundu
- , Dipak Samanta
- & Rafal Klajn
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Photoinduced reversible switching of porosity in molecular crystals based on star-shaped azobenzene tetramers
Rigid star-shaped azobenzene tetramers form a porous molecular crystal when the azobenzene moieties are in the trans configuration, and a non-porous amorphous material on their isomerization to the cis configuration. These two forms are reversibly interconverted in the solid state by light irradiation, thus enabling the photoswitching of optical and gas-capture properties.
- Massimo Baroncini
- , Simone d'Agostino
- & Alberto Credi
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Rise of the nanobots
Bioorthogonal catalysis provides new ways of mediating artificial transformations in living environs. Now, researchers have developed a nanodevice whose catalytic activity can be regulated by host–guest chemistry.
- Asier Unciti-Broceta
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News & Views |
Clamping down on cancer detection
An electrochemical clamp assay that enables the rapid and sensitive detection of nucleic acids containing single base mutations has now been developed. It has been shown to differentiate between cancer patient samples featuring a specific mutation, and controls from healthy donors or other cancer patients, all directly in unprocessed serum.
- Irina A. Gorodetskaya
- & Alon A. Gorodetsky
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News & Views |
Chirality transfer takes a jump
The transfer of chirality is known to occur through chemical bonds. Now, chiral biomolecules have been observed to impart some of their optical properties to a spatially separated achiral dye — with the transfer mediated by plasmon resonance from an achiral metallic nanostructure.
- Vladimiro Mujica
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Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts
Regulation of bioorthogonal catalysis in living systems is challenging because of the complex intracellular environment. Now, the activity of protein-sized bioorthogonal nanozymes has been regulated by binding a supramolecular cucurbit[7]uril ‘gate-keeper’ onto the monolayer surface. This arrangement enables the controlled activation of profluorophores and prodrugs inside living cells for imaging and therapeutic applications.
- Gulen Yesilbag Tonga
- , Youngdo Jeong
- & Vincent M. Rotello
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Through-space transfer of chiral information mediated by a plasmonic nanomaterial
Surface-enhanced resonant Raman optical activity (SERROA) reveals the through-space transfer of chirality from biomolecules to achiral benzotriazole dye-conjugated nanotags. The chiroptical responses generated by the stereoisomers of ribose and tryptophan establish this as the basis for a stereoselective nanosensor platform.
- Saeideh Ostovar pour
- , Louise Rocks
- & Ewan W. Blanch
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Functionalization of cobalt porphyrin–phospholipid bilayers with his-tagged ligands and antigens
Lipid bilayers containing porphyin-phospholipid that is chelated with cobalt have been shown to capture his-tagged proteins and peptides. This method offers a simple route for functionalizing pre-formed lipid bilayers without disrupting their integrity. Using this approach homing peptides were attached to cargo-loaded liposomes to enable tumour targeting, and an HIV-derived protein fragment elicited antibodies following binding to immunogenic liposomes.
- Shuai Shao
- , Jumin Geng
- & Jonathan F. Lovell
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Stepwise growth of surface-grafted DNA nanotubes visualized at the single-molecule level
DNA nanotubes are attractive building blocks for the assembly of complex arrays. An efficient solid-state synthesis for producing surface-grafted, robust nanotubes has now been devised. Rungs are incorporated in a stepwise manner so that each one is addressable. Using fluorescent tags, the nanotube growth was visualized at the single-molecule level.
- Amani A. Hariri
- , Graham D. Hamblin
- & Gonzalo Cosa
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Intermediate tunnelling–hopping regime in DNA charge transport
Charge transport in molecular systems is typically through coherent tunnelling over a short distance or incoherent hopping over a long distance. An intermediate regime between those two transport mechanisms has now been found for DNA systems with stacked guanine–cytosine sequences.
- Limin Xiang
- , Julio L. Palma
- & Nongjian Tao