Showing papers in "Nature Materials in 2009"

A metal-free polymeric photocatalyst for hydrogen production from water under visible light

Abstract: The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.

Understanding biophysicochemical interactions at the nano–bio interface

Abstract: Rapid growth in nanotechnology is increasing the likelihood of engineered nanomaterials coming into contact with humans and the environment. Nanoparticles interacting with proteins, membranes, cells, DNA and organelles establish a series of nanoparticle/biological interfaces that depend on colloidal forces as well as dynamic biophysicochemical interactions. These interactions lead to the formation of protein coronas, particle wrapping, intracellular uptake and biocatalytic processes that could have biocompatible or bioadverse outcomes. For their part, the biomolecules may induce phase transformations, free energy releases, restructuring and dissolution at the nanomaterial surface. Probing these various interfaces allows the development of predictive relationships between structure and activity that are determined by nanomaterial properties such as size, shape, surface chemistry, roughness and surface coatings. This knowledge is important from the perspective of safe use of nanomaterials.

A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries

Abstract: The Li-S battery has been under intense scrutiny for over two decades, as it offers the possibility of high gravimetric capacities and theoretical energy densities ranging up to a factor of five beyond conventional Li-ion systems. Herein, we report the feasibility to approach such capacities by creating highly ordered interwoven composites. The conductive mesoporous carbon framework precisely constrains sulphur nanofiller growth within its channels and generates essential electrical contact to the insulating sulphur. The structure provides access to Li+ ingress/egress for reactivity with the sulphur, and we speculate that the kinetic inhibition to diffusion within the framework and the sorption properties of the carbon aid in trapping the polysulphides formed during redox. Polymer modification of the carbon surface further provides a chemical gradient that retards diffusion of these large anions out of the electrode, thus facilitating more complete reaction. Reversible capacities up to 1,320 mA h g(-1) are attained. The assembly process is simple and broadly applicable, conceptually providing new opportunities for materials scientists for tailored design that can be extended to many different electrode materials.

Ionic-liquid materials for the electrochemical challenges of the future.

Abstract: Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide

Abstract: Graphene, a single monolayer of graphite, has recently attracted considerable interest owing to its novel magneto-transport properties, high carrier mobility and ballistic transport up to room temperature. It has the potential for technological applications as a successor of silicon in the post Moore's law era, as a single-molecule gas sensor, in spintronics, in quantum computing or as a terahertz oscillator. For such applications, uniform ordered growth of graphene on an insulating substrate is necessary. The growth of graphene on insulating silicon carbide (SiC) surfaces by high-temperature annealing in vacuum was previously proposed to open a route for large-scale production of graphene-based devices. However, vacuum decomposition of SiC yields graphene layers with small grains (30-200 nm; refs 14-16). Here, we show that the ex situ graphitization of Si-terminated SiC(0001) in an argon atmosphere of about 1 bar produces monolayer graphene films with much larger domain sizes than previously attainable. Raman spectroscopy and Hall measurements confirm the improved quality of the films thus obtained. High electronic mobilities were found, which reach mu=2,000 cm (2) V(-1) s(-1) at T=27 K. The new growth process introduced here establishes a method for the synthesis of graphene films on a technologically viable basis.

Ultralong spin coherence time in isotopically engineered diamond

Abstract: As quantum mechanics ventures into the world of applications and engineering, materials science faces the necessity to design matter to quantum grade purity. For such materials, quantum effects define their physical behaviour and open completely new (quantum) perspectives for applications. Carbon-based materials are particularly good examples, highlighted by the fascinating quantum properties of, for example, nanotubes or graphene. Here, we demonstrate the synthesis and application of ultrapure isotopically controlled single-crystal chemical vapour deposition (CVD) diamond with a remarkably low concentration of paramagnetic impurities. The content of nuclear spins associated with the (13)C isotope was depleted to 0.3% and the concentration of other paramagnetic defects was measured to be <10(13) cm(-3). Being placed in such a spin-free lattice, single electron spins show the longest room-temperature spin dephasing times ever observed in solid-state systems (T2=1.8 ms). This benchmark will potentially allow observation of coherent coupling between spins separated by a few tens of nanometres, making it a versatile material for room-temperature quantum information processing devices. We also show that single electron spins in the same isotopically engineered CVD diamond can be used to detect external magnetic fields with a sensitivity reaching 4 nT Hz(-1/2) and subnanometre spatial resolution.

Biodegradable luminescent porous silicon nanoparticles for in vivo applications.

Abstract: Nanomaterials that can cir culate in the body hold great potential to diagnose and treat disease 1‐4 . For such applications, it is important that the nanomaterials be harmlessly eliminated from the body in a reasonable period of time after they carry out their diagnostic or therapeutic function. Despite efforts to improve their targeting efficiency, significant quantities of systemically administered nanomaterials are cleared by the mononuclear phagocytic system before finding their targets, increasing the likelihood of unintended acute or chronic toxicity. However, there has been little effort to engineer the self-destruction of errant nanoparticles into non-toxic, systemically eliminated products. Here, we present luminescent porous silicon nanoparticles (LPSiNPs) that can carry a drug payload and of which the intrinsic near-infrared photoluminescence enables monitoring of both accumulation and degradation in vivo. Furthermore, in contrast to most optically active nanomaterials (carbon nanotubes, gold nanoparticles and quantum dots), LPSiNPs self-destruct in a mouse model into renally cleared components in a relatively short period of time with no evidence of toxicity. As a preliminary in vivo application, we demonstrate tumour imaging using dextran-coated LPSiNPs (D-LPSiNPs). These results demonstrate a new type of multifunctional nanostructure with a low-toxicity degradation pathway forinvivo applications. The in vivo use of nanomaterials as therapeutic and diagnostic agents is of intense interest owing to their unique properties such as large specific capacity for drug loading 2 , strong superparamagnetism 3 ,efficientphotoluminescence 1,5 ordistinctive Raman signatures 4 , among others. Materials with sizes in the range of 20200nm can avoid renal filtration, leading to prolonged resi

Plasmonic analogue of electromagnetically induced transparency at the Drude damping limit.

Abstract: In atomic physics, the coherent coupling of a broad and a narrow resonance leads to quantum interference and provides the general recipe for electromagnetically induced transparency (EIT). A sharp resonance of nearly perfect transmission can arise within a broad absorption profile. These features show remarkable potential for slow light, novel sensors and low-loss metamaterials. In nanophotonics, plasmonic structures enable large field strengths within small mode volumes. Therefore, combining EIT with nanoplasmonics would pave the way towards ultracompact sensors with extremely high sensitivity. Here, we experimentally demonstrate a nanoplasmonic analogue of EIT using a stacked optical metamaterial. A dipole antenna with a large radiatively broadened linewidth is coupled to an underlying quadrupole antenna, of which the narrow linewidth is solely limited by the fundamental non-radiative Drude damping. In accordance with EIT theory, we achieve a very narrow transparency window with high modulation depth owing to nearly complete suppression of radiative losses. Plasmonic nanostructures enable the concentration of large electric fields into small spaces. The classical analogue of electromagnetically induced transparency has now been achieved in such devices, leading to a narrow resonance in their absorption spectrum. This combination of high electric-field concentration and sharp resonance offers a pathway to ultracompact sensors with extremely high sensitivity.

Stretchable active-matrix organic light-emitting diode display using printable elastic conductors

Abstract: Stretchability will significantly expand the applications scope of electronics, particularly for large-area electronic displays, sensors and actuators. Unlike for conventional devices, stretchable electronics can cover arbitrary surfaces and movable parts. However, a large hurdle is the manufacture of large-area highly stretchable electrical wirings with high conductivity. Here, we describe the manufacture of printable elastic conductors comprising single-walled carbon nanotubes (SWNTs) uniformly dispersed in a fluorinated rubber. Using an ionic liquid and jet-milling, we produce long and fine SWNT bundles that can form well-developed conducting networks in the rubber. Conductivity of more than 100 S cm(-1) and stretchability of more than 100% are obtained. Making full use of this extraordinary conductivity, we constructed a rubber-like stretchable active-matrix display comprising integrated printed elastic conductors, organic transistors and organic light-emitting diodes. The display could be stretched by 30-50% and spread over a hemisphere without any mechanical or electrical damage.

Plasmonic nanorod metamaterials for biosensing.

Abstract: Label-free plasmonic biosensors rely either on surface plasmon polaritons or on localized surface plasmons on continuous or nanostructured noble-metal surfaces to detect molecular-binding events. Despite undisputed advantages, including spectral tunability, strong enhancement of the local electric field and much better adaptability to modern nanobiotechnology architectures, localized plasmons demonstrate orders of magnitude lower sensitivity compared with their guided counterparts. Here, we demonstrate an improvement in biosensing technology using a plasmonic metamaterial that is capable of supporting a guided mode in a porous nanorod layer. Benefiting from a substantial overlap between the probing field and the active biological substance incorporated between the nanorods and a strong plasmon-mediated energy confinement inside the layer, this metamaterial provides an enhanced sensitivity to refractive-index variations of the medium between the rods (more than 30,000 nm per refractive-index unit). We demonstrate the feasibility of our approach using a standard streptavidin-biotin affinity model and record considerable improvement in the detection limit of small analytes compared with conventional label-free plasmonic devices.

Complexity in biomaterials for tissue engineering

Abstract: The molecular and physical information coded within the extracellular milieu is informing the development of a new generation of biomaterials for tissue engineering. Several powerful extracellular influences have already found their way into cell-instructive scaffolds, while others remain largely unexplored. Yet for commercial success tissue engineering products must be not only efficacious but also cost-effective, introducing a potential dichotomy between the need for sophistication and ease of production. This is spurring interest in recreating extracellular influences in simplified forms, from the reduction of biopolymers into short functional domains, to the use of basic chemistries to manipulate cell fate. In the future these exciting developments are likely to help reconcile the clinical and commercial pressures on tissue engineering.

Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions

Abstract: Recent advances in colloidal synthesis enabled the precise control of the size, shape and composition of catalytic metal nanoparticles, enabling their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here, we report the design of a high-temperature-stable model catalytic system that consists of a Pt metal core coated with a mesoporous silica shell (Pt@mSiO2). Inorganic silica shells encaged the Pt cores up to 750 ∘C in air and the mesopores providing direct access to the Pt core made the Pt@mSiO2 nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt@mSiO2 nanoparticles enabled high-temperature CO oxidation studies, including ignition behaviour, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt@mSiO2 nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept used in the Pt@mSiO2 core–shell catalyst can be extended to other metal/metal oxide compositions. Colloidal synthesis can help to precisely control the shape and composition of catalytic metal nanoparticles, but it has so far proved difficult to use these particles in high-temperature reactions. Core–shell structures capable of isolating Pt-mesoporous silica nanoparticles have now been shown to be catalytically active for ethylene hydrogenation and CO oxidation at high temperature.

An optical cloak made of dielectrics

Abstract: Invisibility devices have captured the human imagination for many years. Recent theories have proposed schemes for cloaking devices using transformation optics and conformal mapping. Metamaterials, with spatially tailored properties, have provided the necessary medium by enabling precise control over the flow of electromagnetic waves. Using metamaterials, the first microwave cloaking has been achieved but the realization of cloaking at optical frequencies, a key step towards achieving actual invisibility, has remained elusive. Here, we report the first experimental demonstration of optical cloaking. The optical 'carpet' cloak is designed using quasi-conformal mapping to conceal an object that is placed under a curved reflecting surface by imitating the reflection of a flat surface. The cloak consists only of isotropic dielectric materials, which enables broadband and low-loss invisibility at a wavelength range of 1,400-1,800 nm.

Gold nanocages covered by smart polymers for controlled release with near-infrared light

Abstract: Photosensitive caged compounds have enhanced our ability to address the complexity of biological systems by generating effectors with remarkable spatial/temporal resolutions. The caging effect is typically removed by photolysis with ultraviolet light to liberate the bioactive species. Although this technique has been successfully applied to many biological problems, it suffers from a number of intrinsic drawbacks. For example, it requires dedicated efforts to design and synthesize a precursor compound for each effector. The ultraviolet light may cause damage to biological samples and is suitable only for in vitro studies because of its quick attenuation in tissue. Here we address these issues by developing a platform based on the photothermal effect of gold nanocages. Gold nanocages represent a class of nanostructures with hollow interiors and porous walls. They can have strong absorption (for the photothermal effect) in the near-infrared while maintaining a compact size. When the surface of a gold nanocage is covered with a smart polymer, the pre-loaded effector can be released in a controllable fashion using a near-infrared laser. This system works well with various effectors without involving sophisticated syntheses, and is well suited for in vivo studies owing to the high transparency of soft tissue in the near-infrared region.

High-energy cathode material for long-life and safe lithium batteries

Abstract: Layered lithium nickel-rich oxides, Li[Ni(1-x)M(x)]O(2) (M=metal), have attracted significant interest as the cathode material for rechargeable lithium batteries owing to their high capacity, excellent rate capability and low cost. However, their low thermal-abuse tolerance and poor cycle life, especially at elevated temperature, prohibit their use in practical batteries. Here, we report on a concentration-gradient cathode material for rechargeable lithium batteries based on a layered lithium nickel cobalt manganese oxide. In this material, each particle has a central bulk that is rich in Ni and a Mn-rich outer layer with decreasing Ni concentration and increasing Mn and Co concentrations as the surface is approached. The former provides high capacity, whereas the latter improves the thermal stability. A half cell using our concentration-gradient cathode material achieved a high capacity of 209 mA h g(-1) and retained 96% of this capacity after 50 charge-discharge cycles under an aggressive test profile (55 degrees C between 3.0 and 4.4 V). Our concentration-gradient material also showed superior performance in thermal-abuse tests compared with the bulk composition Li[Ni(0.8)Co(0.1)Mn(0.1)]O(2) used as reference. These results suggest that our cathode material could enable production of batteries that meet the demanding performance and safety requirements of plug-in hybrid electric vehicles.

Physical approaches to biomaterial design.

Abstract: The development of biomaterials for drug delivery, tissue engineering and medical diagnostics has traditionally been based on new chemistries. However, there is growing recognition that the physical as well as the chemical properties of materials can regulate biological responses. Here, we review this transition with regard to selected physical properties including size, shape, mechanical properties, surface texture and compartmentalization. In each case, we present examples demonstrating the significance of these properties in biology. We also discuss synthesis methods and biological applications for designer biomaterials, which offer unique physical properties.

Conduction at domain walls in oxide multiferroics

Abstract: Domain walls may play an important role in future electronic devices, given their small size as well as the fact that their location can be controlled. Here, we report the observation of room-temperature electronic conductivity at ferroelectric domain walls in the insulating multiferroic BiFeO3. The origin and nature of the observed conductivity are probed using a combination of conductive atomic force microscopy, high-resolution transmission electron microscopy and first-principles density functional computations. Our analyses indicate that the conductivity correlates with structurally driven changes in both the electrostatic potential and the local electronic structure, which shows a decrease in the bandgap at the domain wall. Additionally, we demonstrate the potential for device applications of such conducting nanoscale features. Domain walls may be important in future electronic devices, given their small size as well as the fact that their location can be controlled. In the case of insulating multiferroic oxides, domain walls are now discovered to be electrically conductive, suggesting their possible use in logic and memory applications.

The influence of edge structure on the electronic properties of graphene quantum dots and nanoribbons.

Abstract: Graphene shows promise as a future material for nanoelectronics owing to its compatibility with industry-standard lithographic processing, electron mobilities up to 150 times greater than Si and a thermal conductivity twice that of diamond. The electronic structure of graphene nanoribbons (GNRs) and quantum dots (GQDs) has been predicted to depend sensitively on the crystallographic orientation of their edges; however, the influence of edge structure has not been verified experimentally. Here, we use tunnelling spectroscopy to show that the electronic structure of GNRs and GQDs with 2-20 nm lateral dimensions varies on the basis of the graphene edge lattice symmetry. Predominantly zigzag-edge GQDs with 7-8 nm average dimensions are metallic owing to the presence of zigzag edge states. GNRs with a higher fraction of zigzag edges exhibit a smaller energy gap than a predominantly armchair-edge ribbon of similar width, and the magnitudes of the measured GNR energy gaps agree with recent theoretical calculations.

On the origin of the open-circuit voltage of polymer–fullerene solar cells

Abstract: The increasing amount of research on solution-processable, organic donor-acceptor bulk heterojunction photovoltaic systems, based on blends of conjugated polymers and fullerenes has resulted in devices with an overall power-conversion efficiency of 6%. For the best devices, absorbed photon-to-electron quantum efficiencies approaching 100% have been shown. Besides the produced current, the overall efficiency depends critically on the generated photovoltage. Therefore, understanding and optimization of the open-circuit voltage (Voc) of organic solar cells is of high importance. Here, we demonstrate that charge-transfer absorption and emission are shown to be related to each other and Voc in accordance with the assumptions of the detailed balance and quasi-equilibrium theory. We underline the importance of the weak ground-state interaction between the polymer and the fullerene and we confirm that Voc is determined by the formation of these states. Our work further suggests alternative pathways to improve Voc of donor-acceptor devices.

Three-dimensional nanopillar-array photovoltaics on low-cost and flexible substrates

Abstract: Solar energy represents one of the most abundant and yet least harvested sources of renewable energy. In recent years, tremendous progress has been made in developing photovoltaics that can be potentially mass deployed. Of particular interest to cost-effective solar cells is to use novel device structures and materials processing for enabling acceptable efficiencies. In this regard, here, we report the direct growth of highly regular, single-crystalline nanopillar arrays of optically active semiconductors on aluminium substrates that are then configured as solar-cell modules. As an example, we demonstrate a photovoltaic structure that incorporates three-dimensional, single-crystalline n-CdS nanopillars, embedded in polycrystalline thin films of p-CdTe, to enable high absorption of light and efficient collection of the carriers. Through experiments and modelling, we demonstrate the potency of this approach for enabling highly versatile solar modules on both rigid and flexible substrates with enhanced carrier collection efficiency arising from the geometric configuration of the nanopillars.

Anisotropic self-assembly of spherical polymer-grafted nanoparticles

Abstract: It is easy to understand the self-assembly of particles with anisotropic shapes or interactions (for example, cobalt nanoparticles or proteins) into highly extended structures. However, there is no experimentally established strategy for creating a range of anisotropic structures from common spherical nanoparticles. We demonstrate that spherical nanoparticles uniformly grafted with macromolecules ('nanoparticle amphiphiles') robustly self-assemble into a variety of anisotropic superstructures when they are dispersed in the corresponding homopolymer matrix. Theory and simulations suggest that this self-assembly reflects a balance between the energy gain when particle cores approach and the entropy of distorting the grafted polymers. The effectively directional nature of the particle interactions is thus a many-body emergent property. Our experiments demonstrate that this approach to nanoparticle self-assembly enables considerable control for the creation of polymer nanocomposites with enhanced mechanical properties. Grafted nanoparticles are thus versatile building blocks for creating tunable and functional particle superstructures with significant practical applications.

Magnetic memory of a single-molecule quantum magnet wired to a gold surface.

Abstract: In the field of molecular spintronics, the use of magnetic molecules for information technology is a main target and the observation of magnetic hysteresis on individual molecules organized on surfaces is a necessary step to develop molecular memory arrays. Although simple paramagnetic molecules can show surface-induced magnetic ordering and hysteresis when deposited on ferromagnetic surfaces, information storage at the molecular level requires molecules exhibiting an intrinsic remnant magnetization, like the so-called single-molecule magnets (SMMs). These have been intensively investigated for their rich quantum behaviour but no magnetic hysteresis has been so far reported for monolayers of SMMs on various non-magnetic substrates, most probably owing to the chemical instability of clusters on surfaces. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism synchrotron-based techniques, pushed to the limits in sensitivity and operated at sub-kelvin temperatures, we have now found that robust, tailor-made Fe(4) complexes retain magnetic hysteresis at gold surfaces. Our results demonstrate that isolated SMMs can be used for storing information. The road is now open to address individual molecules wired to a conducting surface in their blocked magnetization state, thereby enabling investigation of the elementary interactions between electron transport and magnetism degrees of freedom at the molecular scale.

Electronic and magnetic phase diagram of β-Fe1.01Se with superconductivity at 36.7 K under pressure

Abstract: Superconductivity was recently observed in the binary iron-based compound, FeSe. It is now shown that under pressure, the transition temperature can rise above 36 K. In addition, no static magnetic ordering is observed for this system, contrary to FeAs superconductors. The discovery of new high-temperature superconductors1 based on FeAs has led to a new ‘gold rush’ in high-TC superconductivity. All of the new superconductors share the same common structural motif of FeAs layers and reach TC values up to 55 K (ref. 2). Recently, superconductivity has been reported in FeSe (ref. 3), which has the same iron pnictide layer structure, but without separating layers. Here, we report the magnetic and electronic phase diagram of β-Fe1.01Se as a function of temperature and pressure. The superconducting transition temperature increases from 8.5 to 36.7 K under an applied pressure of 8.9 GPa. It then decreases at higher pressures. A marked change in volume is observed at the same time as TC rises, owing to a collapse of the separation between the Fe2Se2 layers. No static magnetic ordering is observed for the whole p–T phase diagram. We also report that at higher pressures (starting around 7 GPa and completed at 38 GPa), Fe1.01Se transforms to a hexagonal NiAs-type structure and exhibits non-magnetic behaviour.

Engineering light absorption in semiconductor nanowire devices

Abstract: Quantum confinement effects have an important role in photonic devices. However, rather than seeking perfect confinement of light, leaky-mode resonances are shown to be ideally suited for enhancing and spectrally engineering light absorption in nanoscale photonic structures. The use of quantum and photon confinement has enabled a true revolution in the development of high-performance semiconductor materials and devices1,2,3. Harnessing these powerful physical effects relies on an ability to design and fashion structures at length scales comparable to the wavelength of electrons (∼1 nm) or photons (∼1 μm). Unfortunately, many practical optoelectronic devices exhibit intermediate sizes4,5 where resonant enhancement effects seem to be insignificant. Here, we show that leaky-mode resonances, which can gently confine light within subwavelength, high-refractive-index semiconductor nanostructures, are ideally suited to enhance and spectrally engineer light absorption in this important size regime. This is illustrated with a series of individual germanium nanowire photodetectors. This notion, together with the ever-increasing control over nanostructure synthesis opens up tremendous opportunities for the realization of a wide range of high-performance, nanowire-based optoelectronic devices, including solar cells6,7,8, photodetectors9,10,11,12,13, optical modulators14 and light sources 14,15.

Conjugated dicarboxylate anodes for Li-ion batteries.

Abstract: Present Li-ion batteries for portable electronics are based on inorganic electrodes. For upcoming large-scale applications the notion of materials sustainability produced by materials made through eco-efficient processes, such as renewable organic electrodes, is crucial. We here report on two organic salts, Li2C8H4O4 (Li terephthalate) and Li2C6H4O4(Li trans-trans-muconate), with carboxylate groups conjugated within the molecular core, which are respectively capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4 V, giving reversible capacities of 300 and 150 mA h g-1. The activity is maintained at 80 °C with polyethyleneoxide-based electrolytes. A noteworthy advantage of the Li2C8H4O4 and Li2C6H4O4 negative electrodes is their enhanced thermal stability over carbon electrodes in 1 M LiPF6 ethylene carbonate-dimethyl carbonate electrolytes, which should result in safer Li-ion cells. Moreover, as bio-inspired materials, both compounds are the metabolites of aromatic hydrocarbon oxidation, and terephthalic acid is available in abundance from the recycling of polyethylene terephthalate.

Porous organic cages

Abstract: Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer–Emmett–Teller surface areas of 550 and 23 m2 g-1, respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

Printed artificial cilia from liquid-crystal network actuators modularly driven by light.

Abstract: Polymeric microactuators are potentially useful in micromechanical systems and lab-on-a-chip systems. However, manufacturing of miniature polymeric actuators has been complicated owing to the necessity of including electrodes for actuation or using lithographic techniques for patterning. Here, we demonstrate that all-polymer microdevices can be fabricated using inkjet printing technology in combination with self-organizing liquid-crystal network actuators. We exploit the self-assembling properties of the liquid crystal to create large strain gradients, and light-driven actuation is chosen to allow simple and remote addressing. By using multiple inks, microactuators with different subunits are created that can be selectively addressed by changing the wavelength of the light. The actuators mimic the motion of natural cilia. These artificial cilia have the potential to create flow and mixing in wet environments such as lab-on-a-chip applications. The process is easily adapted for roll-to-roll fabrication, allowing for large-scale and low-cost production of miniaturized active polymer systems.

A dual-emissive-materials design concept enables tumour hypoxia imaging

Abstract: Luminescent materials are widely used for imaging and sensing owing to their high sensitivity, rapid response and facile detection by many optical technologies. Typically materials must be chemically tailored to achieve intense, photostable fluorescence, oxygen-sensitive phosphorescence or dual emission for ratiometric sensing, often by blending two dyes in a matrix. Dual-emissive materials combining all of these features in one easily tunable molecular platform are desirable, but when fluorescence and phosphorescence originate from the same dye, it can be challenging to vary relative fluorescence/phosphorescence intensities for practical sensing applications. Heavy-atom substitution alone increases phosphorescence by a given, not variable amount. Here, we report a strategy for modulating fluorescence/phosphorescence for a single-component, dual-emissive, iodide-substituted difluoroboron dibenzoylmethane-poly(lactic acid) (BF(2)dbm(I)PLA) solid-state sensor material. This is accomplished through systematic variation of the PLA chain length in controlled solvent-free lactide polymerization combined with heavy-atom substitution. We demonstrate the versatility of this approach by showing that films made from low-molecular-weight BF(2)dbm(I)PLA with weak fluorescence and strong phosphorescence are promising as 'turn on' sensors for aerodynamics applications, and that nanoparticles fabricated from a higher-molecular-weight polymer with balanced fluorescence and phosphorescence intensities serve as ratiometric tumour hypoxia imaging agents.

Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions

Abstract: Control of the formation of nanostructures during their synthesis can be achieved using either equilibrium conditions, such as in nanostructure templating, or non-equilibrium conditions, such as in reaction–diffusion systems. This review analyses the different method types with the aim of producing guidelines for the rational design of hybrid organic–inorganic nanostructures. Understanding how chemically derived processes control the construction and organization of matter across extended and multiple length scales is of growing interest in many areas of materials research. Here we review present equilibrium and non-equilibrium self-assembly approaches to the synthetic construction of discrete hybrid (inorganic–organic) nano-objects and higher-level nanostructured networks. We examine a range of synthetic modalities under equilibrium conditions that give rise to integrative self-assembly (supramolecular wrapping, nanoscale incarceration and nanostructure templating) or higher-order self-assembly (programmed/directed aggregation). We contrast these strategies with processes of transformative self-assembly that use self-organizing media, reaction–diffusion systems and coupled mesophases to produce higher-level hybrid structures under non-equilibrium conditions. Key elements of the constructional codes associated with these processes are identified with regard to existing theoretical knowledge, and presented as a heuristic guideline for the rational design of hybrid nano-objects and nanomaterials.

An inconvenient truth about thermoelectrics.

Abstract: Despite recent advances, thermoelectric energy conversion will never be as efficient as steam engines. That means thermoelectrics will remain limited to applications served poorly or not at all by existing technology. Bad news for thermoelectricians, but the climate crisis requires that we face bad news head on.