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Phenotypic plasticity, the ability to produce multiple phenotypes from a single genotype, represents an excellent model with which to examine the relationship between gene expression and phenotypes. Analyses of the molecular foundations of phenotypic plasticity are challenging, however, especially in the case of complex social phenotypes. Here we apply a machine learning approach to tackle this challenge by analyzing individual-level gene expression profiles of Polistes dominula paper wasps following the loss of a queen. We find that caste-associated gene expression profiles respond strongly to queen loss, and that this change is partly explained by attributes such as age but occurs even in individuals that appear phenotypically unaffected. These results demonstrate that large changes in gene expression may occur in the absence of outwardly detectable phenotypic changes, resulting here in a socially mediated de-differentiation of individuals at the transcriptomic level but not at the levels of ovarian development or behavior., Connecting genotypes to complex social behaviour is challenging. Taylor et al. use machine learning to show a strong response of caste-associated gene expression to queen loss, wherein individual wasp’s expression profiles become intermediate between queen and worker states, even in the absence of behavioural changes.

Graphene has an extremely high in-plane strength yet considerable out-of-plane softness. High crystalline order of graphene assemblies is desired to utilize their in-plane properties, however, challenged by the easy formation of chaotic wrinkles for the intrinsic softness. Here, we find an intercalation modulated plasticization phenomenon, present a continuous plasticization stretching method to regulate spontaneous wrinkles of graphene sheets into crystalline orders, and fabricate continuous graphene papers with a high Hermans’ order of 0.93. The crystalline graphene paper exhibits superior mechanical (tensile strength of 1.1 GPa, stiffness of 62.8 GPa) and conductive properties (electrical conductivity of 1.1 × 105 S m−1, thermal conductivity of 109.11 W m−1 K−1). We extend the ultrastrong graphene papers to the realistic laminated composites and achieve high strength combining with attractive conductive and electromagnetic shielding performance. The intercalation modulated plasticity is revealed as a vital state of graphene assemblies, contributing to their industrial processing as metals and plastics., Strong but flexible graphene tends to wrinkle, which compromises some properties. Here the authors report a solid plasticization method to prepare continuous graphene papers with high crystalline order, achieving high strength, stiffness, electrical and thermal conductivities.

The effective implantation of conductive and charge storage materials into flexible frames has been strongly demanded for the development of flexible supercapacitors. Here, we introduce metallic cellulose paper-based supercapacitor electrodes with excellent energy storage performance by minimizing the contact resistance between neighboring metal and/or metal oxide nanoparticles using an assembly approach, called ligand-mediated layer-by-layer assembly. This approach can convert the insulating paper to the highly porous metallic paper with large surface areas that can function as current collectors and nanoparticle reservoirs for supercapacitor electrodes. Moreover, we demonstrate that the alternating structure design of the metal and pseudocapacitive nanoparticles on the metallic papers can remarkably increase the areal capacitance and rate capability with a notable decrease in the internal resistance. The maximum power and energy density of the metallic paper-based supercapacitors are estimated to be 15.1 mW cm−2 and 267.3 μWh cm−2, respectively, substantially outperforming the performance of conventional paper or textile-type supercapacitors., With ligand-mediated layer-by-layer assembly between metal nanoparticles and small organic molecules, the authors prepare metallic paper electrodes for supercapacitors with high power and energy densities. This approach could be extended to various electrodes for portable/wearable electronics.

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm−2) delivers a charge capacity of ∼588 mAh g−1electrode (∼393 mAh cm−3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries., Most high-loading silicon-based anodes for lithium-ion batteries suffer from low efficiency and volumetric capacity. Here, the authors show that a paper-like electrode of silicon oxycarbide glass and graphene at mass loading of >2 mg cm−2 can efficiently deliver high energy density for over 1,000 cycles.

Microalgae can accumulate various carbon-neutral products, but their real-world applications are hindered by their CO2 susceptibility. Herein, the transcriptomic changes in a model microalga, Chlamydomonas reinhardtii, in a high-CO2 milieu (20%) are evaluated. The primary toxicity mechanism consists of aberrantly low expression of plasma membrane H+-ATPases (PMAs) accompanied by intracellular acidification. Our results demonstrate that the expression of a universally expressible PMA in wild-type strains makes them capable of not only thriving in acidity levels that they usually cannot survive but also exhibiting 3.2-fold increased photoautotrophic production against high CO2 via maintenance of a higher cytoplasmic pH. A proof-of-concept experiment involving cultivation with toxic flue gas (13 vol% CO2, 20 ppm NOX, and 32 ppm SOX) shows that the production of CO2-based bioproducts by the strain is doubled compared with that by the wild-type, implying that this strategy potentially enables the microalgal valorization of CO2 in industrial exhaust., Microalgae used for CO2 removal in an industrial exhaust gas stream usually has low CO2 tolerance. Here, the authors increase CO2 tolerance by expressing a single H + -pump and enable microalgal valorization of industrial flue gas.

Ubiquitous use of electronic devices has led to an unprecedented increase in related waste as well as the worldwide depletion of reserves of key chemical elements required in their manufacturing. The use of biodegradable and abundant organic (carbon-based) electronic materials can contribute to alleviate the environmental impact of the electronic industry. The pigment eumelanin is a bio-sourced candidate for environmentally benign (green) organic electronics. The biodegradation of eumelanin extracted from cuttlefish ink is studied both at 25 °C (mesophilic conditions) and 58 °C (thermophilic conditions) following ASTM D5338 and comparatively evaluated with the biodegradation of two synthetic organic electronic materials, namely copper (II) phthalocyanine (Cu–Pc) and polyphenylene sulfide (PPS). Eumelanin biodegradation reaches 4.1% (25 °C) in 97 days and 37% (58 °C) in 98 days, and residual material is found to be without phytotoxic effects. The two synthetic materials, Cu–Pc and PPS, do not biodegrade; Cu–Pc brings about the inhibition of microbial respiration in the compost. PPS appears to be potentially phytotoxic. Finally, some considerations regarding the biodegradation test as well as the disambiguation of “biodegradability” and “bioresorbability” are highlighted., Waste build-up from organic electronic components is a major environmental issue; biodegradable electronic materials could be a solution to this. Here, the authors report on the biodegradation of bio-sourced and synthetic electronic materials in industrial compost at different temperatures.

Carbon dots (CDs) have been studied for years as one of the most promising fluorescent nanomaterials. However, CDs with red or solid-state fluorescence are rarely reported. Herein, through a one-pot solvothermal treatment, hydrophobic CDs (H-CDs) with blue dispersed emission and red aggregation-induced emission are obtained. When water is introduced, the hydrophobic interaction leads to aggregation of the H-CDs. The formation of H-CD clusters induces the turning off of the blue emission, as the carbonized cores suffer from π-π stacking interactions, and the turning on of the red fluorescence, due to restriction of the surfaces’ intramolecular rotation around disulfide bonds, which conforms to the aggregation-induced-emission phenomenon. This on-off fluorescence of the H-CDs is reversible when the H-CD powder is completely dissolved. Moreover, the H-CD solution dispersed in filter paper is nearly colorless. Finally, we develop a reversible two switch-mode luminescence ink for advanced anti-counterfeiting and dual-encryption., Carbon dots that display long-wavelength and multicolor emission are desirable for biological and anti-counterfeiting applications. Here, the authors design hydrophobic carbon dots with reversible two-mode fluorescence, which exhibit blue emission when dissolved in solution, and red solid-state fluorescence when aggregated.

Root nodules are agricultural-important symbiotic plant-microbe composites in which microorganisms receive energy from plants and reduce dinitrogen (N2) into fertilizers. Mimicking root nodules using artificial devices can enable renewable energy-driven fertilizer production. This task is challenging due to the necessity of a microscopic dioxygen (O2) concentration gradient, which reconciles anaerobic N2 fixation with O2-rich atmosphere. Here we report our designed electricity-powered biological|inorganic hybrid system that possesses the function of root nodules. We construct silicon-based microwire array electrodes and replicate the O2 gradient of root nodules in the array. The wire array compatibly accommodates N2-fixing symbiotic bacteria, which receive energy and reducing equivalents from inorganic catalysts on microwires, and fix N2 in the air into biomass and free ammonia. A N2 reduction rate up to 6.5 mg N2 per gram dry biomass per hour is observed in the device, about two orders of magnitude higher than the natural counterparts., Root nodules are of key importance in nitrogen fixation. Here, the authors report on an electrically powered artificial root nodule for nitrogen fixation made from silicon-based microwires which can accommodate nitrogen fixing symbiotic bacteria for fixing nitrogen into biomass and free ammonia.

Microbial biophotovoltaic cells exploit the ability of cyanobacteria and microalgae to convert light energy into electrical current using water as the source of electrons. Such bioelectrochemical systems have a clear advantage over more conventional microbial fuel cells which require the input of organic carbon for microbial growth. However, innovative approaches are needed to address scale-up issues associated with the fabrication of the inorganic (electrodes) and biological (microbe) parts of the biophotovoltaic device. Here we demonstrate the feasibility of using a simple commercial inkjet printer to fabricate a thin-film paper-based biophotovoltaic cell consisting of a layer of cyanobacterial cells on top of a carbon nanotube conducting surface. We show that these printed cyanobacteria are capable of generating a sustained electrical current both in the dark (as a ‘solar bio-battery’) and in response to light (as a ‘bio-solar-panel’) with potential applications in low-power devices., Cyanobacteria can be exploited to convert light energy into electrical current, however utilising them efficiently for power generation is a challenge. Here, the authors use a simple commercial inkjet printer to fabricate a thin-film paper-based biophotovoltaic cell capable of driving low-power devices.

7 billion tonnes of alkaline materials are produced globally each year as a product or by-product of industrial activity. The aqueous dissolution of these materials creates high pH solutions that dissolves CO2 to store carbon in the form of solid carbonate minerals or dissolved bicarbonate ions. Here we show that these materials have a carbon dioxide storage potential of 2.9–8.5 billion tonnes per year by 2100, and may contribute a substantial proportion of the negative emissions required to limit global temperature change to, The potential of biomass energy carbon capture and storage is unclear. Here the authors estimated the negative emissions potential from highly alkaline materials, by-products and wastes and showed that these materials have a CO2 storage potential of 2.5–7.5 billion tonnes per year by 2100.

Biological lignin valorization has emerged as a major solution for sustainable and cost-effective biorefineries. However, current biorefineries yield lignin with inadequate fractionation for bioconversion, yet substantial changes of these biorefinery designs to focus on lignin could jeopardize carbohydrate efficiency and increase capital costs. We resolve the dilemma by designing ‘plug-in processes of lignin’ with the integration of leading pretreatment technologies. Substantial improvement of lignin bioconversion and synergistic enhancement of carbohydrate processing are achieved by solubilizing lignin via lowering molecular weight and increasing hydrophilic groups, addressing the dilemma of lignin- or carbohydrate-first scenarios. The plug-in processes of lignin could enable minimum polyhydroxyalkanoate selling price at as low as $6.18/kg. The results highlight the potential to achieve commercial production of polyhydroxyalkanoates as a co-product of cellulosic ethanol. Here, we show that the plug-in processes of lignin could transform biorefinery design toward sustainability by promoting carbon efficiency and optimizing the total capital cost., The current biorefineries yield lignin with inadequate fractionation for bioconversion, yet substantial changes of these biorefinery designs could jeopardize carbohydrate efficiency and increase capital costs. Here the authors resolve the dilemma by designing ‘plug-in processes of lignin’ to enable economic waste valorization.

Current thermochemical methods to generate H2 include gasification and steam reforming of coal and natural gas, in which anthropogenic CO2 emission is inevitable. If biomass is used as a source of H2, the process can be considered carbon-neutral. Seaweeds are among the less studied types of biomass with great potential because they do not require freshwater. Unfortunately, reaction pathways to thermochemically convert salty and wet biomass into H2 are limited. In this study, a catalytic alkaline thermal treatment of brown seaweed is investigated to produce high purity H2 with substantially suppressed CO2 formation making the overall biomass conversion not only carbon-neutral but also potentially carbon-negative. High-purity 69.69 mmol-H2/(dry-ash-free)g-brown seaweed is produced with a conversion as high as 71%. The hydroxide is involved in both H2 production and in situ CO2 capture, while the Ni/ZrO2 catalyst enhanced the secondary H2 formation via steam methane reforming and water-gas shift reactions., While biomass may serve as a renewable source of carbon-neutral hydrogen, it is challenging both to utilize as-found bio-resources and to suppress CO2 formation. Here, authors convert wet, salty seaweed using alkaline thermal treatment to produce high-purity hydrogen and suppress carbon emission.

Organic electronics is emerging for large-area applications such as photovoltaic cells, rollable displays or electronic paper. Its future development and integration will require a simple, low-power organic memory, that can be written, erased and readout electrically. Here we demonstrate a non-volatile memory in which the ferroelectric polarisation state of an organic tunnel barrier encodes the stored information and sets the readout tunnel current. We use high-sensitivity piezoresponse force microscopy to show that films as thin as one or two layers of ferroelectric poly(vinylidene fluoride) remain switchable with low voltages. Submicron junctions based on these films display tunnel electroresistance reaching 1,000% at room temperature that is driven by ferroelectric switching and explained by electrostatic effects in a direct tunnelling regime. Our findings provide a path to develop low-cost, large-scale arrays of organic ferroelectric tunnel junctions on silicon or flexible substrates., Ferroelectric organic materials can be used for tunnel barriers in memory devices as a cheaper and eco-friendly replacement of their inorganic counterparts. Here, Tian et al. use poly(vinylidene fluoride) with 1–2 layer thickness to achieve giant tunnel electroresistance of 1,000% at room temperature.

Maximizing the conversion of biogenic carbon feedstocks into chemicals and fuels is essential for fermentation processes as feedstock costs and processing is commonly the greatest operating expense. Unfortunately, for most fermentations, over one-third of sugar carbon is lost to CO2 due to the decarboxylation of pyruvate to acetyl-CoA and limitations in the reducing power of the bio-feedstock. Here we show that anaerobic, non-photosynthetic mixotrophy, defined as the concurrent utilization of organic (for example, sugars) and inorganic (for example, CO2) substrates in a single organism, can overcome these constraints to increase product yields and reduce overall CO2 emissions. As a proof-of-concept, Clostridium ljungdahlii was engineered to produce acetone and achieved a mass yield 138% of the previous theoretical maximum using a high cell density continuous fermentation process. In addition, when enough reductant (that is, H2) is provided, the fermentation emits no CO2. Finally, we show that mixotrophy is a general trait among acetogens., Microbial fermentation yield is limited by CO2 loss in glycolysis. Here, the authors engineered Clostridium ljungdahlii for the anaerobic, non-photosynthetic mixotrophy production of acetone, increasing carbon product yield while reducing CO2 emissions from a biogenic feedstock fermentation.

The degradation of intrinsic properties of graphene during the transfer process constitutes a major challenge in graphene device fabrication, stimulating the need for direct growth of graphene on dielectric substrates. Previous attempts of metal-induced transformation of diamond and silicon carbide into graphene suffers from metal contamination and inability to scale graphene growth over large area. Here, we introduce a direct approach to transform polycrystalline diamond into high-quality graphene layers on wafer scale (4 inch in diameter) using a rapid thermal annealing process facilitated by a nickel, Ni thin film catalyst on top. We show that the process can be tuned to grow single or multilayer graphene with good electronic properties. Molecular dynamics simulations elucidate the mechanism of graphene growth on polycrystalline diamond. In addition, we demonstrate the lateral growth of free-standing graphene over micron-sized pre-fabricated holes, opening exciting opportunities for future graphene/diamond-based electronics., Direct growth of large-area graphene on dielectric substrates is a promising route to wafer scale integration. Here the authors use a rapid thermal annealing process to grow graphene layers on four-inch diameter polycrystalline diamond, eliminating the need for transfer.

Graphene-based membranes demonstrating ultrafast water transport, precise molecular sieving of gas and solvated molecules shows great promise as novel separation platforms; however, scale-up of these membranes to large-areas remains an unresolved problem. Here we demonstrate that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially adaptable method to produce large-area membranes (13 × 14 cm2) in 90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30–40%) retention of monovalent and divalent salts. The highly ordered graphene sheets in the plane of the membrane make organized channels and enhance the permeability (71±5 l m−2 hr−1 bar−1 for 150±15 nm thick membranes)., Membranes made from graphene have ultra-fast water transport and precise molecular sieving properties. Here, the authors show how large-area membranes can be manufactured by a rapid and scalable process based on shear alignment of graphene-oxide liquid crystals for unlocking industrial applications.

Culture contamination, end-product toxicity, and energy efficient product recovery are long-standing bioprocess challenges. To solve these problems, we propose a high-pressure fermentation strategy, coupled with in situ extraction using the abundant and renewable solvent supercritical carbon dioxide (scCO2), which is also known for its broad microbial lethality. Towards this goal, we report the domestication and engineering of a scCO2-tolerant strain of Bacillus megaterium, previously isolated from formation waters from the McElmo Dome CO2 field, to produce branched alcohols that have potential use as biofuels. After establishing induced-expression under scCO2, isobutanol production from 2-ketoisovalerate is observed with greater than 40% yield with co-produced isopentanol. Finally, we present a process model to compare the energy required for our process to other in situ extraction methods, such as gas stripping, finding scCO2 extraction to be potentially competitive, if not superior., End-product toxicity, culture contamination, and energy efficient product recovery are long-standing issues in bioprocessing. Here, the authors address these problems using a fermentation strategy that combines microbial production of branched alcohols with supercritical carbon dioxide extraction.

The high thermal conductivity of graphene and few-layer graphene undergoes severe degradations through contact with the substrate. Here we show experimentally that the thermal management of a micro heater is substantially improved by introducing alternative heat-escaping channels into a graphene-based film bonded to functionalized graphene oxide through amino-silane molecules. Using a resistance temperature probe for in situ monitoring we demonstrate that the hotspot temperature was lowered by ∼28 °C for a chip operating at 1,300 W cm−2. Thermal resistance probed by pulsed photothermal reflectance measurements demonstrated an improved thermal coupling due to functionalization on the graphene–graphene oxide interface. Three functionalization molecules manifest distinct interfacial thermal transport behaviour, corroborating our atomistic calculations in unveiling the role of molecular chain length and functional groups. Molecular dynamics simulations reveal that the functionalization constrains the cross-plane phonon scattering, which in turn enhances in-plane heat conduction of the bonded graphene film by recovering the long flexural phonon lifetime., The high thermal conductivity of graphene is considerably reduced when the two-dimensional material is in contact with a substrate. Here, the authors show that thermal management of a micro heater is improved using graphene-based films covalently bonded by amino-silane molecules to graphene oxide.

The interest in mechanical properties of two-dimensional materials has emerged in light of new device concepts taking advantage of flexing, adhesion and friction. Here we demonstrate an effective method to measure adhesion of graphene atop highly ordered pyrolytic graphite, utilizing atomic-scale ‘blisters' created in the top layer by neon atom intercalates. Detailed analysis of scanning tunnelling microscopy images is used to reconstruct atomic positions and the strain map within the deformed graphene layer, and demonstrate the tip-induced subsurface translation of neon atoms. We invoke an analytical model, originally devised for graphene macroscopic deformations, to determine the graphite adhesion energy of 0.221±0.011 J m−2. This value is in excellent agreement with reported macroscopic values and our atomistic simulations. This implies mechanical properties of graphene scale down to a few-nanometre length. The simplicity of our method provides a unique opportunity to investigate the local variability of nanomechanical properties in layered materials., Analysis of the mechanical properties of two-dimensional materials is important for device development. Here, the authors report a microscopic method for measuring the adhesion of graphene on top of highly ordered pyrolytic graphite, which exploits atomic-scale blisters formed upon neon atom intercalation.

Herein, we report on a significant discovery, namely, the quantitative discharging of reduced graphite forms, such as graphite intercalation compounds, graphenide dispersions and graphenides deposited on surfaces with the simple solvent benzonitrile. Because of its comparatively low reduction potential, benzonitrile is reduced during this process to the radical anion, which exhibits a red colour and serves as a reporter molecule for the quantitative determination of negative charges on the carbon sheets. Moreover, this discovery reveals a very fundamental physical–chemical phenomenon, namely a quantitative solvent reduction induced and electrostatically driven mass transport of K+ ions from the graphite intercalation compounds into the liquid. The simple treatment of dispersed graphenides suspended on silica substrates with benzonitrile leads to the clean conversion to graphene. This unprecedented procedure represents a rather mild, scalable and inexpensive method for graphene production surpassing previous wet-chemical approaches., Graphite intercalation compounds are promising precursors for the reductive exfoliation of graphene. Here, the authors unveil the discharging mechanism of reduced graphitic compounds in a solid/liquid phase reaction, and further demonstrate its practical use for graphene production.

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites., The development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here, the authors report and evaluate a catalyst based on a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide.