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Graphene oxide nanomaterials have been developed for wide-ranging applications, but has potential safety concerns for human health. Controlled inhalation exposures in human volunteers have been a vital means to determine the effects and mechanisms of ultrafine particles in air pollution, however, few studies have used this approach to explore the effects of nanomaterials. We conducted a double-blind randomised controlled study to determine whether inhalation of graphene oxide affects pulmonary or cardiovascular function. A high purity graphene oxide was synthesised with a thickness of 1-2 layers in two sizes: ‘small’ (lateral dimensions: 100-1700 nm) and ‘ultrasmall’ (30-500 nm). Graphene oxide particles at 200 µg/m3, or filtered air, were inhaled for 2 hours by 14 young healthy volunteers on repeated visits, with measurement of cardiorespiratory parameters before and across 4 hours after exposure. Graphene oxide exposure was well-tolerated with no adverse effects. Heart rate, blood pressure, lung function and inflammatory markers were unaffected by graphene oxide irrespective of particle size. GO did not change blood biomarkers of coagulation, however, there was a mild increase in thrombus formation in an ex vivo model of arterial injury. Proteomics revealed very few differential plasma proteins. Overall, acute inhalation of graphene oxide was not associated with overt detrimental effects in healthy humans. These findings demonstrate the feasibility of carefully controlled human exposures for risk assessment of graphene nanomaterials.

The growing production of graphene oxide (GO) and GO-based products has led to an increased risk of human exposure and caused scientific and public concern about human health and safety. Even though human exposure to GO can occur via different pathways, the main exposure route for airborn GO is through the lungs, thus placing the respiratory tract at particular risk. Occupational exposure to GO might occur repeatedly over a prolonged period of time but insights on lung toxicity of long-term repeated GO administration is largely lacking. Moreover, there is a risk that GO co-exposure with prevalent lung pathogens (e.g. Streptococcus pneumoniae (SP)) could increase the susceptibility to lung infections. In this study, we aimed to investigate the impact of repeated and prolonged GO exposure in healthy and SP-infected lungs using well-characterized materials with distinct properties and reconstituted primary human bronchial epithelial cultures. Our results revealed that GO had no major toxicity effects on healthy airway epithelium even upon prolonged exposure, but alterations in inflammatory/immune signaling was apparent and showed a correlation with the lateral particle size. GO pre-exposure slightly altered the response of the airway epithelium towards subsequent SP infection as evidenced by a decreased mitochondrial activity, increased bacterial translocation and altered inflammatory/immune responses. Whole genome transcriptomic profiling is ongoing to gain insights in deregulated genes and pathways following chronic GO administration. Our findings on the health risks of GO inhalation in healthy and infected human lung is important to risk assessment and management of this promising material.

Nanocomposites have received significant interest in recent years, as they offer improved properties compared to conventional materials for various applications. Among many available nanofillers, graphene nanoplatelets (GNP) have shown promising results for polymer-based nanocomposite applications. This paper investigates the mechanical and thermal properties of GNP-reinforced virgin and recycled polycarbonate (PC) nanocomposites blended via a twin-screw extruder. Effects of various key processing parameters such as filler concentration, processing speed, barrel/die set temperature, and PC type (virgin and recycled) on the reinforced composites were examined. Mechanical properties were characterised by tensile testing, while thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to characterise the thermal properties. The results show that the processing speed and barrel/die set temperature have a slight influence, while the filler concentration significantly affects the properties of PC/GNPs composites. The Young's modulus and yield strength were enhanced with increasing GNP loading, where the maximum enhancement of Young's modulus was obtained as ∼33% for virgin-PC/GNP and ∼39.5% for recycled-PC/GNP composites at 10 wt.-% GNP loading. However, the failure strain was reduced with the increased GNP loading for both virgin and recycled PC/GNP composites. Embedding GNP into the PC matrix only slightly influenced the thermal stability and glassy transition temperature (Tg). The highest thermal stability for virgin PC/GNP composites was observed with 1 wt.-% (2.74% increase with respect to virgin PC), while for recycled PC/GNP, it was observed with 10 wt.-% (2.42% increase with respect to recycled PC) GNP loading. Under the same GNP loading, recycled PC-based composites showed lower thermal stability than virgin PC-based composites. The Tg evaluated from DSC showed a rise under 1 wt.-% GNP for virgin PC/GNP and decrease afterwards with higher filler loading, while an irregular variation for recycled PC/GNP was observed.

Spintronics involves the development of low-dimensional electronic systems with potential use in quantum-based computation. In graphene, there has been significant progress in improving spin transport characteristics by encapsulation and reducing impurities, but the influence of standard two-dimensional (2D) tunnel contacts, via pinholes and doping of the graphene channel, remains difficult to eliminate. Here, we report the observation of spin injection and tuneable spin signal in fully-encapsulated graphene, enabled by van der Waals heterostructures with one-dimensional (1D) contacts. This architecture prevents significant doping from the contacts, enabling high-quality graphene channels, currently with mobilities up to 130,000 cm$^2$V$^{-1}$s$^{-1}$ and spin diffusion lengths approaching 20 ${\mu}$m. The nanoscale-wide 1D contacts allow spin injection both at room and at low temperature, with the latter exhibiting efficiency comparable with 2D tunnel contacts. At low temperature, the spin signals can be enhanced by as much as an order of magnitude by electrostatic gating, adding new functionality., Comment: Manuscript and Supporting Information

Research on graphene based nanomaterials has flourished in the last decade due their unique properties and emerging socio-economic impact. In the context of their potential exploitation for biomedical applications, there is a growing need for the development of more efficient imaging techniques to track the fate of these materials. Herein we propose the first correlative imaging approach based on the combination of radioimaging and mass spectrometry imaging for the detection of Graphene Oxide (GO) labelled with carbon-14 in mice. In this study, 14C-graphene oxide nanoribbons were produced from the oxidative opening of 14C-carbon nanotubes, and were then intensively sonicated to provide nano-size 14C-GO flakes. After Intravenous administration in mice, 14C-GO distribution was quantified by radioimaging performed on tissue slices. On the same slices, MS-imaging provided a highly resolved distribution map of the nanomaterial based on the detection of specific radical anionic carbon clusters ranging from C2˙− to C9˙− with a base peak at m/z 72 (12C) and 74 (14C) under negative laser desorption ionization mass spectrometry (LDI-MS) conditions. This proof of concept approach synergizes the strength of each technique and could be advantageous in the pre-clinical development of future Graphene-based biomedical applications.

Carbon-fibre-reinforced polymer (CFRP) composites are promising materials for non-metallic pipe applications in the oil and gas industry owing to their high corrosion resistance, specific strength and stiffness. However, CFRP has poor gas barrier performance meaning that a liner has to be inserted. Graphene-based nanomaterials have been demonstrated to improve gas barrier properties in thermoplastic polymers, and thus, a CFRP–graphene hybrid composite could provide an alternative to lined pipes. In this work, a method combining spray coating with vacuum-assisted resin infusion was developed to fabricate CFRP hybrid composites with preferred in-plane aligned graphene nanoplatelets. Tensile and flexural properties, as well as CO2 gas permeability, were evaluated. It was illustrated that both tensile and flexural properties performed better under relatively low GNP loadings ( Graphical abstract

An important aspect of immunotherapy is the ability of dendritic cells (DCs) to prime T cell immunity, an approach that has yielded promising results in some early phase clinical trials. However, novel approaches are required to improve DC therapeutic efficacy by enhancing their uptake of, and activation by, disease relevant antigens. The carbon nano-material graphene oxide (GO) may provide a unique way to deliver antigen to innate immune cells and modify their ability to initiate effective adaptive immune responses. We have assessed whether GO of various lateral sizes affects DC activation and function in vitro and in vivo, including their ability to take up, process and present the well-defined model antigen ovalbumin (OVA). We have found that GO flakes are internalised by DCs, while having minimal effect on their viability, activation phenotype or cytokine production. Although adsorption of OVA protein to either small or large GO flakes promoted its uptake into DCs, large GO interfered with OVA processing. In terms of modulation of DC function, delivery of OVA via small GO flakes significantly enhanced DC ability to induce proliferation of OVA-specific CD4 T cells, promoting granzyme B secretion in vitro. On the other hand, delivery of OVA via large GO flakes augmented DC ability to induce proliferation of OVA-specific CD8 T cells, and their production of IFN-γ and granzyme B. Together, these data demonstrate the capacity of GO of different lateral dimensions to act as a promising delivery platform for DC modulation of distinct facets of the adaptive immune response, information that could be exploited for future development of targeted immunotherapies., his work was supported by the Engineering and Physical Sciences Research Council (EPSRC) under the 2D-Health Programme Grant [EP/P00119X/1]. The Nanomedicine Group at ICN2 is partially supported by the CERCA programme, Generalitat de Catalunya, and the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (AEI, grant no. SEV-2017-0706).

Engineered 2D nanomaterials such as graphene oxide (GO) and hexagonal boron nitride (hBN) are an emerging but growing aspect of human technology. However, research is still inconclusive on the respiratory system response to such 2D materials. One area of recent concern is the generation of innate immune memory (IIM). Innate imprinting can be defined as the acquisition by innate cells of memory like characteristics in the form of epigenetic modifications. If triggered, these modifications may induce altered immune responses to environmental stimuli, such as allergens, engineered nanomaterials or air pollution related particles. These altered responses could result in detrimental consequences for those environmentally exposed and for therapeutic applications.In the present study bone marrow derived macrophages (BMDM) were exposed for 24 h to either GO or hBN, and then re-exposed to the same materials after 5 days. Cytokine secretion, uptake, gene expression and epigenetic markers were then measured to determine the generation of inflammation and IIM related epigenetic modifications. Raman mapping and confocal microscopy indicated that both materials were being taken up by BMDM in detectable quantities. However, GO did not induce inflammation or IIM in BMDM upon multiple exposures. In addition, exposure to GO did not change the response of BMDM to secondary stimuli such as lipopolysaccharide and β-glucan. On the other hand, hBN induced an inflammatory response associated to iNOS-related pathways after both one and multiple exposures. Nevertheless, analysis of the epigenetics after hBN exposure did not indicate the significant presence of epigenetic markers related to IIM.It was concluded that for direct in vitro exposure, endotoxin free GO could be considered ‘inert’ eliciting no detectible response from BMDM. In contrast endotoxin free hBN can induce an inflammatory state in BMDM but not any long-term epigenetic modifications related to IIM. The lack of long-term epigenetic responses is a beneficial outcome for the overall safety of the materials. It suggests that the innate system response would not change over repeated long-term but low dose exposures to 2D materials, as would be expected in an occupational exposure scenario. These results provide further understanding of the safety profile of 2D materials at a time when their applications in consumer products is growing at fast pace.

Van der Waals (vdW) heterostructures continue to attract intense interest as a route of designing materials with novel properties that cannot be found in naturally occurring materials. Unfortunately, this approach is currently limited to only a few layers that can be stacked on top of each other. Here we report a bulk material consisting of superconducting monolayers interlayered with monolayers displaying charge density waves (CDW). This bulk vdW heterostructure is created by phase transition of 1T-TaS2 to 6R at 800 {\deg}C in an inert atmosphere. Electron microscopy analysis directly shows the presence of alternating 1T and 1H monolayers within the resulting bulk 6R phase. Its superconducting transition (Tc) is found at 2.6 K, exceeding the Tc of the bulk 2H phase of TaS2. The superconducting temperature can be further increased to 3.6 K by exfoliating 6R-TaS2 and then restacking its layers. Using first-principles calculations, we argue that the coexistence of superconductivity and CDW within 6R-TaS2 stems from amalgamation of the properties of adjacent 1H and 1T monolayers, where the former dominates the superconducting state and the latter the CDW behavior.

Glioblastoma (GBM) is the most common and advanced form of primary malignant tumor occurring in the adult central nervous system, and it is frequently associated with epilepsy, a debilitating comorbidity. Seizures are observed both pre- and post-surgical resection, indicating that several pathophysiological mechanisms are shared but also prompting questions about how the process of epileptogenesis evolves throughout GBM progression. Molecular mutations commonly seen in primary GBM, i.e., in PTEN and p53, and their associated downstream effects are known to influence seizure likelihood. Similarly, various intratumoral mechanisms, such as GBM-induced blood-brain barrier breakdown and glioma-immune cell interactions within the tumor microenvironment are also cited as contributing to network hyperexcitability. Substantial alterations to peri-tumoral glutamate and chloride transporter expressions, as well as widespread dysregulation of GABAergic signaling are known to confer increased epileptogenicity and excitotoxicity. The abnormal characteristics of GBM alter neuronal network function to result in metabolically vulnerable and hyperexcitable peri-tumoral tissue, properties the tumor then exploits to favor its own growth even post-resection. It is evident that there is a complex, dynamic interplay between GBM and epilepsy that promotes the progression of both pathologies. This interaction is only more complicated by the concomitant presence of spreading depolarization (SD). The spontaneous, high-frequency nature of GBM-associated epileptiform activity and SD-associated direct current (DC) shifts require technologies capable of recording brain signals over a wide bandwidth, presenting major challenges for comprehensive electrophysiological investigations. This review will initially provide a detailed examination of the underlying mechanisms that promote network hyperexcitability in GBM. We will then discuss how an investigation of these pathologies from a network level, and utilization of novel electrophysiological tools, will yield a more-effective, clinically-relevant understanding of GBM-related epileptogenesis. Further to this, we will evaluate the clinical relevance of current preclinical research and consider how future therapeutic advancements may impact the bidirectional relationship between GBM, SDs, and seizures., This review is supported by the Medical Research Council (MRC), grant reference MR/W019752/1. KH is sponsored by the Graphene NOWNANO PhD programme at the University of Manchester. RW is supported by a Senior Research Fellowship awarded by the Worshipful Company of Pewterers.

Aqueous zinc‐ion hybrid supercapacitors are a promising energy storage technology, owing to their high safety, low cost, and long‐term stability. At present, however, there is a lack of understanding of the potential window and self‐discharge of this aqueous energy storage technology. This study concerns a systematic investigation of the potential window of this device by cyclic voltammetry and galvanostatic charge–discharge. Hybrid supercapacitors based on commercial activated carbon (AC) demonstrate a wide and stable potential window (0.2 V to 1.8 V), high specific capacitances (308 F g−1 at 0.5 A g−1 and 110 F g−1 at 30 A g−1), good cycling stability (10000 cycles with 95.1 % capacitance retention), and a high energy density (104.8 Wh kg−1 at 383.5 W kg−1), based on the active materials. The mechanism involves simultaneous adsorption–desorption of ions on the AC cathode and zinc ion plating/stripping on the Zn anode. This work leads to better understanding of such devices and will aid future development of practical high‐performance aqueous zinc‐ion hybrid supercapacitors based on commercial carbon materials, thus accelerating the deployment of these hybrid supercapacitors and filling the gap between supercapacitors and batteries., A window into self‐discharge: A systematic investigation of the potential window and self‐discharge in aqueous zinc‐ion hybrid supercapacitors based on commercial activated carbon (AC) and Zn foil with nontoxic electrolyte is carried out by cyclic voltammetry and galvanostatic charge–discharge methods, with a view to filling the gap between supercapacitors and batteries.

Graphene oxide (GO) nanosheet suspension is not stable in physiological ionic fluids. To improve stability, surfactants such as Pluronic 103 (P103) have been tested. Going further, this work investigated whether conferring positive surface charge to the surfactant may improve the adsorption ability of P103 micelles on GO sheets. Positive charge on the surfactant was induced by adding dodecyltrimethylammonium bromide (DTAB, a cationic surfactant) in P103 micelles. Subsequent changes in aggregation parameters were investigated through dynamic light scattering and small-angle neutron scattering studies. DTAB incorporation was accompanied by a steady increase in the ζ potential and mixed micelle formation. At high surface charge density, the interaction between adjacent head groups was distorted, which led to dissociation of mixed micelles. Structural developments during the adsorption of mixed micelles on the sheet surface (mass fractal formation) were monitored in terms of changes in the scattering features of aggregates. These fractals emerged as a result of electrostatic interactions. Our observations point toward the existence of small-sized building blocks at low DTAB concentration (≤4 mM). With a superior adsorption, mixed micelles are expected to occupy the intersheet space and maintain a hydration layer. However, at a higher DTAB concentration (≥10 mM), micelles dissociate to produce DTAB-rich unimers and P103-rich loose aggregates. At this point, sheets tend to aggregate in the solvent, regardless of fractal formation.

Fabrics—materials consisting of layers of woven fibres—are some of the most important materials in everyday life1. Previous nanoscale weaves2–16 include isotropic crystalline covalent organic frameworks12–14 that feature rigid helical strands interlaced in all three dimensions, rather than the two-dimensional17,18 layers of flexible woven strands that give conventional textiles their characteristic flexibility, thinness, anisotropic strength and porosity. A supramolecular two-dimensional kagome weave15 and a single-layer, surface-supported, interwoven two-dimensional polymer16 have also been reported. The direct, bottom-up assembly of molecular building blocks into linear organic polymer chains woven in two dimensions has been proposed on a number of occasions19–23, but has not previously been achieved. Here we demonstrate that by using an anion and metal ion template, woven molecular ‘tiles’ can be tessellated into a material consisting of alternating aliphatic and aromatic segmented polymer strands, interwoven within discrete layers. Connections between slowly precipitating pre-woven grids, followed by the removal of the ion template, result in a wholly organic molecular material that forms as stacks and clusters of thin sheets—each sheet up to hundreds of micrometres long and wide but only about four nanometres thick—in which warp and weft single-chain polymer strands remain associated through periodic mechanical entanglements within each sheet. Atomic force microscopy and scanning electron microscopy show clusters and, occasionally, isolated individual sheets that, following demetallation, have slid apart from others with which they were stacked during the tessellation and polymerization process. The layered two-dimensional molecularly woven material has long-range order, is birefringent, is twice as stiff as the constituent linear polymer, and delaminates and tears along well-defined lines in the manner of a macroscopic textile. When incorporated into a polymer-supported membrane, it acts as a net, slowing the passage of large ions while letting smaller ions through. An anion and metal ion template is used to form woven polymer patches that are joined together by polymerization into a fully woven, two-dimensional, molecular patchwork.

[Background] A key aspect of any new material safety assessment is the evaluation of their in vivo genotoxicity. Graphene oxide (GO) has been studied for many promising applications, but there are remaining concerns about its safety profile, especially after inhalation. Herein we tested whether GO lateral dimension, comparing micrometric (LGO) and nanometric (USGO) GO sheets, has a role in the formation of DNA double strand breaks in mouse lungs. We used spatial resolution and differential cell type analysis to measure DNA damages in both epithelial and immune cells, after either single or repeated exposure., [Results] GO induced DNA damages were size and dose dependent, in both exposure scenario. After single exposure to a high dose, both USGO and LGO induced significant DNA damage in the lung parenchyma, but only during the acute phase response (p < 0.05 for USGO; p < 0.01 for LGO). This was followed by a fast lung recovery at day 7 and 28 for both GOs. When evaluating the chronic impact of GO after repeated exposure, only a high dose of LGO induced long-term DNA damages in lung alveolar epithelia (at 84 days, p < 0.05). Regardless of size, low dose GO did not induce any significant DNA damage after repeated exposure. A multiparametric correlation analysis of our repeated exposure data revealed that transient or persistent inflammation and oxidative stress were associated to either recovery or persistent DNA damages. For USGO, recovery from DNA damage was correlated to efficient recovery from acute inflammation (i.e., significant secretion of SAA3, p < 0.001; infiltration of neutrophils, p < 0.01). In contrast, the persistence of LGO in lungs was associated to a long-lasting presence of multinucleated macrophages (up to 84 days, p < 0.05), an underlying inflammation (IL-1α secretion up to 28 days, p < 0.05) and the presence of persistent DNA damages at 84 days., [Conclusions] Overall these results highlight the importance of the exposure scenario used. We showed that LGO was more genotoxic after repeated exposure than single exposure due to persistent lung inflammation. These findings are important in the context of human health risk assessment and toward establishing recommendations for a safe use of graphene based materials in the workplace., The present study was supported by the UK Research and Innovation Engineering and Physical Sciences Research Council (UKRI-EPSRC) Centre for Doctoral Training programme Graphene NOWNANO (EP/L01548X/1), and the European Union (EU) 8th Framework Programme for Research and Technological Development, H2020 Future and Emerging Technologies, GrapheneFlagship project (H2020-FET- GrapheneCore2 - #785219 and H2020-FET- GrapheneCore3 - #881603). The ICN2 is funded by the CERCA programme, Generalitat de Catalunya, and is supported by the Severo Ochoa Centres of Excellence programme by the Spanish Research Agency (AEI, grant no. SEV-2017-0706).

Graphene-related materials (GRMs) are subject to intensive investigations and considerable progress has been made in recent years in terms of safety assessment. However, limited information is available concerning the hazard potential of GRM-containing products such as graphene-reinforced composites. In the present study, we conducted a comprehensive investigation of the potential biological effects of particles released through an abrasion process from reduced graphene oxide (rGO)-reinforced composites of polyamide 6 (PA6), a widely used engineered thermoplastic polymer, in comparison to as-produced rGO. First, a panel of well-established in vitro models, representative of the immune system and possible target organs such as the lungs, the gut, and the skin, was applied. Limited responses to PA6-rGO exposure were found in the different in vitro models. Only as-produced rGO induced substantial adverse effects, in particular in macrophages. Since inhalation of airborne materials is a key occupational concern, we then sought to test whether the in vitro responses noted for these materials would translate into adverse effects in vivo. To this end, the response at 1, 7 and 28 days after a single pulmonary exposure was evaluated in mice. In agreement with the in vitro data, PA6-rGO induced a modest and transient pulmonary inflammation, resolved by day 28. In contrast, rGO induced a longer-lasting, albeit moderate inflammation that did not lead to tissue remodeling within 28 days. Taken together, the present study suggests a negligible impact on human health under acute exposure conditions of GRM fillers such as rGO when released from composites at doses expected at the workplace., This work was supported by the European Union (EU) 8th Framework Program for Research and Technological Development, Graphene Flagship project (H2020-FET- GrapheneCore2 - #785219 and H2020-FET- GrapheneCore3 - #881603). Part of this work was supported by the University of Trieste, the Agence Nationale de la Recherche (ANR) through the LabEx project Chemistry of Complex Systems (ANR-10-LABX- 0026_CSC), the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency – Grant No. MDM-2017-0720 and the Swiss National Science Foundation (Grant 310030_169207).

Wearable e-textiles have gained huge tractions due to their potential for non-invasive health monitoring. However, manufacturing of multifunctional wearable e-textiles remains challenging, due to poor performance, comfortability, scalability, and cost. Here, we report a fully printed, highly conductive, flexible, and machine-washable e-textiles platform that stores energy and monitor physiological conditions including bio-signals. The approach includes highly scalable printing of graphene-based inks on a rough and flexible textile substrate, followed by a fine encapsulation to produce highly conductive machine-washable e-textiles platform. The produced e-textiles are extremely flexible, conformal, and can detect activities of various body parts. The printed in-plane supercapacitor provides an aerial capacitance of ∼3.2 mFcm−2 (stability ∼10,000 cycles). We demonstrate such e-textiles to record brain activity (an electroencephalogram, EEG) and find comparable to conventional rigid electrodes. This could potentially lead to a multifunctional garment of graphene-based e-textiles that can act as flexible and wearable sensors powered by the energy stored in graphene-based textile supercapacitors.

The availability of accessible fabrication methods based on deterministic transfer of atomically thin crystals has been essential for the rapid expansion of research into van der Waals heterostructures. An inherent issue of these techniques is the deformation of the polymer carrier film during the transfer, which can lead to highly non-uniform strain induced in the transferred two-dimensional material. Here, using a combination of optical spectroscopy, atomic force and Kelvin probe force microscopy, we show that the presence of nanometer scale wrinkles formed due to transfer-induced stress relaxation can lead to strong changes in the optical properties of MoSe$_2$/WSe$_2$ heterostructures and the emergence of the linearly polarized interlayer exciton photoluminescence. We attribute these changes to the local breaking of crystal symmetry in the nanowrinkles, which act as efficient accumulation centers for the interlayer excitons due to the strain-induced interlayer band gap reduction. The surface potential images of the rippled heterobilayer samples acquired using Kelvin probe force microscopy reveal the variation of the local work function consistent with the strain-induced band gap modulation, while the potential offset observed at the ridges of the wrinkles shows a clear correlation with the value of the tensile strain estimated from the wrinkle geometry. Our findings highlight the important role of the residual strain in defining optical properties of van der Waals heterostructures and suggest novel approaches for interlayer exciton manipulation by local strain engineering.

Liquid- phase exfoliation (LPE) is the principal method of producing two-dimensional (2D) materials such as graphene in large quantities with a good balance between quality and cost and is now widely adopted by both the academic and industrial sectors. The fragmentation and exfoliation mechanisms involved have usually been simply attributed to the force induced by ultrasound and the interaction with the solvent molecules. Nonetheless, little is known about how they actually occur, i.e., how thick and large graphite crystals can be exfoliated into thin and small graphene flakes. Here, we demonstrate that during ultrasonic LPE the transition from graphite flakes to graphene takes place in three distinct stages. First, sonication leads to the rupture of large flakes and the formation of kink band striations on the flake surfaces, primarily along zigzag directions. Second, cracks form along these striations, and together with intercalation of solvent, lead to the unzipping and peeling off of thin graphite strips that in the final stage are exfoliated into graphene. The findings will be of great value in the quest to optimize the lateral dimensions, thickness, and yield of graphene and other 2D materials in large-scale LPE for various applications.

Membrane capacitive deionization (MCDI) for water desalination is an innovative technique that could help to solve the global water scarcity problem. However, the development of the MCDI field is hindered by the limited choice of ion-exchange membranes. Desalination by MCDI removes the salt (solute) from the water (solvent); which can drastically reduce energy consumption compared to traditional desalination practices such as distillation. Herein, we outline the fabrication and characterization of quaternized anion-exchange membranes (AEMs) based on polymer blends of polyethylenimine (PEI) and polybenzimidazole (PBI) that provides an efficient membrane for MCDI. Flat sheet polymer membranes were prepared by solution casting, heat treatment and phase inversion, followed by modification to impart anion-exchange character. Scanning electron microscopy (SEM), atomic force microscopy (AFM), nuclear magnetic resonance (NMR) and Fourier-Transform infrared (FTIR) spectroscopy were used to characterize the morphology and chemical composition of the membranes. The as-prepared membranes displayed high ion-exchange capacity (IEC), hydrophilicity, permselectivity and low area resistance. Due to the addition of PEI, the high density of quaternary ammonium groups increased the IEC and permselectivity of the membranes, while reducing the area resistance relative to pristine PBI AEMs. Our PEI/PBI membranes were successfully employed in asymmetric MCDI for brackish water desalination and exhibited an increase in both salt adsorption capacity (>3x) and charge efficiency (>2x) relative to membrane-free CDI. The use of quaternized polymer blend membranes could help to achieve the greater realization of industrial scale MCDI.

Van der Waals heterostructures form a massive interdisciplinary research field, fueled by the rich material science opportunities presented by layer assembly of artificial solids with controlled composition, order and relative rotation of adjacent atomic planes. Here we use atomic resolution transmission electron microscopy and multiscale modeling to show that the lattice of MoS$_2$ and WS$_2$ bilayers twisted to a small angle, $\theta

Electron-electron interactions play a critical role in many condensed matter phenomena, and it is tempting to find a way to control them by changing the interactions’ strength. One possible approach is to place a studied system in proximity of a metal, which induces additional screening and hence suppresses electron interactions. Here, using devices with atomically-thin gate dielectrics and atomically-flat metallic gates, we measure the electron-electron scattering length in graphene and report qualitative deviations from the standard behavior. The changes induced by screening become important only at gate dielectric thicknesses of a few nm, much smaller than a typical separation between electrons. Our theoretical analysis agrees well with the scattering rates extracted from measurements of electron viscosity in monolayer graphene and of umklapp electron-electron scattering in graphene superlattices. The results provide a guidance for future attempts to achieve proximity screening of many-body phenomena in two-dimensional systems., Experimental control of electron-electron interactions in materials is challenging. Here, the authors control the interactions by proximity screening with gate dielectrics of nanometer thickness, revealing qualitative changes in concentration and temperature dependences, and validating their analysis using electron hydrodynamics and umklapp scattering approaches.

Two-dimensional (2D) barrier materials such as graphene, boron nitride, and molybdenum disulfide hold great promise for important applications such as DNA sequencing, desalination, and biomolecular sensing. The 2D materials commonly span pores through an insulating membrane, and electrical fields are applied to drive cross-barrier transport of charged solvated species. While the low-voltage transmembrane transport is well-understood and controllable, high-voltage phenomena are uncontrolled and result in the apparent breakdown of the 2D material's critical insulating properties. Here we use suspended graphene over a 50 nm silicon nitride nanopore as a model system and show that delamination of the 2D material occurs at higher voltages and can directly cause a number of the puzzling high-voltage transport observations. We confirm the occurrence of delamination and observe via atomic force microscopy measurement a micron-scale delaminated patch in a system using chemical vapor deposition graphene. Furthermore, we show that the conductivity of the same system is strongly correlated to the area of delamination via coincident current measurements and optical imaging of the delaminated area. Finally, we demonstrate that delamination alone can cause a dramatic breakdown of barrier function through observation of a reversible increase in conductance of samples prepared with pristine defect-free graphene. These findings should have a great impact on the design and interpretation of 2D barrier material for both experiments and applications.

We report room temperature Hall mobility measurements, low temperaturemagnetoresistance analysis and low-frequency noise characterization of inkjet-printed graphene films on fused quartz and SiO2/Si substrates. We found that thermal annealing in vacuum at 450 C is a necessary step in order to stabilize the Hall voltage across the devices, allowing their electrical characterization. The printed films present a minimum sheet resistance of 23.3 W/sq after annealing, and are n-type doped, with carrier concentrations in the low 1020 cm􀀀3 range. The charge carrier mobility is found to increase with increasing film thickness, reaching a maximum value of 33 cm2 V􀀀1 s􀀀1 for a 480 nm-thick film printed on SiO2/Si. Low-frequency noise characterization shows a 1/f noise behavior and a Hooge parameter in the range of 0.1 – 1. These results represent thefirst in-depth electrical and noise characterization of transport in inkjet-printed graphene films, able to provide physical insights on the mechanisms at play.

Twistronic heterostructures have recently emerged as a new class of quantum electronic materials with properties determined by the twist angle between the adjacent two-dimensional materials. Here we study moir\'e superlattice minibands in graphene (G) encapsulated in hexagonal boron nitride (hBN) with an almost perfect alignment with both the top and bottom hBN crystals. We show that, for such an orientation of the unit cells of the hBN layers that locally breaks inversion symmetry of the graphene lattice, the hBN/G/hBN structure features a Kagom\'e network of topologically protected chiral states with energies near the miniband edge, propagating along the lines separating the areas with different miniband Chern numbers., Comment: 6 pages, 3 figures (Supplemental Material: 7 pages, 5 figures, 1 table)

In thermodynamic equilibrium, current in metallic systems is carried by electronic states near the Fermi energy whereas the filled bands underneath contribute little to conduction. Here we describe a very different regime in which carrier distribution in graphene and its superlattices is shifted so far from equilibrium that the filled bands start playing an essential role, leading to a critical-current behavior. The criticalities develop upon the velocity of electron flow reaching the Fermi velocity. Key signatures of the out-of-equilibrium state are current-voltage characteristics resembling those of superconductors, sharp peaks in differential resistance, sign reversal of the Hall effect, and a marked anomaly caused by the Schwinger-like production of hot electron-hole plasma. The observed behavior is expected to be common for all graphene-based superlattices., Comment: 22 pages, 11 figures

Graphene has drawn a lot of interest in the material community due to unique physicochemical properties. Owing to a high surface area to volume ratio and free oxygen groups, the oxidized derivative, graphene oxide (GO) has promising potential as a drug delivery system. Here, the lung tolerability of two distinct GO varying in lateral dimensions is investigated, to reveal the most suitable candidate platform for pulmonary drug delivery. Following repeated chronic pulmonary exposure of mice to GO sheet suspensions, the innate and adaptive immune responses are studied. An acute and transient influx of neutrophils and eosinophils in the alveolar space, together with the replacement of alveolar macrophages by interstitial ones and a significant activation toward anti-inflammatory subsets, are found for both GO materials. Micrometric GO give rise to persistent multinucleated macrophages and granulomas. However, neither adaptive immune response nor lung tissue remodeling are induced after exposure to micrometric GO. Concurrently, milder effects and faster tissue recovery, both associated to a faster clearance from the respiratory tract, are found for nanometric GO, suggesting a greater lung tolerability. Taken together, these results highlight the importance of dimensions in the design of biocompatible 2D materials for pulmonary drug delivery system., A.F. and A.A would like to acknowledge studentships co-funded by the Lloyds Register Foundation funded International Consortium on Nanotechnology (LRF-ICON) and the UK Research and Innovation Engineering and Physical Sciences Research Council (UKRI-EPSRC) Centre for Doctoral Training programme Graphene NOWNANO (EP/L01548X/1). This work was also supported by the European Union (EU) 8th Framework Programme for Research and Technological Development, GrapheneFlagship project (H2020-FET-GrapheneCore2—#785219 and H2020-FET-GrapheneCore3—#881603). The authors also thank Dr. Adrian Esteban Arranz, Dr. Miguel Arellano, Irene Rebollido, and Angeliki Karakasidi for their contributions to the synthesis and characterization of the GO materials used in the present study. Matthew Drummond and Abbie Dodd are acknowledged for their contributions to the tissue collection. In addition, the authors would like to acknowledge the following groups at ICN2 (Catalan Institute of Nanoscience and Nanotechnology, Barcelona, Spain): Advanced Electronic Materials and Devices led by Prof. Jose Garrido for the AFM and Raman instrumentation and assistance, and Supramolecular NanoChemistry and Materials led by Prof. Daniel Maspoch for the UV–vis equipment and assistance. The ICN2 is funded by the CERCA programme, Generalitat de Catalunya, and is supported by the Severo Ochoa Centres of Excellence programme by the Spanish Research Agency (AEI, grant no. SEV-2017-0706).

We report on finite bias spectroscopy measurements of the two-electron spectrum in a gate defined bilayer graphene (BLG) quantum dot for varying magnetic fields. The spin and valley degree of freedom in BLG give rise to multiplets of 6 orbital symmetric and 10 orbital anti-symmetric states. We find that orbital symmetric states are lower in energy and separated by $\approx 0.4 - 0.8$ meV from orbital anti-symmetric states. The symmetric multiplet exhibits an additional energy splitting of its 6 states of $\approx 0.15 - 0.5$ meV due to lattice scale interactions. The experimental observations are supported by theoretical calculations, which allow to determine that inter-valley scattering and 'current-current' interaction constants are of the same magnitude in BLG., Comment: 6 pages, 3 figures

Background: Adverse cardiovascular events are a leading cause of perioperative morbidity and mortality. The definitions of perioperative cardiovascular adverse events are heterogeneous. As part of the international Standardized Endpoints in Perioperative Medicine initiative, this study aimed to find consensus amongst clinical trialists on a set of standardised and valid cardiovascular outcomes for use in future perioperative clinical trials. Methods: We identified currently used perioperative cardiovascular outcomes by a systematic review of the anaesthesia and perioperative medicine literature (PubMed/Ovid, Embase, and Cochrane Library). We performed a three-stage Delphi consensus-gaining process that involved 55 clinician researchers worldwide. Cardiovascular outcomes were first shortlisted and the most suitable definitions determined. These cardiovascular outcomes were then assessed for validity, reliability, feasibility, and clarity. Results: We identified 18 cardiovascular outcomes. Participation in the three Delphi rounds was 100% (n=19), 71% (n=55), and 89% (n=17), respectively. A final list of nine cardiovascular outcomes was elicited from the consensus: myocardial infarction, myocardial injury, cardiovascular death, non-fatal cardiac arrest, coronary revascularisation, major adverse cardiac events, pulmonary embolism, deep vein thrombosis, and atrial fibrillation. These nine cardiovascular outcomes were rated by the majority of experts as valid, reliable, feasible, and clearly defined. Conclusions: These nine consensus cardiovascular outcomes can be confidently used as endpoints in clinical trials designed to evaluate perioperative interventions with the goal of improving perioperative outcomes.

Bloch states of electrons in honeycomb two-dimensional crystals with multi-valley band structure and broken inversion symmetry have orbital magnetic moments of a topological nature. In crystals with two degenerate valleys, a perpendicular magnetic field lifts the valley degeneracy via a Zeeman effect due to these magnetic moments, leading to magnetoelectric effects which can be leveraged for creating valleytronic devices. In this work, we demonstrate that trilayer graphene with Bernal stacking, (ABA TLG) hosts topological magnetic moments with a large and widely tunable valley g-factor, reaching a value 1050 at the extreme of the studied parametric range. The reported experiment consists in sublattice-resolved scanning tunneling spectroscopy under perpendicular electric and magnetic fields that control the TLG bands. The tunneling spectra agree very well with the results of theoretical modeling that includes the full details of the TLG tight-binding model and accounts for a quantum-dot-like potential profile formed electrostatically under the scanning tunneling microscope tip., Manuscript and Supporting Information updated

Stress transfer has been investigated for exfoliated hexagonal boron nitride (hBN) nanosheets (BNNSs) through the use of Raman spectroscopy. Single BNNSs of different thicknesses of up to 100 nm (300 layers) were deposited upon a poly(methyl methacrylate) (PMMA) substrate and deformed in unixial tension. The Raman spectra from the BNNSs were relatively weak compared to graphene, but the in-plane E2g Raman mode (the G band) could be distinguished from the spectrum of the PMMA substrate. It was found that G band down-shifted during tensile deformation and that the rate of band shift per unit strain decreased as the thickness of the BNNSs increased, as is found for multi-layer graphene. The efficiency of internal stress transfer between the different hBN layers was found to be of the order of 99% compared to 60%–80% for graphene, as a result of the stronger bonding between the hBN layers in the BNNSs. The reduction in bandshift rate can be related to the effective Young’s modulus of the 2D material in a nanocomposites and the findings show that it would be expected that even 100 layer BNNSs should have a Young’s modulus of more than half that of hBN monolayer. Interfacial stress transfer between a single hBN nanosheet and the PMMA substrate has been evaluated using shear lag theory. It is found that the interfacial shear stress between the BNNS and the substrate is of the order of 10 MPa, a factor of around 4 higher than that for a graphene monolayer. These findings imply that BNNSs should give better mechanical reinforcement than graphene in polymer-based nanocomposites as a result of good internal interlayer stress transfer within the nanosheets and better interfacial stress transfer to the polymer matrix.

The functional form of Coulomb interactions in the transition metal dichalcogenides (TDMs) and other van der Waals solids is critical to many of their unique properties, e.g. strongly-correlated electron states, superconductivity and emergent ferromagnetism. This paper presents measurements of key excitonic energy levels in MoSe2/WSe2 heterostructures. These measurements are obtained from resonance Raman experiments on specific Raman peaks only observed at excited states of the excitons. This data is used to validate a model of the Coulomb potential in these structures which predicts the exciton energies to within ∼5 meV. This model is used to determine the effect of heterostructure formation on the single-particle band gaps of the layers and will have a wide applicability in designing the next generation of more complex TDM structures.

Spintronic devices operating with pure spin currents represent a new paradigm in nanoelectronics, with higher energy efficiency and lower dissipation as compared to charge currents. This technology, however, will be viable only if the amount of spin current diffusing in a nanochannel can be tuned on demand while guaranteeing electrical compatibility with other device elements, to which it should be integrated in high-density three-dimensional architectures. Here, we address these two crucial milestones and demonstrate that pure spin currents can effectively propagate in metallic nanochannels with a three-dimensional curved geometry. Remarkably, the geometric design of the nanochannels can be used to reach an independent tuning of spin transport and charge transport characteristics. These results put the foundation for the design of efficient pure spin current based electronics, which can be integrated in complex three-dimensional architectures., Comment: 3 figures, plus Supporting Information

Current methods for the decontamination of radioactively contaminated surfaces in nuclear facilities typically rely on the use of liquid agents to remove radionuclides. This generates large volumes of highly hazardous liquid waste which must then be treated in costly processes which often require purpose built plant. For the first time we report a nitric acid loaded polymer hydrogel based approach which gives a high decontamination factor for the removal of 137Cs and 90Sr on 304 L grade stainless steel surfaces. The generation of minimal liquid waste and no lateral spread or increased penetration of radionuclides helps mitigate many of the intrinsic hazards of liquid based decontamination methods. Once dried these gels are able to retain the contaminants for treatment as solid waste resulting in a concentrated, less mobile waste form presenting significantly reduced hazards and treatment constraints.

PubMed: 31426634, Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

Rapid, large-scale, and low-cost coating methods that enable precise control of the crystal growth of organic semiconductors are essential to deliver high performance devices that are robust and reproducible. In this work, a novel method is presented, based on a gas blow coating technique, enabling the deposition of thin films of organic semiconductors, whose morphology can be optimized by adjusting the deposition parameters. We demonstrate the deposition of aligned single crystals of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pentacene) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) by gas blow coating and their use as active layers in organic field-effect transistor (OFET) devices. The OFETs of TIPS-Pentacene and C8-BTBT have charge mobilities of 0.15 and 1.4 cm2 V-1 s-1, respectively, with low threshold voltages and on/off ratios exceeding 105. This coating method can also be extended to polymeric semiconductors: films based on poly(3-hexylthiophene) (P3HT) and poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPPTTT) are realized, establishing gas blow coating as a novel and efficient technique for the deposition of thin films of organic semiconductors.

Graphical abstract, Cell-based therapies have shown significant promise in tissue engineering with one key challenge being the delivery and retention of cells. As a result, significant efforts have been made in the past decade to design injectable biomaterials to host and deliver cells at injury sites. Intervertebral disc (IVD) degeneration, a major cause of back pain, is a particularly relevant example where a minimally-invasive cellular therapy could bring significant benefits specifically at the early stages of the disease, when a cell-driven process starts in the gelatinous core of the IVD, the nucleus pulposus (NP). In this present study we explore the use of graphene oxide (GO) as nano-filler for the reinforcement of FEFKFEFK (β-sheet forming self-assembling peptide) hydrogels. Our results confirm the presence of strong interactions between FEFKFEFK and GO flakes with the peptide coating and forming short thin fibrils on the surface of the flakes. These strong interactions were found to affect the bulk properties of hybrid hydrogels. At pH 4 electrostatic interactions between the peptide fibres and the peptide-coated GO flakes are thought to govern the final bulk properties of the hydrogels while at pH 7, after conditioning with cell culture media, electrostatic interactions are removed leaving the hydrophobic interactions to govern hydrogel final properties. The GO-F820 hybrid hydrogel, with mechanical properties similar to the NP, was shown to promote high cell viability and retained cell metabolic activity in 3D over the 7 days of culture and therefore shown to harbour significant potential as an injectable hydrogel scaffold for the in-vivo delivery of NP cells. Statement of Significance Short self-assembling peptide hydrogels (SAPHs) have attracted significant interest in recent years as they can mimic the natural extra-cellular matrix, holding significant promise for the ab initio design of cells’ microenvironments. Recently the design of hybrid hydrogels for biomedical applications has been explored through the incorporation of specific nanofillers. In this study we exploited graphene oxide (GO) as nanofiller to design hybrid injectable 3Dscaffolds for the delivery of nucleus pulposus cells (NPCs) for intervertebral disc regeneration. Our work clearly shows the presence of strong interactions between peptide and GO, mimicking the mechanical properties of the NP tissue and promoting high cell viability and metabolic activity. These hybrid hydrogels therefore harbour significant potential as injectable scaffolds for the in vivo delivery of NPCs.

The electrochemical activity of the basal plane and edge plane of graphite has long been a subject of an extensive debate. While significant advances have been made, several gaps still exist in our understanding of this issue, namely regarding the relative differences in the electrochemical activity of the perfect basal plane and perfect edge plane, and the dependence of measureable electrochemical quantities on the edge/defect density of the basal plane. In this work, we employ a micro-droplet electrochemical cell technique and atomic force microscopy to measure localized electrochemical properties of the graphitic surface with known edge coverage. The electron transfer rate, capacitance, and density of electronic states of the perfect basal plane and perfect edge plane are estimated and a qualitative model is proposed for the dependence of the electrochemical quantities on the defect density of the basal plane.

A comparison of the performance of graphene‐based supercapacitors is difficult, owing to the variety of production methods used to prepare the materials. To the best of our knowledge, there has been no systematic investigation into the effect of the graphene production method on the supercapacitor performance. In this work, we compare graphene produced through several routes. This includes anodic and cathodic electrochemically exfoliated graphene, liquid phase exfoliated graphene, graphene oxide, reduced graphene oxide, and graphene nanoribbons. Graphene oxide exhibited the highest capacitance of approximately 154 F g−1 in 6 M KOH at 0.5 A g−1 attributed to oxygen functional groups giving an additional pseudocapacitance and preventing significant restacking; however, the capacitance retention was poor, owing to the low conductivity. In comparison, the anodic electrochemically exfoliated graphene exhibited a capacitance of approximately 44 F g−1, the highest of the ‘pure’ graphene materials, which all exhibited superior capacitance retention, owing to their higher conductivity. The cyclability of all of the materials, with the exception of reduced graphene oxide (70 %), was found to be greater than 95 % after 10 000 cycles. These results highlight the importance of matching the graphene production method with a specific application; for example, graphene oxide and anodic electrochemically exfoliated graphene would be best suited for high energy and power applications, respectively.

A variety of physical phenomena associated with nanoscale electron transport often results in non-trivial spatial voltage and current patterns, particularly in nonlocal transport regimes. While numerous techniques have been devised to image electron flows, the need remains for a nanoscale probe capable of simultaneously imaging current and voltage distributions with high sensitivity and minimal invasiveness, in a magnetic field, across a broad range of temperatures and beneath an insulating surface. Here we present a technique for spatially mapping electron flows based on a nanotube single-electron transistor, which achieves high sensitivity for both voltage and current imaging. In a series of experiments using high-mobility graphene devices, we demonstrate the ability of our technique to visualize local aspects of intrinsically nonlocal transport, as in ballistic flows, which are not easily resolvable via existing methods. This technique should aid in understanding the physics of two-dimensional electronic devices and enable new classes of experiments that image electron flow through buried nanostructures in the quantum and interaction-dominated regimes.

A green and low-cost method is presented to fabricate graphene fibre electrodes by electrochemical exfoliation of thin strips of graphite foil. When assembled into micro-supercapacitors, the graphene fibres achieved an excellent electrochemical capacitance (∼247.6 mF cm−2 at ∼2 mA cm−2) and low equivalent series resistance (∼2.4 Ω), a significant improvement over the typically used graphene oxide based fibres. This excellent capacitive performance indicates these graphene-based energy storage devices could be ideal for microelectronics applications. Additionally, an all-solid-state flexible micro-supercapacitor was fabricated using a gel electrolyte (H3PO4/PVA) and exhibited a high areal capacitance of 70.6 mF cm−2 and a superior cycling stability of ∼96% capacitance retention after 2400 cycles, suggesting possible applications for flexible energy storage. The easily scalable and facile single step strategy presented here outperforms the conventionally used graphene oxide based methods, which typically require harmful chemicals and involve a more complex synthesis procedure.

Carboxylic acid-terminated pyrrolidine functionalities were covalently bonded to the surface of graphene nanoplatelets via a solvent-free approach and characterized by Boehm titration. In this work, the functionalization of graphene nanoplatelets (GNPs) performed by a solvent-free cycloaddition reaction on GNPs with iminodiacetic acid (IDA) and paraformaldehyde (PFA), and the functionality analysis of the resulting functionalized GNPs (f-GNPs) by Boehm titration are introduced. The f-GNPs synthesized at different temperatures were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM) for structural and morphological properties. Back titration of the f-GNPs selectively identified 3 types of functional groups on the f-GNP surface, carboxylic, lactonic and phenolic, and suggested that 200 °C gives the highest carboxylic group functionality. With the reaction temperature increasing from 180 to 220 °C, a decrease in the phenolic functionality and an increase in that of lactonic are observed. In the case of 250 °C reactions, it was found that the carboxylic functionality is greatly reduced, while the phenolic functionality showed a significant increase. The f-GNP samples were further characterized by thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS), the results of which showed a good agreement with the titration analysis.

Liquid-phase exfoliation (LPE) of graphite shows great potential as mass scalable and low-cost method for production of solution-processed graphene, which can be used for a wide range of applications. Due to the hydrophobic nature of graphene, a stabilising agent is needed to exfoliate graphite in water - in particular, pyrene derivatives have been shown to be very effective at exfoliating graphite, by producing either positively or negatively charged dispersions, depending on the functional group used.In this work we have synthesised amphoteric amino acid-based pyrene derivatives, using amino acid-based functional groups (lysine and taurine), and tested them as exfoliating agent for the LPE of graphene. Atomic Force Microscopy shows the flakes to have average size between 100 – 300 nm, while qualitative Raman analysis shows the dispersion to be composed mainly by single and few-layer flakes, as also confirmed by Transmission Electron Microscopy. Finally, we demonstrate that the surface charge of graphene can be adjusted by a systematic change of the pH level. Although both stabilisers demonstrated to be able to exfoliate graphite in water, pyrene-based lysine produces more concentrated and stable graphene dispersion, whose surface charge changes between positive to negative depending on pH level. In contrast, sedimentation of the dispersed material was observed at extreme pH for graphene dispersions obtained with pyrene-substituted taurine. This is attributed to the low pKa of the sulfonic group in taurine, which remains negatively charged even at very low pH.

This study presents preliminary experimental data suggesting that sodium 4-(pyrene-1-yl)butane-1-sulfonate (PBSA), 5, an analogue of sodium pyrene-1-sulfonate (PSA), 1, enhances the stability of aqueous reduced graphene oxide (RGO) graphene dispersions. We find that RGO and exfoliated graphene dispersions prepared in the presence of 5 are approximately double the concentration of those made with commercially available PSA, 1. Quantum mechanical and molecular dynamics simulations provide key insights into the behavior of these molecules on the graphene surface. The seemingly obvious introduction of a polar sulfonate head group linked via an appropriate alkyl spacer to the aromatic core results in both more efficient binding of 5 to the graphene surface and more efficient solvation of the polar head group by bulk solvent (water). Overall, this improves the stabilization of the graphene flakes by disfavoring dissociation of the stabilizer from the graphene surface and inhibiting reaggregation by electrostatic and steric repulsion. These insights are currently the subject of further investigations in an attempt to develop a rational approach to the design of more effective dispersing agents for rGO and graphene in aqueous solution.

The prominent discrepancy between the significant investment towards plasma biomarker discovery and the very low number of biomarkers currently in clinical use stresses the need for novel discovery technologies. The discovery of protein biomarkers present in human blood by proteomics is tremendously challenging, owing to the large dynamic concentration range of blood proteins. Here, we describe the use of blood-circulating lipid-based nanoparticles (NPs) as a scavenging tool to comprehensively analyse the blood circulation proteome. We aimed to exploit the spontaneous interaction of NPs with plasma proteins once injected in the bloodstream, known as ‘protein corona’ and to facilitate the discovery of previously unreported biomarker molecules for cancer diagnostics. We employed two different tumor models, a subcutaneous melanoma model (B16-F10) and human lung carcinoma xenograft model (A549) and comprehensively compared by mass spectrometry the in vivo protein coronas formed onto clinically used liposomes, intravenously administered in healthy and tumor-bearing mice. The results obtained demonstrated the ability of blood-circulating liposomes to surface-capture and amplify low molecular weight (MW) and low abundant tumor specific proteins (intracellular products of tissue leakage) that could not be detected by plasma analysis, performed in comparison. Most strikingly, the NP (liposomal) corona formed in the xenograft model was found to consist of murine host response proteins, as well as human proteins released from the inoculated and growing human cancer cells. This study offers direct evidence that the in vivo NP protein corona could be deemed as a valuable tool of the blood proteome in experimental disease models to allow the discovery of potential biomarkers.ToC Graphic

High free volume glassy polymers or polymers of intrinsic microporosity such as poly[1-trimethylsilyl-1-propyne] (PTMSP) and polybenzodioxane (PIM-1) are extra high gas permeability membrane materials. One of their major drawbacks is low gas selectivity. In this study, thin film composite (TFC) membranes have been developed with high CO2 permeance and superior CO2/N2 selectivity due to a strong synergistic effect. The TFC membranes, comprising a thin layer (0.29–0.42 μm) of PIM-1 atop a cross-linked PTMSP gutter layer (2.07–3.44 μm) on a porous backing material, were fabricated by coating PIM-1 solution on the cross-linked PTMSP support. A key element is that for coating PIM-1 a mixed solvent of chloroform and trichloroethylene (1 : 1) was successfully implemented for the first time. All membrane samples demonstrated a strong synergistic enhancement of CO2/N2 selectivity (α = 35.8–55.7) compared to PIM-1 (α = 18.5) and cross-linked PTMSP (α = 3.7). SEM, TEM and laser interferometry studies revealed that the synergistic enhancement of gas selectivity in the TFC membranes is most likely due to the creation of a very thin boundary layer between PIM-1 and the cross-linked PTMSP gutter layer. The aged TFC membranes (after three months) showed a severe drop in gas permeance while keeping nearly the same high selectivity. Thus, future success in the prevention of polymer physical aging, together with the synergy effect in selectivity reported for the first time in this work, will give new opportunities for application of polymers of intrinsic microporosity.

The high temperature performance of water-in-salt electrolytes was investigated using a carbon-based electrode with commercial cell components. Supercapacitors using 21 m Li bis(trifluoromethylsulphonyl)imide (TFSI) and 21 m LiTFSI + 7 m Li trifluoromethanesulphonyl electrolytes are shown to operate at a voltage of 2 V at 100 °C and 120 °C, respectively, with gravimetric capacitances exceeding 100 F g−1.

The addition of fillers has become a common method of improving the performance of composites. Therefore, many types of fillers are commercially available while several other types are being investigated. The understanding of the effect of additives on the processing and product quality is crucial for manufacturing products economically and with the desired qualities. This study focuses on investigating the possible effects of graphene and fumed silica nanoparticle fillers on polymer processing and product properties. Three polymeric materials were processed with these two fillers via a Mini-Lab twin screw extruder to obtain a better dispersion, and then the properties of samples produced were explored with a number of different testing techniques (e.g., tensile testing, SEM, DSC and rheometer). The Young's modulus of amorphous materials was strongly affected by the filler content, while crystalline materials were not that sensitive to the filler content/level. The Young's modulus of polystyrene-based polymer nanocomposites (PNCs) with 8 wt% fillers at 200 °C and 50 rpm was found to be of approximately 1786 MPa. Also, as clearly recognized by the SEM images and one glass transition temperature (Tg) value rather than two Tg values, it can be ensured that the particles are finely dispersed within PNCs regardless the filler type/content. And then, the rheological results further confirmed that the properties of PNCs are affected by the filler content and set conditions, while the Tg of PNCs was mainly dependent on the matrix and have slightly influenced by the degree of filler dispersion. Moreover, the energy demand was also explored during all the experimental trials for possible comparison and indicated that the energy consumption increased with the filler content but the magnitude of increase was different with different polymer type.

Nonspecific molecular adsorption like airborne contamination occurs on most surfaces including those of 2D materials and alters their properties. While the surface contamination is studied using a plethora of techniques, the effect of contamination on a confined system such as nanochannels, nanopores leading to their clogging is still lacking. We report a systematic investigation of hydrocarbon adsorption in the angstrom slit channels of varied heights. Hexane is chosen to mimic the hydrocarbon contamination and the clogging of the angstrom-channels is evaluated via a Helium gas flow measurement. The level of the hexane adsorption, in other words, the degree of clogging depends on the size difference between the channels and hexane. A dynamic transition of the clogging and revival process is shown in sub-2 nm thin channels. Long-term storage and stability of our angstrom-channels is demonstrated here up to three years, alleviating the contamination and unclogging the channels using thermal treatment. This study highlights the importance of the nanochannels stability and demonstrates self-cleansing nature of sub-2 nm thin channels enabling a robust platform for molecular transport and separation studies. We provide a method to assess the cleanliness of the nanoporous membranes, which is vital for the practical applications of nanofluidics in various fields such as molecular sensing, separation and power generation.

2D nanoslit devices, where two crystals with atomically flat surfaces are separated by only a few nanometers, have attracted considerable attention because their tunable control over the confinement allows for the discovery of unusual transport behavior of gas, water, and ions. Here, the passage of double-stranded DNA molecules is studied through nanoslits fabricated from exfoliated 2D materials, such as graphene or hexagonal boron nitride, and the DNA polymer behavior is examined in this tight confinement. Two types of events are observed in the ionic current: long current blockades that signal DNA translocation and short spikes where DNA enters the slits but withdraws. DNA translocation events exhibit three distinct phases in their current-blockade traces—loading, translation, and exit. Coarse-grained molecular dynamics simulation allows the different polymer configurations of these phases to be identified. DNA molecules, including folds and knots in their polymer structure, are observed to slide through the slits with near-uniform velocity without noticeable frictional interactions of DNA with the confining graphene surfaces. It is anticipated that this new class of 2D-nanoslit devices will provide unique ways to study polymer physics and enable lab-on-a-chip biotechnology.

Its anatomical localization, a highly heterogeneous and drug-resistant tumor cell population and a “cold” immune microenvironment, all challenge the treatment of glioblastoma. Nanoscale drug delivery systems, including graphene oxide (GO) flakes, may circumvent some of these issues bypassing biological barriers, delivering multiple cargoes to impact several pathways simultaneously, or targeting the immune compartment. Here, the interactions of GO flakes with in vitro (U-87 MG three-dimensional spheroids, without stromal or immune compartments) and in vivo (U-87 MG orthotopic xenograft) models of glioblastoma are investigated. In vitro, GO flakes translocated deeply into the spheroids with little internalization in tumor cells. In vivo, intracranially administered GO also show extensive distribution throughout the tumor and demonstrate no impact on tumor growth and progression for the duration of the study. Internalization within tumor cells is also scarce, with the majority of flakes preferentially taken up by microglia/macrophages. The results indicate that GO flakes could offer deep and homogenous distribution throughout glioblastoma tumors and a means to target their myeloid compartment. Further studies are warranted to investigate the mechanisms of GO flakes transport within the tumor mass and their capacity to deliver bioactive cargoes but, ultimately, this information could inform the development of immunotherapies against glioblastoma., K.K., P.S., S.V., and M.S. would like to acknowledge the United Kingdom Research and Innovation (UKRI) Engineering and Physical Sciences Research Council (EPSRC) for funding most of this work under the 2D-Health Programme Grant (EP/P00119X/1). K.K. and I.d.L. would also like to acknowledge the UKRI (EPSRC) for an International Centre-to-Centre grant (EP/S030719/1) between the University of Manchester and Harvard University that funded part of this work. T.K. would like to thank the UKRI (EPSRC and Medical Research Council, MRC) Center for Doctoral Training (CDT) in Regenerative Medicine (EP/L014904/1) for a funded PhD studentship. The authors would like to thank Dr. Marta Quintanilla and Dr. David Spiller for help with LSFM. The equipment at the University of Manchester Bioimaging and Genomic Technologies facilities used in this study were purchased with grants from the Biotechnology and Biological Sciences Research Council (BBSRC), Wellcome Trust, and the University of Manchester Strategic Fund. A.Y., C.G., and H.T. would like to thank the project “G-IMMUNOMICS” funded under the Joint Transnational Call (JTC) Graphene 2015. A.Y. is thankful to the Turkish Academy of Sciences (TUBA) for the financial support.