In-process monitoring of graphene nanoplatelet production using Raman spectroscopy and NMR relaxation.

As the range of applications of graphene related 2D materials (GR2Ms) widens, the production volumes of these materials are also increasing. To maintain confidence in the quality of the GR2M feedstock, industry requires in situ measurement methods that can be deployed easily in a production environment and provide reliable results quickly. In this paper, we demonstrate the potential of 1H nuclear magnetic resonance (NMR) relaxation and Raman spectroscopy to address this need. 1H NMR relaxation measurements performed at-line were able to provide results in under one minute, providing near real-time feedback for production monitoring. Alongside this, Raman spectroscopy was deployed in-line to enable obtaining real-time information from production, without the need to manually sample the material. By comparing the results against existing measurement methods, as well as laboratory-based Raman spectroscopy and 1H NMR relaxation measurements, we demonstrate potential quality control approaches for GR2M production.

Crystallization of molecular layers produced under confinement onto a surface.

It is well known that molecules confined very close to a surface arrange into molecular layers. Because solid-liquid interfaces are ubiquitous in the chemical, biological and physical sciences, it is crucial to develop methods to easily access molecular layers and exploit their distinct properties by producing molecular layered crystals. Here we report a method based on crystallization in ultra-thin puddles enabled by gas blowing, which allows to produce molecular layered crystals with thickness down to the monolayer onto a surface, making them directly accessible for characterization and further processing. By selecting four molecules with different types of polymorphs, we observed exclusive crystallization of polymorphs with Van der Waals interlayer interactions, which have not been observed with traditional confinement methods. In conclusion, the gas blowing approach unveils the opportunity to perform materials chemistry under confinement onto a surface, enabling the formation of distinct crystals with selected polymorphism.

Electrochemical exfoliation of 2D materials beyond graphene.

After the discovery of graphene in 2004, the field of atomically thin crystals has exploded with the discovery of thousands of 2-dimensional materials (2DMs) with unique electronic and optical properties, by making them very attractive for a broad range of applications, from electronics to energy storage and harvesting, and from sensing to biomedical applications. In order to integrate 2DMs into practical applications, it is crucial to develop mass scalable techniques providing crystals of high quality and in large yield. Electrochemical exfoliation is one of the most promising methods for producing 2DMs, as it enables quick and large-scale production of solution processable nanosheets with a thickness well below 10 layers and lateral size above 1 µm. Originally, this technique was developed for the production of graphene; however, in the last few years, this approach has been successfully extended to other 2DMs, such as transition metal dichalcogenides, black phosphorous, hexagonal boron nitride, MXenes and many other emerging 2D materials. This review first provides an introduction to the fundamentals of electrochemical exfoliation and then it discusses the production of each class of 2DMs, by introducing their properties and giving examples of applications. Finally, a summary and perspective are given to address some of the challenges in this research area.

Wearable Sensors for Breath Monitoring Based on Water-Based Hexagonal Boron Nitride Inks Made with Supramolecular Functionalization.

Wearable humidity sensors are attracting strong attention as they allow for real-time and continuous monitoring of important physiological information by enabling activity tracking as well as air quality assessment. Amongst 2Dimensional (2D) materials, graphene oxide (GO) is very attractive for humidity sensing due to its tuneable surface chemistry, high surface area, processability in water, and easy integration onto flexible substrates. However, strong hysteresis, low sensitivity, and cross-sensitivity issues limit the use of GO in practical applications, where continuous monitoring is preferred. Herein, a wearable and wireless impedance-based humidity sensor made with pyrene-functionalized hexagonal boron nitride (h-BN) nanosheets is demonstrated. The device shows enhanced sensitivity towards relative humidity (RH) (>1010 Ohms/%RH in the range from 5% to 100% RH), fast response (0.1 ms), no appreciable hysteresis, and no cross-sensitivity with temperature in the range of 25-60 °C. The h-BN-based sensor is able to monitor the whole breathing cycle process of exhaling and inhaling, hence enabling to record in real-time the subtlest changes of respiratory signals associated with different daily activities as well as various symptoms of flu, without requiring any direct contact with the individual.

Fully printed memristors made with MoS2 and graphene water-based inks.

2-Dimensional materials (2DMs) offer an attractive solution for the realization of high density and reliable memristors, compatible with printed and flexible electronics. In this work we fabricate a fully inkjet printed MoS2-based resistive switching memory, where graphene is used as top electrode and silver is used as bottom electrode. Memristic effects are observed only after annealing of each printed component. The printed memory on silicon shows low SET/RESET voltage, short switching times (less than 0.1 s) and resistance switching ratios of 103-105, comparable or superior to the performance obtained in devices with both printed silver electrodes on rigid substrates. The same device on Kapton shows resistance switching ratios of 102-103 and remains stable at least up to 2% of strain. The memristor resistance switching is attributed to the formation of Ag conductive filaments, which can be suppressed by integrating graphene grown by chemical vapour deposition (CVD) onto the silver electrode. Temperature-dependent electrical measurements starting from 200 K show that memristic behavior appears at a temperature of ∼300 K, confirming that an energy threshold is needed to form the conductive filament. This work shows that inkjet printing is a very powerful technique for the fabrication of 2DMs-based resistive switches onto rigid and flexible substrates.

Novel Anticounterfeiting Solution Based on 2D Materials Produced by Electrochemical Exfoliation.

This work demonstrates the use of 2D materials (2DMs) as identification tags by exploiting their unique shape. Electrochemical exfoliation enables the production of large quantities of optically accessible 2DMs with diverse morphology and large lateral sizes up to 20 µm. Image processing techniques are used to facilitate shape identification and matching within a dataset of 500 unique nanosheets. Rotational and translation invariant shape matching with no false positive matches between over 100 000 unique shape pairings is shown. The approach enables individual nanosheets to be deposited onto products, such as packaging of luxury goods, pharmaceuticals, banknotes, etc., as a unique seal of authenticity. Quick inspection of the nanoscale tag by optical microscopy allows the shape to be compared against the genuine dataset, enabling unique identification. The optical features of 2D materials, such as Raman and/or photoluminescence signals can be used as an additional chemical fingerprint, making the anticounterfeiting solution very robust.

Introduction to nanomaterials for printed electronics.

An introduction to the Nanoscale themed collection on nanomaterials for printed electronics, featuring exciting research on a variety of nanomaterials and techniques used for printed electronics.

Defect-free graphene enhances enzyme delivery to fibroblasts derived from patients with lysosomal storage disorders.

Enzyme replacement therapy shows remarkable clinical improvement in treating lysosomal storage disorders. However, this therapeutic approach is hampered by limitations in the delivery of the enzyme to cells and tissues. Therefore, there is an urgent, unmet clinical need to develop new strategies to enhance the enzyme delivery to diseased cells. Graphene-based materials, due to their dimensionality and favourable pattern of interaction with cells, represent a promising platform for the loading and delivery of therapeutic cargo. Herein, the potential use of graphene-based materials, including defect-free graphene with positive or negative surface charge and graphene oxide with different lateral dimensions, was investigated for the delivery of lysosomal enzymes in fibroblasts derived from patients with Mucopolysaccharidosis VI and Pompe disease. We report excellent biocompatibility of all graphene-based materials up to a concentration of 100 µg mL-1 in the cell lines studied. In addition, a noticeable difference in the uptake profile of the materials was observed. Neither type of graphene oxide was taken up by the cells to a significant extent. In contrast, the two types of graphene were efficiently taken up, localizing in the lysosomes. Furthermore, we demonstrate that cationic graphene flakes can be used as carriers for arylsulfatase B enzyme, for the delivery of the lacking enzyme to the lysosomes of Mucopolysaccharidosis VI fibroblasts. Arylsulfatase B complexed with cationic graphene flakes not only retained the enzymatic activity, but also exerted biological effects almost twice as high as arylsulfatase B alone in the clearance of the substrate in Mucopolysaccharidosis VI fibroblasts. This study lays the groundwork for the potential use of graphene-based materials as carriers for enzyme replacement therapy in lysosomal storage disorders.

Water-based 2-dimensional anatase TiO2 inks for printed diodes and transistors.

2-Dimensional (2D) materials are attracting strong interest in printed electronics because of their unique properties and easy processability, enabling the fabrication of devices with low cost and mass scalable methods such as inkjet printing. For the fabrication of fully printed devices, it is of fundamental importance to develop a printable dielectric ink, providing good insulation and the ability to withstand large electric fields. Hexagonal boron nitride (h-BN) is typically used as a dielectric in printed devices. However, the h-BN film thickness is usually above 1 µm, hence limiting the use of h-BN in low-voltage applications. Furthermore, the h-BN ink is composed of nanosheets with broad lateral size and thickness distributions, due to the use of liquid-phase exfoliation (LPE). In this work, we investigate anatase TiO2 nanosheets (TiO2-NS), produced by a mass scalable bottom-up approach. We formulate the TiO2-NS into a water-based and printable solvent and demonstrate the use of the material with sub-micron thickness in printed diodes and transistors, hence validating the strong potential of TiO2-NS as a dielectric for printed electronics.

Etch and Print: Graphene-Based Diodes for Silicon Technology.

The graphene-silicon junction is one of the simplest conceivable interfaces in graphene-integrated semiconductor technology that can lead to the development of future generation of electronic and optoelectronic devices. However, graphene's integration is currently expensive and time-consuming and shows several challenges in terms of large-scale device fabrication, effectively preventing the possibility of implementing this technology into industrial processes. Here, we show a simple and cost-effective fabrication technique, based on inkjet printing, for the realization of printed graphene-silicon rectifying devices. The printed graphene-silicon diodes show an ON/OFF ratio higher than 3 orders of magnitude and a significant photovoltaic effect, resulting in a fill factor of ∼40% and a photocurrent efficiency of ∼2%, making the devices suitable for both electronic and optoelectronic applications. Finally, we demonstrate large-area pixeled photodetectors and compatibility with back-end-of-line fabrication processes.

Anisotropic Thermal Conductivity of Inkjet-Printed 2D Crystal Films: Role of the Microstructure and Interfaces.

Two-dimensional (2D) materials are uniquely suited for highly anisotropic thermal transport, which is important in thermoelectrics, thermal barrier coatings, and heat spreaders. Solution-processed 2D materials are attractive for simple, low-cost, and large-scale fabrication of devices on, virtually, any substrate. However, to date, there are only few reports with contrasting results on the thermal conductivity of graphene films, while thermal transport has been hardly measured for other types of solution-processed 2D material films. In this work, inkjet-printed graphene, h-BN and MoS2 films are demonstrated with thermal conductivities of ∼10 Wm-1K-1 and ∼0.3 Wm-1K-1 along and across the basal plane, respectively, giving rise to an anisotropy of ∼30, hardly dependent on the material type and annealing treatment. First-principles calculations indicate that portion of the phonon spectrum is cut-off by the quality of the thermal contact for transport along the plane, yet the ultra-low conductivity across the plane is associated with high-transmissivity interfaces. These findings can drive the design of highly anisotropic 2D material films for heat management applications.

Effects of Lateral Size, Thickness, and Stabilizer Concentration on the Cytotoxicity of Defect-Free Graphene Nanosheets: Implications for Biological Applications.

In this work, we apply liquid cascade centrifugation to highly concentrated graphene dispersions produced by liquid-phase exfoliation in water with an insoluble bis-pyrene stabilizer to obtain fractions containing nanosheets with different lateral size distributions. The concentration, stability, size, thickness, and the cytotoxicity profile are studied as a function of the initial stabilizer concentration for each fraction. Our results show that there is a critical initial amount of stabilizer (0.4 mg/mL) above which the dispersions show reduced concentration, stability, and biocompatibility, no matter the lateral size of the flakes.

Synthesis of 2D anatase TiO2 with highly reactive facets by fluorine-free topochemical conversion of 1T-TiS2 nanosheets.

Two-dimensional (2D) anatase titanium dioxide (TiO2) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO2 is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO2 with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS2 for the production of single crystalline 2D anatase TiO2, exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO2 nanoparticles. Because of the strong potential of TiO2 in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO2 with well controlled and highly reactive exposed facets.

Flexible and digestible wood caused by viral-induced alteration of cell wall composition.

Woody plant material represents a vast renewable resource that has the potential to produce biofuels and other bio-based products with favorable net CO2 emissions.1,2 Its potential has been demonstrated in a recent study that generated novel structural materials from flexible moldable wood.3 Apple rubbery wood (ARW) disease is the result of a viral infection that causes woody stems to exhibit increased flexibility.4 Although ARW disease is associated with the presence of an RNA virus5 known as apple rubbery wood virus (ARWV), how the unique symptoms develop is unknown. We demonstrate that the symptoms of ARWV infections arise from reduced lignification within the secondary cell wall of xylem fibers and result in increased wood digestibility. In contrast, the mid-lamellae region and xylem ray cells are largely unaffected by the infection. Gene expression and proteomic data from symptomatic xylem clearly show the downregulation of phenylalanine ammonia lyase (PAL), the enzyme catalyzing the first committed step in the phenylpropanoid pathway leading to lignin biosynthesis. A large increase in soluble phenolics in symptomatic xylem, including the lignin precursor phenylalanine, is also consistent with PAL downregulation. ARWV infection results in the accumulation of many host-derived virus-activated small interfering RNAs (vasiRNAs). PAL-derived vasiRNAs are among the most abundant vasiRNAs in symptomatic xylem and are likely the cause of reduced PAL activity. Apparently, the mechanism used by the virus to alter lignin exhibits similarities to the RNAi strategy used to alter lignin in genetically modified trees to generate comparable improvements in wood properties.6-8.

Two-Dimensional Transition Metal Dichalcogenides Trigger Trained Immunity in Human Macrophages through Epigenetic and Metabolic Pathways.

Trained immunity is a recently described phenomenon whereby cells of the innate immune system undergo long-term epigenetic and/or metabolic reprogramming following a short-term interaction with microbes or microbial products. Here, it is shown that 2D transition metal dichalcogenides (TMDs) trigger trained immunity in primary human monocyte-derived macrophages. First, aqueous dispersions of 2D crystal formulations of MoS2 and WS2 are tested, and no cytotoxicity is found despite avid uptake of these materials by macrophages. However, when macrophages are pre-exposed to TMDs, followed by a resting period, this causes a marked modulation of immune-specific gene expression upon subsequent challenge with a microbial agent (i.e., bacterial lipopolysaccharides). Specifically, MoS2 triggers trained immunity through an epigenetic pathway insofar as the histone methyltransferase inhibitor methylthioadenosine reverses these effects. Furthermore, MoS2 triggers an elevation of cyclic adenosine monophosphate (cAMP) levels in macrophages and increased glycolysis is also evidenced in cells subjected to MoS2 training, pointing toward a metabolic rewiring of the cells. Importantly, it is observed that MoS2 triggers the upregulation of Mo-dependent enzymes in macrophages, thus confirming that Mo is bioavailable in these cells. In conclusion, MoS2 is identified as a novel inducer of trained immunity. Thus, TMDs could potentially be harnessed as immunomodulatory agents.

Electrolyte-Gated Organic Field-Effect Transistors for Quantitative Monitoring of the Molecular Dynamics of Crystallization at the Solid-Liquid Interface.

Quantitative measurements of molecular dynamics at the solid-liquid interface are of crucial importance in a wide range of fields, such as heterogeneous catalysis, energy storage, nanofluidics, biosensing, and crystallization. In particular, the molecular dynamics associated with nucleation and crystal growth is very challenging to study because of the poor sensitivity or limited spatial/temporal resolution of the most widely used analytical techniques. We demonstrate that electrolyte-gated organic field-effect transistors (EGOFETs) are able to monitor in real-time the crystallization process in an evaporating droplet. The high sensitivity of these devices at the solid-liquid interface, through the electrical double layer and signal amplification, enables the quantification of changes in solute concentration over time and the transport rate of molecules at the solid-liquid interface during crystallization. Our results show that EGOFETs offer a highly sensitive and powerful, yet simple approach to investigate the molecular dynamics of compounds crystallizing from water.

Hybrid MoS2/PEDOT:PSS transporting layers for interface engineering of nanoplatelet-based light-emitting diodes.

Colloidal semiconductor nanoplatelets (NPLs) are a subgroup of quantum confined materials that have recently emerged as promising active materials for solution processed light-emitting diodes (LEDs) thanks to their peculiar structural and electronic properties as well as their reduced dimensionality. Nowadays, the conventional structure for NPL-based LEDs makes use of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as a hole transporting layer (HTL). This is a well-known conjugated conductive polymer because it leads to high LED efficiency, though it has limited stability in air due to its intrinsic acidity and hygroscopicity. Here, we develop a nanocomposite aqueous ink, obtained by blending commercial PEDOT:PSS with water-based, stable and highly concentrated molybdenum disulfide (MoS2) nanosheets, obtained via liquid phase exfoliation (LPE), which is suitable as a HTL for solution processed NPL-based LEDs. We demonstrate that the MoS2 additive effectively works as a performance booster in unpackaged devices, thereby prolonging the lifetime up to 1000 hours under ambient conditions. Moreover, the addition of MoS2 induces a modification of the anode interface properties, including a change in the work function and a significant enhancement of the permittivity of the HTL.

Viscoelastic surface electrode arrays to interface with viscoelastic tissues.

Living tissues are non-linearly elastic materials that exhibit viscoelasticity and plasticity. Man-made, implantable bioelectronic arrays mainly rely on rigid or elastic encapsulation materials and stiff films of ductile metals that can be manipulated with microscopic precision to offer reliable electrical properties. In this study, we have engineered a surface microelectrode array that replaces the traditional encapsulation and conductive components with viscoelastic materials. Our array overcomes previous limitations in matching the stiffness and relaxation behaviour of soft biological tissues by using hydrogels as the outer layers. We have introduced a hydrogel-based conductor made from an ionically conductive alginate matrix enhanced with carbon nanomaterials, which provide electrical percolation even at low loading fractions. Our combination of conducting and insulating viscoelastic materials, with top-down manufacturing, allows for the fabrication of electrode arrays compatible with standard electrophysiology platforms. Our arrays intimately conform to the convoluted surface of the heart or brain cortex and offer promising bioengineering applications for recording and stimulation.

Gamma Radiation-Induced Oxidation, Doping, and Etching of Two-Dimensional MoS2 Crystals.

Two-dimensional (2D) MoS2 is a promising material for future electronic and optoelectronic applications. 2D MoS2 devices have been shown to perform reliably under irradiation conditions relevant for a low Earth orbit. However, a systematic investigation of the stability of 2D MoS2 crystals under high-dose gamma irradiation is still missing. In this work, absorbed doses of up to 1000 kGy are administered to 2D MoS2. Radiation damage is monitored via optical microscopy and Raman, photoluminescence, and X-ray photoelectron spectroscopy techniques. After irradiation with 500 kGy dose, p-doping of the monolayer MoS2 is observed and attributed to the adsorption of O2 onto created vacancies. Extensive oxidation of the MoS2 crystal is attributed to reactions involving the products of adsorbate radiolysis. Edge-selective radiolytic etching of the uppermost layer in 2D MoS2 is attributed to the high reactivity of active edge sites. After irradiation with 1000 kGy, the monolayer MoS2 crystals appear to be completely etched. This holistic study reveals the previously unreported effects of high-dose gamma irradiation on the physical and chemical properties of 2D MoS2. Consequently, it demonstrates that radiation shielding, adsorbate concentrations, and required device lifetimes must be carefully considered, if devices incorporating 2D MoS2 are intended for use in high-dose radiation environments.