Inhibition of α-glucosidase activity by curcumin loaded on ZnO@rGO nanocarrier for potential treatment of diabetes mellitus.

Curcumin (Cur) is an acidic polyphenol with some effects on α-glucosidase (α-Glu), but Cur has disadvantages such as being a weak target, lacking passing the blood-brain barrier and having low bioavailability. To enhance the curative effect of Cur, the hybrid composed of ZnO nanoparticles decorated on rGO was used to load Cur (ZnO@rGO-Cur). The use of the multispectral method and enzyme inhibition kinetics analysis certify the inhibitory effect and interaction mechanism of ZnO@rGO-Cur with α-Glu. The static quenching of α-Glu with both Cur and ZnO@rGO-Cur is primarily driven by hydrogen bond and van der Waals interactions. The conformation-changing ability by binding to the neighbouring phenolic hydroxyl group of Cur increased their ability to alter the secondary structure of α-Glu, resulting in the inhibition of enzyme activity. The inhibition constant (Ki, Cur > Kis,ZnO@rGO-Cur ) showed that the inhibition effect of ZnO@rGO-Cur on α-Glu was larger than that of Cur. The CCK-8 experiments proved that ZnO@rGO nanocomposites have good biocompatibility. These results suggest that the therapeutic potential of ZnO@rGO-Cur composite is an emerging nanocarrier platform for drug delivery systems for the potential treatment of diabetes mellitus.

International Interlaboratory Comparison of Thermogravimetric Analysis of Graphene-Related Two-Dimensional Materials.

Research on graphene-related two-dimensional (2D) materials (GR2Ms) in recent years is strongly moving from academia to industrial sectors with many new developed products and devices on the market. Characterization and quality control of the GR2Ms and their properties are critical for growing industrial translation, which requires the development of appropriate and reliable analytical methods. These challenges are recognized by International Organization for Standardization (ISO 229) and International Electrotechnical Commission (IEC 113) committees to facilitate the development of these methods and standards which are currently in progress. Toward these efforts, the aim of this study was to perform an international interlaboratory comparison (ILC), conducted under Versailles Project on Advanced Materials and Standards (VAMAS) Technical Working Area (TWA) 41 "Graphene and Related 2D Materials" to evaluate the performance (reproducibility and confidence) of the thermogravimetric analysis (TGA) method as a potential new method for chemical characterization of GR2Ms. Three different types of representative and industrially manufactured GR2Ms samples, namely, pristine few-layer graphene (FLG), graphene oxide (GO), and reduced graphene oxide (rGO), were used and supplied to ILC participants to complete the study. The TGA method performance was evaluated by a series of measurements of selected parameters of the chemical and physical properties of these GR2Ms including the number of mass loss steps, thermal stability, temperature of maximum mass change rate (Tp) for each decomposition step, and the mass contents (%) of moisture, oxygen groups, carbon, and impurities (organic and non-combustible residue). TGA measurements determining these parameters were performed using the provided optimized TGA protocol on the same GR2Ms by 12 participants across academia, industry stakeholders, and national metrology institutes. This paper presents these results with corresponding statistical analysis showing low standard deviation and statistical conformity across all participants that confirm that the TGA method can be satisfactorily used for characterization of these parameters and the chemical characterization and quality control of GR2Ms. The common measurement uncertainty for each parameter, key contribution factors were identified with explanations and recommendations for their elimination and improvements toward their implementation for the development of the ISO/IEC standard for chemical characterization of GR2Ms.

Accounting Carbonaceous Counterfeits in Graphene Materials Using the Thermogravimetric Analysis (TGA) Approach.

Counterfeits in the supply chain of high-value advanced materials such as graphene and their derivatives have become a concerning problem with a potential negative impact on this growing and emerging industry. Recent studies have revealed alarming facts that a large percentage of manufactured graphene materials on market are not graphene, raising considerable concerns for the end users. The common and recommended methods for the characterization of graphene materials, such as transmission electron microscopy (TEM), atomic force microscopy (AFM), and Raman spectroscopy based on spot analysis and probing properties of individual graphene particles, are limited to provide the determination of the properties of "bulk" graphene powders at a large scale and the identification of non-graphene components or purposely included additives. These limitations are creating counterfeit opportunities by adding low-cost black carbonaceous materials into manufactured graphene powders. To address this problem, it is critical to have reliable characterization methods, which can probe the specific properties of graphene powders at bulk scale, confirm their typical graphene signature, and detect the presence of unwanted additional compounds, where the thermogravimetric analysis (TGA) method is one of the most promising methods to perform this challenging task. This paper presents the evaluation of the TGA method and its ability to detect low-cost carbon additives such as graphite, carbon black, biochar, and activated carbon as potential counterfeiting materials to graphene materials and their derivatives such as graphene oxide (GO) and reduced GO. The superior performance of the TGA method is demonstrated here, showing its excellent capability to successfully detect these additives when mixed with graphene materials, which is not possible by two other comparative methods (Raman spectroscopy and powder X-ray diffraction (XRD)), which are used as the common characterization methods for graphene materials.

High-yield preparation of edge-functionalized and water dispersible few-layers of hexagonal boron nitride (hBN) by direct wet chemical exfoliation.

Owing to many fascinating properties including high thermal and chemical stability, excellent electrical insulation, fire-retardant and antibacterial properties, hexagonal boron nitride (hBN) has emerged as a prominent 2D material for broad applications. However, the production of high quality of hBN by chemical exfoliation from its precursor is still challenging. This paper presents a high-yield (+83%), low-cost and energy-efficient wet chemical exfoliation strategy, which produces few-layers (FL, 3-6 layers) of edge-functionalized (OH) hBN nanosheets with uniform size (486 ± 51 nm). This optimized preparation is established based on a comprehensive investigation on the key exfoliation parameters such as exfoliation temperature, time and amount of the oxidant (potassium permanganate). High quality of FL-hBN was confirmed by various characterization techniques including scanning electron microscopy coupled with energy dispersive X-ray, transmission electron microscopy, Raman, Fourier transform infrared spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy analyses. The outcome of this study paves a promising pathway to effectively produce hBN through a cost-efficient exfoliation approach, which has a significant impact on industrial applications.

Graphene powders as new contact nanopesticides: Revealing key parameters on their insecticidal activity for stored product insects.

The overuse and reliance on pesticides has caused insects to develop resistance with global concerns. To address this problem extensive research is directed to find new and sustainable alternatives using chemical-free and resistance-free solutions for pest control. This paper presents a comprehensive investigation of the insecticidal properties of several types of industrially produced graphene powder materials such as graphene and graphene oxide (GO) with micro- and nano size and different structural and chemical properties as new contact nanopesticides against three major stored grain insects: the rice weevil Sitophilus oryzae (L.), the lesser grain borer, Rhyzopertha dominica (F.)˙ and the larger grain borer, Prostephanus truncatus Horn. Bioassays were performed using different concentrations, i.e., 0, 100, 500 and 1000 ppm of graphene powders on the mortality of selected adult insects recorded after 3, 7, 14, and 21 days of exposure and progeny production after 65 days. Results showed that graphene oxide (GO) has no insecticidal efficacy while graphene powders with nano-size particles showed significantly enhanced insecticidal performance compared to micron-size graphene powders. The observed insecticidal effects are explained by the higher probability that nano-sized graphene particles adhere on the insect body compared to large particles. The mortality is proposed as the result of physical mode of action of attached graphene nanoparticles causing stronger interruption of the protective cuticle layer, gas respiratory functions and faster mortality. The findings of this study revealed that it is important to select graphene materials with optimal structural and interfacial properties to achieve the highest insecticidal performance in potential development of a new generation of sustainable insecticides.

New insights on energetic properties of graphene oxide (GO) materials and their safety and environmental risks.

Graphene oxide (GO) has been recognized as a thermally unstable and energetic material, but surprisingly its environmental and safety risks were not fully explored, defined, and regulated. In this study, systematic explosivity and flammability characterizations of commercial GO materials were conducted to evaluate the influence of key parameters such as physical forms (paste, powders, films, and aerogels), temperature, heating rate, mass, and heating environment, as well as their potential safety and environmental impacts. Results based on thermogravimetric analysis (TGA) showed that GO in paste and powder forms have lower temperature thresholds (>180-192 °C) to initiate micro-explosions compared to GO film and aerogels (> 205 °C and 213 °C) regardless of the environment (inert, air, or oxygen). The observed explosive behavior can be explained by thermal runaway reactions as a result of thermal deoxygenation and decomposition of oxygen functional groups. Flammability rating and limiting oxygen index (LOI) results confirmed that GO films are flammable materials that can spontaneously propagate flame in a low oxygen environment (~11 %). These results provided new insights about potential safety and environmental risks of GO materials, which somehow were not considered, suggesting urgent actions to improve current safety protocols for labeling, handling, transporting, and storage practices from manufacturers to the end-users.

Graphene ink for 3D extrusion micro printing of chemo-resistive sensing devices for volatile organic compound detection.

Printed electronic sensors offer a breakthrough in the availability of low-cost sensor devices for improving the quality of human life. Conductive ink is the core of printing technology and also one of the fastest growing sector among all ink industries. Among many developed conductive inks, graphene-based inks are especially recognized as very promising for future fabrication of devices due to their low cost, unique properties, and compatibility with various platforms such as plastics, textiles, and paper. The development of graphene ink formulations for achieving high conductivity and high resolution printing is highly realized in 2D inkjet printing. Unfortunately, the ongoing development of graphene inks is possibly hampered by the non-uniform particle size and structures (e.g., different shapes and number of layers), which adversely affect printing resolution, conductivity, adhesion, and structural integrity. This study presents an environmentally sustainable route to produce graphene inks specifically designed for 3D extrusion-printing. The application of the prepared ink is demonstrated by mask-free automatic patterning of sensing devices for the detection of volatile organic compounds (VOCs). The sensing devices fabricated with this new ink display high-resolution patterning (average height/thickness of ∼12 µm) and a 10-fold improvement in the surface area/volume (SA/V) ratio compared to a conventional drop casting method. The extrusion printed sensors show enhanced sensing characteristics in terms of sensitivity and selectivity towards trace amount of VOC (e.g. 5 ppm ethanol) at room temperature (20 °C), which highlights that our method has highly promising potential in graphene printing technology for sensing applications.

Fractal Design for Advancing the Performance of Chemoresistive Sensors.

The rapid advancement of internet of things (IoT)-enabled applications along with connected automation in sensing technologies is the heart of future intelligent systems. The probable applications have significant implications, from chemical process monitoring to agriculture, mining, space, wearable electronics, industrial manufacturing, smart cities, and point-of-care (PoC) diagnostics. Advancing sensor performance such as sensitivity to detect trace amounts (ppb-ppm) of analytes (gas/VOCs), selectivity, portability, and low cost is critical for many of these applications. These advancements are mainly achieved by selecting and optimizing sensing materials by their surface functionalization and/or structural optimization to achieve favorable transport characteristics or chemical binding/reaction sites. Surprisingly, the sensor geometry, shapes, and patterns were not considered as critical parameters, and most of these sensors were designed by following simple planar and interdigitated electrode geometry. In this study, we introduce a new bioinspired fractal approach to design chemoresistive sensors with fractal geometry, which grasp the architecture of fern leaves represented by the geometric group of space-filling curves of fractal patterns. These fractal sensors were printed by an extrusion process on a flexible substrate (PET) using specially formulated graphene ink as a sensing material, which provided significant enhancement of the active surface area to volume ratio and allowed high-resolution fractal patterning along with a reduced current transportation path. To demonstrate the advantages and influence of fractal geometry on sensor performance, here, three different kinds of sensors were fabricated based on different fractal geometrics (Sierpinski, Peano, and Hilbert), and the sensing performance was explored toward different VOC analytes (e.g., ethanol, methanol, and acetone). Among all these fractal-designed sensors including interdigitate sensors, the Hilbert-designed printed sensor shows enhanced sensing properties in terms of fast response time (6 s for 30 ppm), response value (14%), enhanced detection range (5-100 ppm), high selectivity, and low interference to humidity (up to RH 80%) for ethanol at room temperature (20 °C). Moreover, a significant improvement of this sensor performance was observed by applying the mechanical deformation (positive bending) technique. The practical application of this sensor was successfully demonstrated by monitoring food spoilage using a commercial box of strawberries as a model. Based on these presented results, this biofractal biomimetic VOC sensor is demonstrated for a prospective application in food monitoring.

Converging 2D Nanomaterials and 3D Bioprinting Technology: State-of-the-Art, Challenges, and Potential Outlook in Biomedical Applications.

The development of next-generation of bioinks aims to fabricate anatomical size 3D scaffold with high printability and biocompatibility. Along with the progress in 3D bioprinting, 2D nanomaterials (2D NMs) prove to be emerging frontiers in the development of advanced materials owing to their extraordinary properties. Harnessing the properties of 2D NMs in 3D bioprinting technologies can revolutionize the development of bioinks by endowing new functionalities to the current bioinks. First the main contributions of 2D NMS in 3D bioprinting technologies are categorized here into six main classes: 1) reinforcement effect, 2) delivery of bioactive molecules, 3) improved electrical conductivity, 4) enhanced tissue formation, 5) photothermal effect, 6) and stronger antibacterial properties. Next, the recent advances in the use of each certain 2D NMs (1) graphene, 2) nanosilicate, 3) black phosphorus, 4) MXene, 5) transition metal dichalcogenides, 6) hexagonal boron nitride, and 7) metal-organic frameworks) in 3D bioprinting technology are critically summarized and evaluated thoroughly. Third, the role of physicochemical properties of 2D NMSs on their cytotoxicity is uncovered, with several representative examples of each studied 2D NMs. Finally, current challenges, opportunities, and outlook for the development of nanocomposite bioinks are discussed thoroughly.

Fast response hydrogen gas sensor based on Pd/Cr nanogaps fabricated by a single-step bending deformation.

The development of low-cost and high performing hydrogen gas sensors is important across many sectors, including mining, energy and defense using hydrogen (H2) gas. Herein, we demonstrate a new concept of H2 sensors based on Pd/Cr nanogaps created by using a simple mechanical bending deformation technique. These nanogap sensors can selectively detect the H2 gas based on transduction of the volume expansion after H2 uptake into an electrical signal by palladium-based metal-hydrides that allows closure of nanogaps for electrons flowing or tunneling. While this break-junction architecture, according to literature, can provide several advantages with research gaps in terms of fabricating nanogap sensors with ultra-fast response (≤4 s), the size of nanogap (≤20 nm) and their relationship with time response and recovery as addressed in this paper. Based on the computational modelling outcome, the size of the nanogaps can be investigated in order to optimize the fabrication conditions. Indeed, a single nanogap with optimum width (15 nm) acts as an on-off switch for best performing hydrogen detection. Moreover, with the unique design of Pd/Cr nanogap, the developed sensing device meets major requirement of advanced H2 gas sensor including room temperature (25 °C) operation, detection of trace amounts (10-40,000 ppm), good linearity, ultra-fast response-recovery time (3/4.5 s) and high selectivity. The presented economical lithography-free fabrication method has simple circuitry, low power consumption, recyclability, and favorable aging properties that promises great potential to be used for many practical applications of H2 detection.

Functional inks and extrusion-based 3D printing of 2D materials: a review of current research and applications.

Graphene and related 2D materials offer an ideal platform for next generation disruptive technologies and in particular the potential to produce printed electronic devices with low cost and high throughput. Interest in the use of 2D materials to create functional inks has exponentially increased in recent years with the development of new ink formulations linked with effective printing techniques, including screen, gravure, inkjet and extrusion-based printing towards low-cost device manufacturing. Exfoliated, solution-processed 2D materials formulated into inks permits additive patterning onto both rigid and conformable substrates for printed device design with high-speed, large-scale and cost-effective manufacturing. Each printing technique has some sort of clear advantages over others that requires characteristic ink formulations according to their individual operational principles. Among them, the extrusion-based 3D printing technique has attracted heightened interest due to its ability to create three-dimensional (3D) architectures with increased surface area facilitating the design of a new generation of 3D devices suitable for a wide variety of applications. There still remain several challenges in the development of 2D material ink technologies for extrusion printing which must be resolved prior to their translation into large-scale device production. This comprehensive review presents the current progress on ink formulations with 2D materials and their broad practical applications for printed energy storage devices and sensors. Finally, an outline of the challenges and outlook for extrusion-based 3D printing inks and their place in the future printed devices ecosystem is presented.

Multifunctional Binding Chemistry on Modified Graphene Composite for Selective and Highly Efficient Adsorption of Mercury.

Engineering of multifunctional binding chemistry on graphene composites using thiol-ene click reaction for selective and highly efficient adsorption of mercury(II) is demonstrated. Graphene oxide (GO) is used as an initial material for covalent attachment of cysteamine molecules by thiol-ene click reaction on C═C groups to achieve a partially reduced graphene surface with multiple binding chemistry such as O, S, and N. Batch adsorption studies showed remarkable adsorption rate with only 1 mg L-1 dosage of adsorbent used to remove 95% Hg (II) (∼1.5 mg L-1) within 90 min. The high adsorption capacity of 169 ± 19 mg g-1, high selectivity toward Hg in the presence of 30 times higher concentration of competing ions (Cd, Cu, Pb) and high regeneration ability (>97%) for five consecutive adsorption-desorption cycles were achieved. Comparative study with commercial activated carbon using spiked Hg (II) river water confirmed the high performance and potential of this adsorbent for real mercury remediation of environmental and drinking waters.

Tuning the Multifunctional Surface Chemistry of Reduced Graphene Oxide via Combined Elemental Doping and Chemical Modifications.

The synthesis of graphene materials with multiple surface chemistries and functionalities is critical for further improving their properties and broadening their emerging applications. We present a simple chemical approach to obtain bulk quantities of multifunctionalized reduced graphene oxide (rGO) that combines chemical doping and functionalization using the thiol-ene click reaction. Controllable modulation of chemical multifunctionality was achieved by simultaneous nitrogen doping and gradual chemical reduction of graphene oxide (GO) using ammonia and hydrazine, followed by covalent attachment of amino-terminated thiol molecules using the thiol-ene click reaction. A series of N-doped rGO (N-rGO) precursors with different levels of oxygen groups were synthesized by adjusting the amount of reducing agent (hydrazine), followed by subsequent covalent attachment of cysteamine via the thermal thiol-ene click reaction to yield different ratios of mixed functional groups including N (pyrrolic N, graphitic N, and aminic N), S (thioether S, thiophene S, and S oxides), and O (hydroxyl O, carbonyl O, and carboxyl O) on the reduced GO surface. Detailed XPS analysis confirmed the disappearance of unstable pyridinic N in cys-N-rGO and the reduction degree threshold of N-rGO for effective cysteamine modification to take place. Our study establishes a strong correlation between different reduction degrees of N-rGO with several existing oxygen functional groups and addition of new tunable functionalities including covalently attached nitrogen (amino) and sulfur (C-S-C, C=S, and S-O). This simple and versatile approach provides a valuable contribution for practical designing and synthesis of a broad range of functionalized graphene materials with tailorable functionalities, doping levels, and interfacial properties for potential applications such as polymer composites, supercapacitors, electrocatalysis, adsorption, and sensors.

Optimization of reaction parameters in hydrothermal synthesis: a strategy towards the formation of CuS hexagonal plates.

BACKGROUND: For decades, copper sulphide has been renowned as the superior optical and semiconductor materials. Its potential applications can be ranged from solar cells, lithium-ion batteries, sensors, and catalyst systems. The synthesis methodologies of copper sulphide with different controlled morphology have been widely explored in the literature. Nevertheless, the understanding on the formation chemistry of CuS is still limited. The ultimate approach undertaking in this article is to investigate the formation of CuS hexagonal plates via the optimization of reaction parameters in hydrothermal reaction between copper (II) nitrate and sodium thiosulphate without appending any assistant agent. RESULTS: COVELLITE (CUS) HEXAGONAL PLATES WERE FORMED AT COPPER ION: thiosulphate ion ([Formula: see text]) mole ratio of 1:2 under hydrothermal treatment of 155°C for 12 hours. For synthesis conducted at reaction temperature lower than 155°C, copper sulphate (CuSO4), krohnite (NaCu2(SO4)(H2O)2] and cyclooctasulphur (S8) were present as main impurities with covellite (CuS). When [Formula: see text] mole ratio was varied to 1: 1 and 1: 1.5, phase pure plate-like natrochalcite [NaCu2(SO4)(H2O)] and digenite (Cu9S5) were produced respectively. Meanwhile, mixed phases of covellite (CuS) and cyclooctasulphur (S8) were both identified when [Formula: see text] mole ratio was varied to 1: 2.5, 1: 3 and 1: 5 as well as when reaction time was shortened to 1 hour. CONCLUSIONS: CuS hexagonal plates with a mean edge length of 1 µm, thickness of 100 nm and average crystallite size of approximately (45 ± 2) nm (Scherrer estimation) were successfully synthesized via assisting agent- free hydrothermal method. Under a suitable [Formula: see text] mole ratio, we evidenced that the formation of covellite (CuS) is feasible regardless of the reaction temperature applied. However, a series of impurities were attested with CuS if reaction temperature was not elevated high enough for the additional crystallite phase decomposition. It was also identified that [Formula: see text] mole ratio plays a vital role in controlling the amount of cyclooctasulphur (S8) in the final powder obtained. Finally, reaction time was recognized as an important parameter in impurity decomposition as well as increasing the crystallite size and crystallinity of the CuS hexagonal plates formed.