One-Pot Synthesis of Functionalised rGO/AgNPs Hybrids as Pigments for Highly Conductive Printing Inks.

This work provides a method for the development of conductive water-based printing inks for gravure, flexography and screen-printing incorporating commercial resins that are already used in the printing industry. The development of the respective conductive materials/pigments is based on the simultaneous (in one step) reduction of silver salts and graphene oxide in the presence of 2,5-diaminobenzenesulfonic acid that is used for the first time as the common in-situ reducing agent for these two reactions. The presence of aminophenylsulfonic derivatives is essential for the reduction procedure and in parallel leads to the enrichment of the graphene surface with aminophenylsulfonic groups that provide a high hydrophilicity to the final materials/pigments.

2D Non-van der Waals Nanoplatelets of Hematene and Magnetene: Nonlinear Optical Response and Optical Limiting Performance from UV to NIR.

Recently, the preparation of some hematene and magnetene ultrathin non van der Waals (non-vdW) 2D nanoplatelets was reported starting from hematite and magnetite natural iron ores. The present work reports on the determination and evaluation of the nonlinear optical response and the optical limiting (OL) action of these 2D nanoplatelets dispersed in water under ns laser excitation. The obtained results show that both hematene and magnetene exhibit strong nonlinear absorption and refraction, comparable and even larger than those of other van der Waals (vdW) 2D counterpart materials. In addition, due to their strong nonlinear absorption, both hematene and magnetene show exceptional OL performance from the UV to visible, attaining very low values of optical limiting onset (OLon ), comparable and even lower than that of vdW 2D nanomaterials, such as graphene, graphene oxide, other transition metal dichalcogenides like MoS2 , WS2 and MoSe2 , black phosphorous and antimonene. Moreover, hematene was found to exhibit more efficient OL action than magnetene for all the excitation wavelengths studied, attributed to more efficient ligand to metal charge transfer. The present findings open new possibilities for the potential use of these non-vdW 2D materials in photonics and optoelectronics, e. g., as optical limiters and optical switchers.

Strong Ultrafast Saturable Absorption and Nonlinear Refraction of Some Non-van der Waals 2D Hematene and Magnetene Nanoplatelets for Ultrafast Photonic Applications.

In the present work, some non-van der Waals (non-vdW) 2D materials, namely, hematene and magnetene nanoplatelets, were synthesized starting from hematite and magnetite ores, respectively, using a green synthesis method, and they were dispersed in water. Then, their ultrafast nonlinear optical (NLO) response was studied under 50 fs, 400 nm laser excitation. Both non-vdW 2D materials revealed strong saturable absorption with NLO absorption coefficient ß, saturable intensity, and modulation depth of about -33.2 × 10-15 m/W, 320 GW/cm2, and 19%, respectively, for hematene, and about -21.4 × 10-15 m/W, 500 GW/cm2, and 17% for magnetene. These values are comparable to those of other vdW 2D materials, such as graphene, transition metal dichalcogenides (TMDs) like MoS2, WS2, and MoSe2, black phosphorus (BP), and some MXenes (Ti3C2Tx), recently reported as efficient saturable absorbers. In addition, both hematene and magnetene dispersions displayed strong Kerr type NLO refraction with nonlinear refractive index parameters γ' comparable and even larger than those of van der Waals 2D materials. In all cases, hematene was found exhibiting significantly larger optical nonlinearities than magnetene, most probably due to the formation of a more efficient charge transfer system. The results of the present work are strongly suggesting that hematene and magnetene can have applications in a wide range of photonic and optoelectronic applications.

Spin-Injection in Graphene: An EPR and Raman Study.

In this article, the enrichment of graphene and graphene oxide with free radicals through their functionalization with tyrosine is studied. In contrast with what is commonly observed in the functionalization of graphene with organic species the addition of tyrosine radicals on to the graphene substrate led to a remarkable increase of the aromatic character as indicated by the spectroscopic data. Similar behaviour was observed for the functionalization of graphene oxide. In addition, a brief analysis of the tyrosine functionalized graphene with EPR spectroscopy showed a remarkable enhancement of the spin density that could be useful in spintronics.

Graphene-Based Composites with Silver Nanowires for Electronic Applications.

Graphene/metal nanocomposites have shown a strong potential for use in electronic applications. In particular, the combination of silver nanowires (AgNWs) with graphene derivatives leads to the formation of an efficient conductive network, thus improving the electrical properties of a composite. This work focused on developing highly conductive hydrophilic hybrids of simultaneously functionalized and reduced graphene oxide (f-rGO) and AgNWs in different weight ratios by following two different synthetic routes: (a) the physical mixture of f-rGO and AgNWs, and (b) the in situ reduction of GO in the presence of AgNWs. In addition, the role of AgNWs in improving the electrical properties of graphene derivatives was further examined by mixing AgNWs with a hybrid of few-layered graphene with functionalized multiwalled carbon nanotubes (FLG/MWNT-f-OH). The studied materials showed a remarkable improvement in the overall electrical conductivity due to the synergistic effect of their components, which was proportional to the percentage of Ag and dependent on the procedure of the hybrid formation. One of the f-rGO/AgNWs composites was also selected for the preparation of gravure printing inks that were tested to determine their rheological and printing properties. All of the f-rGO/AgNWs composites were shown to be very promising materials for use as conductive inks for flexible electronics.

Thermomechanical Properties of Carbon Nanocomposites PEGDA Photopolymers.

In this work, UV-curable resin poly (ethylene glycol) diacrylate (PEGDA) was reinforced with three different types of nanofillers: pristine graphene (G), multiwalled carbon nanotubes (MWNTs), and a hybrid of MWNTs and graphene 70/30 in mass ratio (Hyb). PEGDA was mixed homogenously with the nanofiller oligomer by shear mixing and then photopolymerized, affording thin, stable films. The thermomechanical properties of the afforded nanocomposites indicated the superior reinforcing ability of pristine graphene compared with MWNTs and an intermediate behavior of the hybrid.

Biological Response of Human Cancer Cells to Ionizing Radiation in Combination with Gold Nanoparticles.

In the context of improving radiation therapy, high-atomic number (Z) metallic nanoparticles and, more importantly, gold-based nanostructures are developed as radiation enhancers/radiosensitizers. Due to the diversity of cell lines, nanoparticles, as well as radiation types or doses, the resulting biological effects may differ and remain obscure. In this multiparameter study, we aim to shed light on these effects and investigate them further by employing X-irradiation and three human cancer cell lines (PC3, A549, and U2OS cells) treated by multiple techniques. TEM experiments on PC3 cells showed that citrate-capped AuNPs were found to be located mostly in membranous structures/vesicles or autophagosomes, but also, in the case of PEG-capped AuNPs, inside the nucleus as well. The colony-forming capability of cancer cells radiosensitized by AuNPs decreased significantly and the DNA damage detected by cytogenetics, γH2AX immunostaining, and by single (γH2AX) or double (γH2AX and OGG1) immunolocalization via transmission electron microscopy (TEM) was in many cases higher and/or persistent after combination with AuNPs than upon individual exposure to ionizing radiation (IR). Moreover, different cell cycle distribution was evident in PC3 but not A549 cells after treatment with AuNPs and/or irradiation. Finally, cellular senescence was investigated by using a newly established staining procedure for lipofuscin, based on a Sudan Black-B analogue (GL13) which showed that based on the AuNPs' concentration, an increased number of senescent cells might be observed after exposure to IR. Even though different cell lines or different types and concentrations of AuNPs may alter the levels of radiosensitization, our results imply that the complexity of damage might also be an important factor of AuNP-induced radiosensitization.

Highly Elastic Melamine Graphene/MWNT Hybrid Sponge for Sensor Applications.

The rapidly increased interest in multifunctional nanoelectronic devices, such as wearable monitors, smart robots, and electronic skin, motivated many researchers toward the development of several kinds of sensors in recent years. Flexibility, stability, sensitivity, and low cost are the most important demands for exploiting stretchable or compressible strain sensors. This article describes the formation and characteristics of a flexible, low-cost strain sensor by combining a commercial melamine sponge and a graphene/carbon nanotubes hybrid. The composite that emerged by doping the highly elastic melamine sponge with a highly conductive graphene/carbon nanotubes hybrid showed excellent piezoresistive behavior, with low resistivity of 22 kΩ m. Its function as a piezoresistive material exhibited a high sensitivity of 0.050 kPa-1 that combined with a wide detection area ranging between 0 to 50 kPa.

Hydrothermal Unzipping of Multiwalled Carbon Nanotubes and Cutting of Graphene by Potassium Superoxide.

The dual use of potassium superoxide (KO2) to unzip multiwalled carbon nanotubes (MWCNTs) and cut graphene under hydrothermal conditions is described in this work. The KO2-assisted hydrothermal treatment was proven to be a high-yield method for forming graphene nanoribbons and dots or sub-micro-sized graphene nanosheets. Starting with functionalized MWCNTs, the method produces water-dispersible graphene nanoribbons with characteristic photoluminescence depending on their width. Using pristine graphene, the hydrothermal treatment with KO2 produces nanosized graphene sheets and graphene quantum dots with diameters of less than 10 nm. The latter showed a bright white photoluminescence. The effective hydrothermal unzipping of MWNTs and the cutting of large graphene nanosheets is a valuable top-down approach for the preparation of graphene nanoribbons and small nanographenes. Both products with limited dimensions have interesting applications in nanoelectronics and bionanotechnology.

Condensed Clustered Iron Oxides for Ultrahigh Photothermal Conversion and In Vivo Multimodal Imaging.

Magnetic iron oxide nanocrystals (MIONs) are established as potent theranostic nanoplatforms due to their biocompatibility and the multifunctionality of their spin-active atomic framework. Recent insights have also unveiled their attractive near-infrared photothermal properties, which are, however, limited by their low near-infrared absorbance, resulting in noncompetitive photothermal conversion efficiencies (PCEs). Herein, we report on the dramatically improved photothermal conversion of condensed clustered MIONs, reaching an ultrahigh PCE of 71% at 808 nm, surpassing the so-far MION-based photothermal agents and even benchmark near-infrared photothermal nanomaterials. Moreover, their surface passivation is achieved through a simple self-assembly process, securing high colloidal stability and structural integrity in complex biological media. The bifunctional polymeric canopy simultaneously provided binding sites for anchoring additional cargo, such as a strong near-infrared-absorbing and fluorescent dye, enabling in vivo optical and photoacoustic imaging in deep tissues, while the iron oxide core ensures detection by magnetic resonance imaging. In vitro studies also highlighted a synergy-amplified photothermal effect that significantly reduces the viability of A549 cancer cells upon 808 nm laser irradiation. Integration of such-previously elusive-photophysical properties with simple and cost-effective nanoengineering through self-assembly represents a significant step toward sophisticated nanotheranostics, with great potential in the field of nanomedicine.

A Guide for Using Transmission Electron Microscopy for Studying the Radiosensitizing Effects of Gold Nanoparticles In Vitro.

The combined effects of ionizing radiation (IR) with high-z metallic nanoparticles (NPs) such as gold has developed a growing interest over the recent years. It is currently accepted that radiosensitization is not only attributed to physical effects but also to underlying chemical and biological mechanisms' contributions. Low- and high-linear energy transfer (LET) IRs produce DNA damage of different structural types. The combination of IR with gold nanoparticles may increase the clustering of energy deposition events in the vicinity of the NPs due to the production mainly of photoelectrons and Auger electrons. Biological lesions of such origin for example on DNA are more difficult to be repaired compared to isolated lesions and can augment IR's detrimental effects as shown by numerous studies. Transmission electron microscopy (TEM) offers a unique opportunity to study the complexity of these effects on a very detailed cellular level, in terms of structure, including nanoparticle uptake and damage. Cellular uptake and nanoparticle distribution inside the cell are crucial in order to contribute to an optimal dose enhancement effect. TEM is mostly used to observe the cellular localization of nanoparticles. However, it can also provide valuable insights on the NPs' radiosensitization pathways, by studying the biochemical mechanisms through immunogold-labelling of antigenic sites at ultrastructural level under high resolution and magnification. Here, our goal is to describe the possibilities, methodologies and proper use of TEM in the interest of studying NPs-based radiosensitization mechanisms.

Graphene Aerogel Growth on Functionalized Carbon Fibers.

Graphene aerogel (GA) is a lightweight, porous, environmentally friendly, 3D structured material with interesting properties, such as electrical conductivity, a high surface area, and chemical stability, which make it a powerful tool in energy storage, sensing, catalyst support, or environmental applications. However, the poor mechanical stability that often characterizes graphene aerogels is a serious obstacle for their use in such applications. Therefore, we report here the successful mechanical reinforcement of GA with carbon fibers (CFs) by combining reduced graphene oxide (rGO) and CFs in a composite material. The surfaces of the CFs were first successfully desized and enriched with epoxy groups using epichloridrine. Epoxy-functionalized CFs (epoxy-CFs) were further covered by reduced graphene oxide (rGO) nanosheets, using triethylene tetramine (TETA) as a linker. The rGO-covered CFs were finally incorporated into the GA, affording a stiff monolithic aerogel composite. The as-prepared epoxy-CF-reinforced GA was characterized by spectroscopic and microscopic techniques and showed enhanced electrical conductivity and compressive strength. The improved electrical and mechanical properties of the GA-CFs composite could be used, among other things, as electrode material or strain sensor applications.

Layer-by-Layer Assembly of Clay-Carbon Nanotube Hybrid Superstructures.

Much of the research effort concerning layered materials is directed toward their use as building blocks for the development of hybrid nanostructures with well-defined dimensions and behavior. Here, we report the fabrication through layer-by-layer deposition and intercalation chemistry of a new type of clay-based hybrid film, where functionalized carbon nanotubes are sandwiched between nanometer-sized smectite clay platelets. Single-walled carbon nanotubes (SWCNTs) were covalently functionalized in a single step with phenol groups, via 1,3-dipolar cycloaddition, to allow for stable dispersion in polar solvents. For the production of hybrid thin films, a bottom-up approach combining self-assembly with Langmuir-Schaefer deposition was applied. Smectite clay nanoplatelets act as a structure-directing interface and reaction media for grafting functionalized carbon nanotubes in a bidimensional array, allowing for a controllable layer-by-layer growth at a nanoscale. Hybrid clay/SWCNT multilayer films deposited on various substrates were characterized by X-ray reflectivity, Raman, and X-ray photoelectron spectroscopies, as well as atomic force microscopy.

Interfacial Asymmetric Post-Functionalization of Graphene: Amphiphilic Graphene Derivatives Self-Assembled to 3D Superstructures.

The interfacial asymmetric post-functionalization of graphene nanosheets and their self-assembly into superstructures is presented. By performing two sequential functionalizations, graphene nanosheets lying in the interface of a biphasic aqueous-organic system become amphiphilic, thereby generating an organophilic side and a hydrophilic side. The as-prepared Janus type amphiphilic graphene nanosheets are then self-assembled to generate different interesting superstructures, depending on the nature of the solvent in which they are dispersed.

Solid phase extraction for the purification of violet, blue, green and yellow emitting carbon dots.

In this work, we describe a simple and general procedure for the purification of carbon dots. Following a hydrothermal heating procedure, the reaction mixture usually contains unreacted starting material and by-products alongside the carbon dots, which often appear among otherwise intense photoluminescence. The proposed purification method is based on a solid phase extraction technique, where the reaction mixture is absorbed on porous alumina and the carbon dots are isolated from the by-products and unreacted organics using proper solvents, and are finally recovered from the alumina using a simple extraction.

Highly Conductive Water-Based Polymer/Graphene Nanocomposites for Printed Electronics.

The preparation and characterization of highly conductive carbon inks is described based on nanocomposites that combine a polystyrene-acrylic resin or water-soluble polymers with a hydrophilic graphene/carbon nanotube hybrid. The water-based carbon inks showed high electrical conductivity and could be effectively used in advanced technologies such as gravure printing for printed electronics. Moreover, the conductivity was shown to be increased with a power law of the nanohybrid volume fraction, with an exponent close to that predicted from the percolation theory, indicating a limited impact of the polymer tunneling barrier on the electrical conductivity of such nanocomposites.

Cyanographene and Graphene Acid: Emerging Derivatives Enabling High-Yield and Selective Functionalization of Graphene.

Efficient and selective methods for covalent derivatization of graphene are needed because they enable tuning of graphene's surface and electronic properties, thus expanding its application potential. However, existing approaches based mainly on chemistry of graphene and graphene oxide achieve only limited level of functionalization due to chemical inertness of the surface and nonselective simultaneous attachment of different functional groups, respectively. Here we present a conceptually different route based on synthesis of cyanographene via the controllable substitution and defluorination of fluorographene. The highly conductive and hydrophilic cyanographene allows exploiting the complex chemistry of -CN groups toward a broad scale of graphene derivatives with very high functionalization degree. The consequent hydrolysis of cyanographene results in graphene acid, a 2D carboxylic acid with pKa of 5.2, showing excellent biocompatibility, conductivity and dispersibility in water and 3D supramolecular assemblies after drying. Further, the carboxyl groups enable simple, tailored and widely accessible 2D chemistry onto graphene, as demonstrated via the covalent conjugation with a diamine, an aminothiol and an aminoalcohol. The developed methodology represents the most controllable, universal and easy to use approach toward a broad set of 2D materials through consequent chemistries on cyanographene and on the prepared carboxy-, amino-, sulphydryl-, and hydroxy- graphenes.

Remarkable enhancement of the electrical conductivity of carbon nanostructured thin films after compression.

In this work, we demonstrate a significant improvement in the electrical conductivity of carbon nanostructured thin films, composed of graphene nanosheets and multiwalled carbon nanotubes, by compression/polishing. It is shown that the sheet resistance of compressed thin films of carbon nanostructures and hybrids is remarkably decreased in comparison with that of as-deposited films. The number of the interconnections, the distance between the nanostructures as well as their orientation are highly altered by the compression favoring the electrical conductivity of the compressed samples.

Noncovalent Functionalization of Graphene and Graphene Oxide for Energy Materials, Biosensing, Catalytic, and Biomedical Applications.

This Review focuses on noncovalent functionalization of graphene and graphene oxide with various species involving biomolecules, polymers, drugs, metals and metal oxide-based nanoparticles, quantum dots, magnetic nanostructures, other carbon allotropes (fullerenes, nanodiamonds, and carbon nanotubes), and graphene analogues (MoS2, WS2). A brief description of π-π interactions, van der Waals forces, ionic interactions, and hydrogen bonding allowing noncovalent modification of graphene and graphene oxide is first given. The main part of this Review is devoted to tailored functionalization for applications in drug delivery, energy materials, solar cells, water splitting, biosensing, bioimaging, environmental, catalytic, photocatalytic, and biomedical technologies. A significant part of this Review explores the possibilities of graphene/graphene oxide-based 3D superstructures and their use in lithium-ion batteries. This Review ends with a look at challenges and future prospects of noncovalently modified graphene and graphene oxide.

Highly dispersible disk-like graphene nanoflakes.

We present the preparation of disk-like graphene nanoflakes, highly dispersible in dimethylformamide (DMF), with uniform size and thickness. The preparation procedure includes an overnight mild sonication of natural graphite in DMF, followed by a purification step using ultra-centrifugation. The mean diameter of the as produced well defined round shaped graphene nanoflakes is about 100 nm and they consisted of less than twenty graphenic layers.