Highly Water Dispersible Functionalized Graphene by Thermal Thiol-Ene Click Chemistry

Functionalization of pristine graphene to achieve high water dispersibility remains as a key obstacle owing to the high hydrophobicity and absence of reactive functional groups on the graphene surface. Herein, a green and simple modification approach to prepare highly dispersible functionalized graphene via thermal thiol-ene click reaction was successfully demonstrated on pristine graphene. Specific chemical functionalities (–COO, –NH₂ and –S) on the thiol precursor (L-cysteine ethyl ester) were clicked directly on the sp² carbon of graphene framework with grafting density of 1 unit L-cysteine per 113 carbon atoms on graphene. This functionalized graphene was confirmed with high atomic content of S (4.79 at % S) as well as the presence of C–S–C and N–H species on the L-cysteine functionalized graphene (FG-CYS). Raman spectroscopy evidently corroborated the modification of graphene to FG-CYS with an increased intensity ratio of D and G band, I_D/I_G ratio (0.3 to 0.7), full-width at half-maximum of G band, FWHM [G] (20.3 to 35.5) and FWHM [2D] (64.8 to 90.1). The use of ethanol as the reaction solvent instead of common organic solvents minimizes the chemical hazards exposure to humans and the environment. This direct attachment of multifunctional groups on the surface of pristine graphene is highly demanded for graphene ink formulations, coatings, adsorbents, sensors and supercapacitor applications.     

DABCO Derived Nitrogen-Doped Carbon Nanotubes for Oxygen Reduction Reaction (ORR) and Removal of Hexavalent Chromium from Contaminated Water

Though chemically-derived reduced graphene oxide (CDG) from graphite oxide (GO) precursors is a widely practiced procedure for the large-scale production of graphene, the quality and quantity of thus obtained CDG is dependent on the reduction strategy used. In this work, we report an all-solid-state, residue-free, microwave process for the reduction of graphene oxide and subsequent growth of carbon nanotube ‘separators’ from a single precursor, namely DABCO (1,4-diazabicyclo[2.2.2]octane). The utility of our newly developed technique in efficiently and effectively reducing graphene oxide and in growing nitrogen-doped carbon nanotubes via catalysts like palladium and iron into unique mesoporous, 3-D hierarchical carbon nanostructures is demonstrated. The applicability of the thus obtained palladium embedded in Pd@NCNT-rGO nanoarchitectures for the oxygen reduction reaction (ORR) is investigated. When carbon fiber (CF) was used as the substrate, three-dimensional Fe@NCNT-CF were obtained, whose capability as versatile adsorbents for hexavalent chromium ion removal from contaminated waters was also demonstrated.     

Reinforced 3D Composite Structures of γ-, α-Al2O3 with Carbon Nanotubes and Reduced GO Ribbons Printed from Boehmite Gels

The ability of boehmite to form printable inks has sparked interest in the manufacturing of 3D alumina (Al₂O₃) and composite structures by enabling direct ink writing methods while avoiding the use of printing additives. These materials may exhibit high porosity due to the printing and sintering procedures, depending on the intended application. The 3D-printed porous composite structures of γ-Al₂O₃ and α-Al₂O₃ containing 2 wt.% of carbon nanotubes or reduced graphene oxide ribbons were fabricated from boehmite gels, followed by different heat treatments. The reinforcing effect of these carbon nanostructures was evidenced by compression tests carried out on the different alumina structures. A maximum relative increase of 50% in compressive strength was achieved for the γ-Al₂O₃ composite structure reinforced with reduced graphene oxide ribbons, which was also accompanied by an increase in the specific surface area.     

Catalytic Reduction of Organic Dyes by Multilayered Graphene Platelets and Silver Nanoparticles in Polyacrylic Acid Hydrogel

Graphene oxide has been widely used in the oxidative degradation of environmental pollutants. However, its catalytic role can be questioned as graphene oxide with oxygen-containing functional groups may also act as reactant in oxidative reactions. Herein, hydrogel composites loaded with multilayered graphene platelets showed excellent catalytic performance for the reduction of a wastewater organic pollutant (methylene blue) under NaBH₄, which proved the catalytic role of multilayered graphene platelets. The liquid-based direct exfoliation method was used to prepare two-dimensional materials, which is compatible with other liquid phase methods to prepare nanomaterials. Hydrogel composites composed of multilayered graphene platelets, silver nanoparticles, and polyacrylic acid hydrogels were synthesized in water solution under irradiation with ultraviolet light, demonstrating the advantages of synthesizing nanocomposites using the liquid-based direct exfoliation method.     

Fabrication of Graphene/Zinc Oxide Nano-Heterostructure for Hydrogen Sensing

In this study, hydrogen (H₂) and methane (CH₄) were used as reactive gases, and chemical vapor deposition (CVD) was used to grow single-layer graphene on a copper foil substrate. The single-layer graphene obtained was transferred to a single-crystal silicon substrate by PMMA transfer technology for the subsequent growth of nano zinc oxide. The characteristics of CVD-deposited graphene were analyzed by a Raman spectrometer, an optical microscope, a four-point probe, and an ultraviolet/visible spectrometer. The sol–gel method was applied to prepare the zinc oxide seed layer film with the spin-coating method, with methanol, zinc acetate, and sodium hydroxide as the precursors for growing ZnO nanostructures. On top of the ZnO seed layer, a one-dimensional zinc oxide nanostructure was grown by a hydrothermal method at 95 °C, using a zinc nitrate and hexamethylenetetramine mixture solution. The characteristics of the nano zinc oxide were analyzed by scanning electron microscope(SEM),x-ray diffractometer(XRD), and Raman spectrometer. The obtained graphene/zinc oxide nano-heterostructure sensor has a sensitivity of 1.06 at a sensing temperature of 205 °C and a concentration of hydrogen as low as 5 ppm, with excellent sensing repeatability. The main reason for this is that the zinc oxide nanostructure has a large specific surface area, and many oxygen vacancy defects exist on its surface. In addition, the P–N heterojunction formed between the n-type zinc oxide and the p-type graphene also contributes to hydrogen sensing.     

Electron Spin Relaxation in Carbon Materials

This article focuses on EPR relaxation measurements in various carbon samples, e.g., natural carbons—anthracite, coal, higher anthraxolites, graphite; synthetically obtained carbons—glassy carbons, fullerenes, graphene, graphene oxide, reduced graphene oxide, graphite monocrystals, HOPG, nanoribbons, diamonds. The short introduction presents the basics of resonant electron spin relaxation techniques, briefly describing the obtained parameters. This review presents gathered results showing the processes leading to electron spin relaxation and typical ranges of electron spin relaxation rates for many different carbon types.     

Nitrosylation of thiols in vascular homeostasis and disease

Post-translational modification of thiols to form a nitrosothiol (S-nitrosylation) is gaining attention as a mechanism by which nitric oxide can exert some of its effects in the cardiovascular system, as well as in other systems. It has been proposed that this modification would have a particularly important role in cell signaling. However, its study has been hampered by many technical difficulties. In this paper, we summarize current achievements in the field that may help to answer the questions that have been posed about the functional role of this modification. Some of these achievements have arisen from methodologic improvements, such as proteomic studies or approaches to identify subcellular localization and tissue distribution of the modification. New functional consequences of the modification of individual proteins are also summarized.     

Role of nitric oxide (NO) in pulmonary dysfunction associated with experimental cirrhosis

We examined the functional role of nitric oxide (NO) and nitric oxide synthase (NOS) isoforms in the pulmonary dysfunction seen in cirrhosis. Lungs were isolated from control and carbon tetrachloride (CCl(4))-induced cirrhotic rats and perfused at constant flow with a whole blood mixture. Ventilation with hypoxic gas resulted in attenuated hypoxic pulmonary vasoconstriction (HPV) in lungs from cirrhotic animals. Administration of the non-selective NOS inhibitor N-omega-Nitro-L-Arginine (L-NNA) resulted in HPV responses that were not different between groups. However, inhibition of inducible nitric oxide synthase (iNOS) did not restore cirrhotic HPV responses. Lungs from cirrhotic rats demonstrated enhanced endothelial-dependent vasodilation to vasopressin when preconstricted with hypoxia but not when preconstricted with thromboxane mimetic. Western blot analysis failed to demonstrate differences in pulmonary endothelial NOS (eNOS) or iNOS levels between groups. Our data suggest that, while NO may play a role in mediating the reduced pulmonary vasoreactivity observed in cirrhosis, other vasoactive factors are likely also important modulators of the pulmonary dysfunction seen in this disease.     

Sustainable Hydrothermal and Solvothermal Synthesis of Advanced Carbon Materials in Multidimensional Applications: A Review

The adoption of green technology is very important to protect the environment and thus there is a need for improving the existing methods for the fabrication of carbon materials. As such, this work proposes to discuss, interrogate, and propose viable hydrothermal, solvothermal, and other advanced carbon materials synthesis methods. The synthesis approaches for advanced carbon materials to be interrogated will include the synthesis of carbon dots, carbon nanotubes, nitrogen/titania-doped carbons, graphene quantum dots, and their nanocomposites with solid/polymeric/metal oxide supports. This will be performed with a particular focus on microwave-assisted solvothermal and hydrothermal synthesis due to their favourable properties such as rapidity, low cost, and being green/environmentally friendly. These methods are regarded as important for the current and future synthesis and modification of advanced carbon materials for application in energy, gas separation, sensing, and water treatment. Simultaneously, the work will take cognisance of methods reducing the fabrication costs and environmental impact while enhancing the properties as a direct result of the synthesis methods. As a direct result, the expectation is to impart a significant contribution to the scientific body of work regarding the improvement of the said fabrication methods.     

Effect of Graphene Oxide on Properties of Alkali-Activated Slag

Alkali-activated materials, a new kind of low-carbon cement, have received extensive attention. While in order to obtain excellent functions, the modification of alkali-activated materials by nano-materials has become one of the important research directions of alkali-activated materials. Therein, the hydration property, mechanical properties, and action mechanism of the alkali-activated slag with and without graphene oxide (GO) were analyzed and evaluated. Results showed the compressive strength of mortar decreased at 3 days and 28 days by adding GO. While the flexural strength of mortar cured for different ages increased with increasing GO content, and the flexural strength increasing rate reached up to 15.94% at 28 days, thus, the toughening effect of GO was significant. GO accelerated the hydration process of alkali-activated slag because the functional groups offered nucleation sites to induce the generation of more hydration products. Furthermore, the addition of GO increased the number of harmless pores and reduced the pore size, but also introduced a large number of harmful pores, resulting in the reduction of compressive strength.     

Graphene-Oxide-Enriched Biomaterials: A Focus on Osteo and Chondroinductive Properties and Immunomodulation

Due to its exceptional physical properties, such as high electronic conductivity, good thermal stability, excellent mechanical strength, and chemical versatility, graphene has sparked a lot of interest in the scientific community for various applications. It has therefore been employed as an antibacterial agent, in photothermal therapy (PTT) and biosensors, in gene delivery systems, and in tissue engineering for regenerative purposes. Since it was first discovered in 1947, different graphene derivatives have been synthetized from pristine graphene. The most adaptable derivate is graphene oxide (GO). Owing to different functional groups, the amphiphilic structure of GO can interact with cells and exogenous or endogenous growth/differentiation factors, allowing cell adhesion, growth, and differentiation. When GO is used as a coating for scaffolds and nanomaterials, it has been found to enhance bone, chondrogenic, cardiac, neuronal, and skin regeneration. This review focuses on the applications of graphene-based materials, in particular GO, as a coating for scaffolds in bone and chondrogenic tissue engineering and summarizes the most recent findings. Moreover, novel developments on the immunomodulatory properties of GO are reported.     

Advances in Drug Delivery Nanosystems Using Graphene-Based Materials and Carbon Nanotubes

Carbon is one of the most abundant elements on Earth. In addition to the well-known crystallographic modifications such as graphite and diamond, other allotropic carbon modifications such as graphene-based nanomaterials and carbon nanotubes have recently come to the fore. These carbon nanomaterials can be designed to help deliver or target drugs more efficiently and to innovate therapeutic approaches, especially for cancer treatment, but also for the development of new diagnostic agents for malignancies and are expected to help combine molecular imaging for diagnosis with therapies. This paper summarizes the latest designed drug delivery nanosystems based on graphene, graphene quantum dots, graphene oxide, reduced graphene oxide and carbon nanotubes, mainly for anticancer therapy.     

Mechanical Reinforcement in Nylon 6 Nanocomposite Fiber Incorporated with Dopamine Reduced Graphene Oxide

The emergence of graphene-based polymer composite fibers provides a new opportunity to study the high-performance and functional chemical fibers. In this work, we have developed an efficient and convenient method with polydopamine (PDA) to functionalize and reduce graphene oxide (GO) simultaneously, and the modified graphene nanosheets can obtain uniform dispersion and strong interfacial bonding in nylon 6 (PA6). Furthermore, the reinforced PA6 composite fibers were prepared through mixing PDA-rGO into the PA6 polymer matrix and then melt spinning. The functional modification was characterized by surface analysis and structural testing including SEM, TEM, FTIR, and Raman. When the addition amount of the modified GO was 0.15 wt%, the tensile strength and Young’s modulus of the composite fiber reached 310.4 MPa and 462.3 MPa, respectively. The results showed a meaningful reinforcement with an effect compared to the pure nylon 6 fiber. Moreover, the composite fiber also exhibited an improved crystallinity and thermal stability, as measured by DSC and TGA.     

Effect of Microwave Treatment in a High Pressure Microwave Reactor on Graphene Oxide Reduction Process—TEM,XRD, Raman,IR and Surface Electron Spectroscopic Studies

Reduced graphene oxide (rGO) was prepared by chemical reduction of graphene oxide (GO) (with a modified Hummers method) in aqueous solutions of hydrazine (N₂H₄), formaldehyde (CH₂O), formic acid (HCO₂H) accompanied by a microwave treatment at 250 °C (MWT) by a high pressure microwave reactor (HPMWR) at 55 bar. The substrates and received products were investigated by TEM, XRD, Raman and IR spectroscopies, XPS, XAES and REELS. MWT assisted reduction using different agents resulted in rGOs of a large number of vacancy defects, smaller than at GO surface C sp³ defects, oxygen groups and interstitial water, interlayer distance and diameter of stacking nanostructures (flakes). The average number of flake layers obtained from XRD and REELS was consistent, being the smallest for CH₂O and then increasing for HCO₂H and N₂H₄. The number of layers in rGOs increases with decreasing content of vacancy, C sp³ defects, oxygen groups, water and flake diameter. MWT conditions facilitate formation of vacancies and additional hydroxyl, carbonyl and carboxyl groups at these vacancies, provide no remarkable modification of flake diameter, what results in more competitive penetration of reducing agent between the interstitial sites than via vacancies. MWT reduction of GO using a weak reducing agent (CH₂O) provided rGO of 8 layers thickness.     

Pollutants Sorbent Made of Cotton Fabric Modified with Chitosan-Glutaraldehyde and Zinc Oxide Particles

The paper reports on the preparation of composite materials by modifying cotton fabric with a layer of crosslinked glutaraldehyde chitosan containing zinc oxide particles. The ability of chitosan to form complexes with zinc ions has been used to control the size, structure, and distribution of the particles on the fiber surface. The three different obtained materials have been characterized by optical and scanning electron microscopy, Fourier-transform infrared spectroscopy (FTIR), and fluorescent analysis. It has been found that the interaction of the ZnO particles with the functional groups of chitosan affects its swelling ability in water and thus determines its sorption properties. The capacity of the materials to wipe water-soluble (textile reactive dye) and water-insoluble (crude oil and oil products) contaminants has been compared. The effect that the amount of zinc oxide has on the ability of the materials to remove contaminants has also been studied. The possibility for adsorption–desorption of the crude oil and reuse of the sorbent material has been investigated as well.     

The Effects of Oxygen Functional Groups on Graphene Oxide on the Efficient Adsorption of Radioactive Iodine

Oxygen-containing functional groups tend to induce a strong interaction between solid adsorbents and iodine molecules, yet have not been systematically investigated. Herein, on the basis of a series of nitric acid-treated graphene oxide (GO) with different contents of oxygen functional groups for iodine adsorption, it was found that the iodine uptake capacity is proportionate to the oxygen content and the diversities of oxygen-containing groups. The density functional theory (DFT) calculation results also suggest that oxygen-containing groups result in strong interactions between iodine molecules and the adsorbents through a covalent bond-forming process, among which -OH groups possess a higher adsorption energy averagely. Such theoretical and experimental work deepens our understanding of the effects of oxygen functional groups on iodine adsorption and provides novel ideas for future design and synthesis of high-performance solid adsorbents for radioactive iodine.     

High-κ oxide nanoribbons as gate dielectrics for high mobility top-gated graphene transistors

Deposition of high-κ dielectrics onto graphene is of significant challenge due to the difficulties of nucleating high quality oxide on pristine graphene without introducing defects into the monolayer of carbon lattice. Previous efforts to deposit high-κ dielectrics on graphene often resulted in significant degradation in carrier mobility. Here we report an entirely new strategy to integrate high quality high-κ dielectrics with graphene by first synthesizing freestanding high-κ oxide nanoribbons at high temperature and then transferring them onto graphene at room temperature. We show that single crystalline Al₂O₃ nanoribbons can be synthesized with excellent dielectric properties. Using such nanoribbons as the gate dielectrics, we have demonstrated top-gated graphene transistors with the highest carrier mobility (up to 23,600 cm²/V·s) reported to date, and a more than 10-fold increase in transconductance compared to the back-gated devices. This method opens a new avenue to integrate high-κ dielectrics on graphene with the preservation of the pristine nature of graphene and high carrier mobility, representing an important step forward to high-performance graphene electronics.     

In situ observation of graphene sublimation and multi-layer edge reconstructions

We induced sublimation of suspended few-layer graphene by in situ Joule-heating inside a transmission electron microscope. The graphene sublimation fronts consisted of mostly {1100} zigzag edges. Under appropriate conditions, a fractal-like “coastline” morphology was observed. Extensive multiple-layer reconstructions at the graphene edges led to the formation of unique carbon nanostructures, such as sp²-bonded bilayer edges (BLEs) and nanotubes connected to BLEs. Flat fullerenes/nanopods and nanotubes tunneling multiple layers of graphene sheets were also observed. Remarkably, >99% of the graphene edges observed during sublimation are BLEs rather than monolayer edges (MLEs), indicating that BLEs are the stable edges in graphene at high temperatures. We reproduced the “coastline” sublimation morphologies by kinetic Monte Carlo (kMC) simulations. The simulation revealed geometrical and topological features unique to quasi-2-dimensional (2D) graphene sublimation and reconstructions. These reconstructions were enabled by bending, which cannot occur in first-order phase transformations of 3D bulk materials. These results indicate that substrate of multiple-layer graphene can offer unique opportunities for tailoring carbon-based nanostructures and engineering novel nano-devices with complex topologies.     

Influence of the Surface Chemistry of Graphene Oxide on the Structure–Property Relationship of Waterborne Poly(urethane urea) Adhesive

Small amounts—0.04 wt.%—graphene oxide derivatives with different surface chemistry (graphene oxide—GO-, amine-functionalized GO—A-GO-, reduced GO—r-GO) were added during prepolymer formation in the synthesis of waterborne poly(urethane urea) dispersions (PUDs). Covalent interactions between the surface groups on the graphene oxide derivatives and the end NCO groups of the prepolymer were created, these interactions differently altered the degree of micro-phase separation of the PUDs and their structure–properties relationships. The amine functional groups on the A-GO surface reacted preferentially with the prepolymer, producing new urea hard domains and higher percentage of soft segments than in the PUD without GO derivative. All GO derivatives were well dispersed into the PU matrix. The PUD without GO derivative showed the most noticeable shear thinning and the addition of the GO derivative reduced the extent of shear thinning differently depending on its functional chemistry. The free urethane groups were dominant in all PUs and the addition of the GO derivative increased the percentage of the associated by hydrogen bond urethane groups. As a consequence, the addition of GO derivative caused a lower degree of micro-phase separation. All PUs containing GO derivatives exhibited an additional thermal decomposition at 190–206 °C which was ascribed to the GO derivative-poly(urethane urea) interactions, the lowest temperature corresponded to PU+A-GO. The PUs exhibited two structural relaxations, their temperatures decreased by adding the GO derivative, and the values of the maximum of tan delta in PU+r-GO and PU+A-GO were significantly higher than in the rest. The addition of the GO derivative increased the elongation-at-break, imparted some toughening, and increased the adhesion of the PUD. The highest T-peel strength values corresponded to the joints made with PUD+GO and PUD+r-GO, and a rupture of the substrate was obtained.