Fully hydrogenated graphene (graphane) and partially hydrogenated graphene materials are expected to possess various fundamentally different properties from graphene. We have prepared highly hydrogenated graphene containing 5% wt of hydrogen via Birch reduction of graphite oxide using elemental sodium in liquid NH3 as electron donor and methanol as proton donor in the reduction. We also investigate the influence of preparation method of graphite oxide, such as the Staudenmaier, Hofmann or Hummers methods on the hydrogenation rate. A control experiment involving NaNH2 instead of elemental Na was also performed. The materials were characterized in detail by electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy both at room and low temperatures, X-ray fluorescence spectroscopy, inductively coupled plasma optical emission spectroscopy, combustible elemental analysis and electrical resistivity measurements. Magnetic measurements are provided of bulk quantities of highly hydrogenated graphene. In the whole temperature range up to room temperature, the hydrogenated graphene exhibits a weak ferromagnetism in addition to a contribution proportional to field that is caused not only by diamagnetism but also likely by an antiferromagnetic influence. The origin of the magnetism is also determined to arise from the hydrogenated graphene itself, and not as a result of any metallic impurities.

The synthesis of graphene materials is typically carried out by oxidizing graphite to graphite oxide followed by a reduction process. Numerous methods exist for both the oxidation and reduction steps, which causes unpredictable contamination from metallic impurities into the final material. These impurities are known to have considerable impact on the properties of graphene materials. We synthesized several reduced graphene oxides from extremely pure graphite using several popular oxidation and reduction methods and tracked the concentrations of metallic impurities at each stage of synthesis. We show that different combinations of oxidation and reduction introduce varying types as well as amounts of metallic elements into the graphene materials, and their origin can be traced to impurities within the chemical reagents used during synthesis. These metallic impurities are able to alter the graphene materials' electrochemical properties significantly and have wide-reaching implications on the potential applications of graphene materials.

Carbonic anhydrase IX (CAIX) is a transmembrane enzyme that regulates pH in hypoxic tumors and promotes tumor cell survival. Its expression is associated with the occurrence of metastases and poor prognosis. Here, we present nine derivatives of the cobalt bis­(dicarbollide)(1−) anion substituted at the boron or carbon sites by alkysulfamide group(s) as highly specific and selective inhibitors of CAIX. Interactions of these compounds with the active site of CAIX were explored on the atomic level using protein crystallography. Two selected derivatives display subnanomolar or picomolar inhibition constants and high selectivity for the tumor-specific CAIX over cytosolic isoform CAII. Both derivatives had a time-dependent effect on the growth of multicellular spheroids of HT-29 and HCT116 colorectal cancer cells, facilitated penetration and/or accumulation of doxorubicin into spheroids, and displayed low toxicity and showed promising pharmacokinetics and a significant inhibitory effect on tumor growth in syngenic breast 4T1 and colorectal HT-29 cancer xenotransplants.

Halogenated graphene derivatives are interesting for their outstanding physical and chemical properties. In this paper, we present various methods for the synthesis of brominated graphene derivatives by the bromination of graphite oxides. Graphite oxides, prepared according to either the Hummers or Hofmann method, were brominated using bromine or hydrobromic acid under reflux or in an autoclave at elevated temperatures and pressures. The influence of both graphite oxide precursors on the resulting brominated graphenes was investigated by characterization of the graphenes, which was carried out using various techniques, including SEM, SEM-EDS, high-resolution XPS, FTIR, STA and Raman spectroscopy. In addition, the resistivity of the brominated graphenes was measured and the electrochemical properties were investigated by cyclic voltammetry. Although the brominated graphenes were structurally similar, they had remarkably different bromine concentrations. The most highly brominated graphene (bromine concentration above 26 wt%) exhibited a C/O ratio above 44 and partial hydrogenation. Brominated graphenes with such properties could be used for reversible bromine storage or as a starting material for further chemical modifications.

Photoactivated micromachines are at the forefront of the micro-and nanomotors field, as light is the main power source of many biological systems. Currently, this rapidly developing field is based on metal-containing segments, typically TiO 2 and precious metals. Herein, we present metal-free tubular micromotors solely based on graphitic carbon nitride, as highly scalable and low-cost micromachines that can be actuated by turning on/off the light source. These micromotors are able to move by a photocatalytic-induced bubble-propelled mechanism under visible light irradiation, without any metal-containing part or biochemical molecule on their structure. Furthermore, they exhibit interesting properties, such as a translucent tubular structure that allows the optical visualization of the O 2 bubble formation and migration inside the microtubes, as well as inherent fluorescence and adsorptive capability. Such properties were exploited for the removal of a heavy metal from contaminated water with the concomitant optical monitoring of its adsorption by fluorescence quenching. This multifunctional approach contributes to the development of metal-free bubble-propelled tubular micromotors actuated under visible light irradiation for environmental applications.

Graphene and its derivatives have been reported in many articles as “metal-free” carbon electrocatalytic materials. Its synthesis procedures are generally based on the chemical oxidation of graphite and subsequent thermal or chemical reduction. Because graphene oxide has a large surface area and typically contains a variety of oxygen functionalities, metallic ions (impurities) from reaction mixtures can be adsorbed on its surface. These impurities can significantly enhance the electrocatalytic activity and thus lead to data misinterpretation; such impure samples are referred to as “metal-free” catalysts. In this paper, we report the synthesis of impurity-free graphene, which is compared with graphene prepared by standard methods based on the thermal and chemical reduction of two graphene oxides. Detailed analysis of graphene prepared by standard methods shows a direct relation between metallic impurities and the electrocatalytic activity of graphene. In contrast, impurity-free graphene exhibits poor electrocatalytic activity.

Self-propelled micromachines have recently attracted attention for environmental remediation, yet their use for radioactive waste management has not been addressed. Engineered micromotors that are able to combine highly adsorptive capabilities together with fast autonomous motion in liquid media are promising tools for the removal of nuclear waste, which is one of the most difficult types to manage. Herein, we fabricate self-propelled micromotors based on metal–organic frameworks (MOFs) via template-based interfacial synthesis and show their potential for efficient removal of radioactive uranium. A crucial challenge of the MOF-based motors is their stability in the presence of fuel (hydrogen peroxide) and acidic media. We have ensured their structural stability by Fe doping of zeolitic imidazolate framework-8 (ZIF-8). The implementation of magnetic ferroferric oxide nanoparticles (Fe3O4 NPs) and catalytic platinum nanoparticles (Pt NPs) results in the magnetically responsive and bubble-propelled micromotors. In the presence of 5 wt % H2O2, these micromotors are propelled at a high speed of ca. 860 ± 230 μm·s–1 (i.e., >60 body lengths per second), which is significantly faster than that of other microrod-based motors in the literature. These micromotors demonstrate a highly efficient removal of uranium (96%) from aqueous solution within 1 h, with the subsequent recovery under magnetic control, as well as stable recycling ability and high selectivity. Such self-propelled magnetically recoverable micromotors could find a role in the management and remediation of radioactive waste.

Water-soluble highly fluorinated graphite oxide is a promising candidate for applications in biosensing and for fluorescent probes due to its variable fluorescence properties. We report on a simple process for the preparation of a fluorinated graphite oxide (FGO). This process is based on fluorination of graphite oxide (GO) in a fluorine atmosphere at an elevated temperature and pressure. We used two different GO precursors, which were prepared by Staudenmaier and Hummers methods. The method of GO synthesis has a strong influence on the concentration of fluorine in the obtained product. The mechanism of GO fluorination is associated with the presence of reactive groups, mostly epoxides, and is accompanied by etching of graphite oxide. Our analyses highlighted that the FGO prepared by Hummers method contains a significantly higher amount of bounded fluorine and can be used as a starting material for the synthesis of chemically reduced fluorine doped graphene. Water soluble fluorinated graphene can be easily processed in aqueous solutions to create hydrophilic particles and films with tunable fluorescence properties. Experimental sectionGraphite oxides were prepared, similarly to Staudenmaier method 21 and Hummers 22 method, from pure graphite microparticles (2-15 mm, 99.9995%, from Alfa Aesar). Sulfuric acid