This paper demonstrated for the first time a simple wet-chemical strategy for synthesizing hemin-graphene hybrid nanosheets (H-GNs) through the π-π interactions. Significantly, this new material possesses the advantages of both hemin and graphene and exhibits three interesting properties. First, H-GNs have intrinsic peroxidase-like activity, which can catalyze the reaction of peroxidase substrate, due to the existence of hemin on the graphene surface. Second, their dispersion follow the 2D Schulze-Hardy rule, that is to say, the coagulation of H-GNs in electrolyte solution results from the interplay between van der Waals attraction and electric double-layer repulsion. Third, H-GNs exhibit the ability to differentiate ss- and ds-DNA in optimum electrolyte concentration, owing to the different affinities of ss- and ds-DNA to the H-GNs. On the basis of these unique properties of the as-prepared H-GNs, we have developed a label-free colorimetric detection system for single-nucleotide polymorphisms (SNPs) in disease-associated DNA. To our knowledge, this is the first report concerning on SNPs detection using functionalized graphene nanosheets. Owing to its easy operation and high specificity, it was expected that the proposed procedure might hold great promise in the pathogenic diagnosis and genetic diseases.

Cyclodextrins (CDs) are oligosaccharides composed of six, seven, or eight glucose units (alpha-, beta-, or gamma-CD, respectively), which are toroidal in shape with a hydrophobic inner cavity and a hydrophilic exterior. These interesting characteristics can enable them to bind selectively various organic, inorganic and biological guest molecules into their cavities to form stable host-guest inclusion complexes or nanostructured supramolecular assemblies in their hydrophobic cavity. On the other hand graphene nanosheet (GN), a rising-star material, holds great promise for potential applications in many technological fields due to its high surface areas, low cost, and high conductivity. If GNs are modified with CDs, it is possible to obtain new materials simultaneously possessing unique properties of GNs and cyclodextrins through combining their individual obvious advantages. In this article, we demonstrate for the first time a simple wet-chemical strategy for the preparation of CD-graphene organic-inorganic hybrid nanosheets (CD-GNs), which exhibited high solubility and stability in polar solvent. The obtained CD-GNs were characterized by UV-vis spectroscopy, static contact angle measurement, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy, and electrochemical impedance spectroscopy, which confirmed that CD had been effectively functionalized on the surface of GNs. Furthermore, the formation mechanism of CD-GNs was also discussed. Interestingly, GNs here could load a number of CD molecules, which was very important for greatly enhancing the supramolecular function of CDs. Electrochemical results obviously reveal that CD-graphene organic-inorganic hybrid nanosheets could exhibit very high supramolecular recognition and enrichment capability and show much higher electrochemical response toward eight probe molecules (biomolecules and drugs) than unmodified GNs and carbon nanotubes, which is probably caused by the synergetic effects from GNs (high conductivity and high surface area) and CD molecules (host-guest recognition and enrichment).

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A facile strategy for the preparation of meso-terakis(4-methoxyl-3-sulfonatophenyl) porphyrin (T(4-Mop)PS 4 )-graphene hybrid nanosheets (TGHNs) was demonstrated for the first time, which combines the features of both graphene (high conductivity and large specific surface area) and porphyrins (photochemical electron-transfer ability and excellent electrochemical activity). The as-obtained TGHNs were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy and cyclic voltammetry, which confirmed that the porphyrin had been effectively functionalized on the surface of graphene. Combined with the high affinity and specificity of an aptamer, a simple, rapid, sensitive and label-free electrochemical aptasensor was successfully fabricated for adenosine triphosphate (ATP) detection. The proposed TGHN-based aptasensor achieved the direct electron transfer of porphyrin and showed good affinity and specificity towards ATP, which avoided interference such as the introduction of labeled-substances and the [Fe(CN) 6 ] 3À/4À probe. The preferable linear range for ATP was from 2.2 nM to 1.3 mM (R ¼ 0.9982) with a detection limit of 0.7 nM.