Covalent-Bonded Reduced Graphene Oxide-Fluorescein Complex as a Substrate for Extrinsic SERS Measurements.

When graphene is used as SERS substrates, it contributes to the chemical mechanism (CM) of enhancement of Raman signal, owing to which the detection limit is very low (lower than mM content of probe molecules). The CM of enhancement depends largely on the interactions between the substrate and the probe molecules. Therefore, in this work, we have investigated the possibility of increasing the SERS activity of graphene by improving the interaction between the probe molecule and the graphene substrate by establishing exclusively strong covalent bonding between them. Fluorescein (Fl) was selected as a probe molecule because it is one of the most commonly used fluorophore in bioscience. As a graphene substrate, reduced graphene oxide (rGO) platelets were used. In addition, silver nanoparticles (AgNPs) were added onto the hybrids to further increase the enhancement by electromagnetic mechanism. Highly enhanced Raman signal of Fl onto neat rGO was achieved for micromolar concentration of the probe molecules. This was attributed to the covalent bonding between them, which introduced hole doping to rGO, decreasing the Fermi level of rGO and bringing it more closely to the LUMO of Fl. This induces aligning of their energy levels, resulting in higher contribution of the nonresonance effect to the charge transfer mechanism of enhancement, which, in this case, occurred intramolecularly. When AgNPs were added onto the rGO substrate, the expected enhancement performance was not observed. On the one hand, this was attributed to small size (∼20 nm) of AgNPs and lack of aggregates and, on the other, due to the unusually high contribution of CM determined.

Reduced graphene oxide hydrogels and xerogels provide efficient platforms for immobilization and laccase production by Trametes pubescens.

Fungal immobilization is an interesting topic in enzyme production and bioprocess development. The properties of graphene (i.e. large surface area, hydrophobicity), together with the possibility of producing it at low cost and with tailor-made properties, make this popular material worthy of investigation as a support for fungal immobilization. In the present paper, 3D-organized structures of reduced graphene oxide (rGO) in hydrogels and their dried derivatives (xerogels) were synthesized, characterized and investigated as potential supports for the immobilization of the white-rot fungus Trametes pubescens. It was found that the morphology of the hydrogels and xerogels was not influenced by the synthesis conditions; however the 3D structure was preserved after drying and formation of xerogels. Both, hydrogels and xerogels have been shown to be suitable supports for the immobilization of T. pubescens. Additionally, xerogels promoted increased laccase activities and maximum activity values of about 20 ± 1 U/mL were attained. These activities were much higher than those obtained with other well-known inert supports. Nevertheless, no relationship between support morphology and productivity was found. The encouraging results obtained have paved the way for the development of novel graphene-based supports for microorganism immobilization.