The continuous decrease in the availability of fossil resources, along with an evident energy crisis, and the growing environmental impact due to their use, has pushed scientific research towards the development of innovative strategies and green routes for the use of renewable resources, not only in the field of energy production but also for the production of novel advanced materials and platform molecules for the modern chemical industry. A new class of promising carbon nanomaterials, especially graphene quantum dots (GQDs), due to their exceptional chemical-physical features, have been studied in many applications, such as biosensors, solar cells, electrochemical devices, optical sensors, and rechargeable batteries. Therefore, this review focuses on recent results in GQDs synthesis by green, easy, and low-cost synthetic processes from eco-friendly raw materials and biomass-waste. Significant advances in recent years on promising recent applications in the field of electrochemical sensors, have also been discussed. Finally, challenges and future perspectives with possible research directions in the topic are briefly summarized.
The timely diagnosis of cancer represents the best chance to increase treatment success and to reduce cancer deaths. Nanomaterials-based biosensors containing graphene quantum dots (GQDs) as a sensing platform show great promise in the early and sensitive detection of cancer biomarkers, due to their unique chemical and physical properties, large surface area and ease of functionalization with different biomolecules able to recognize relevant cancer biomarkers. In this review, we report different advanced strategies for the synthesis and functionalization of GQDs with different agents able to selectively recognize and convert into a signal specific cancer biomarkers such as antigens, enzymes, hormones, proteins, cancer related byproducts, biomolecules exposed on the surface of cancer cells and changes in pH. The developed optical, electrochemical and chemiluminescent biosensors based on GQDs have been shown to ensure the effective diagnosis of several cancer diseases as well as the possibility to evaluate the effectiveness of anticancer therapy. The wide linear range of detection and low detection limits recorded for most of the reported biosensors highlight their great potential in clinics for the diagnosis and management of cancer.
A novel bidentate Schiff base (L) is here proposed for the detection of Zn ions in water. The structure of the synthesized Schiff base L was characterized by FT-IR, 1H NMR and 13C NMR. Optical characteristics were addressed by UV-Visible spectroscopy and Photoluminescence (PL) measurements. PL demonstrated that L displays a “turn-off” type fluorescence quenching in the presence of Zn2+ ion in aqueous solution, indicating its ability to preferentially coordinate this ion. Based on these findings, an L-M (where M is a suitable membrane) modified screen-printed carbon electrode (SPCE) was developed to evaluate the electrochemical behavior of the Schiff base (L) with the final objective of undertaking the electroanalytical determination of Zn ions in water. Using various electrochemical techniques, the modified L-M/SPCE sensor demonstrates high sensitivity and selectivity to Zn ions over some common interferents ions, such as Ca2+, Mg2+, K+, Ni++ and Cd++. The potentiometric response of the L-M/SPCE sensor to Zn ions was found to be linear over a relatively wide concentration range from 1 μM to 100 mM.
The concentration of sodium and potassium ions in biological fluids, such as blood, urine and sweat, is indicative of several basic body function conditions. Therefore, the development of simple methods able to detect these alkaline ions is of outmost importance. In this study, we explored the electrochemical and optical properties of graphene quantum dots (GQDs) combined with the selective chelating ability of the crown ethers 15-crown-5 and 18-crown-6, with the final aim to propose novel composites for the effective detection of these ions. The results obtained comparing the performances of the single GQDs and crown ethers with those of the GQDs-15-crown-5 and GQDs-18-crown-6 composites, have demonstrated the superior properties of these latter. Electrochemical investigation showed that the GQDs based composites can be exploited for the potentiometric detection of Na+ and K+ ions, but selectivity still remains a concern. The nanocomposites showed the characteristic fluorescence emissions of GQDs and crown ethers. The GQDs-18-crown-6 composite exhibited ratiometric fluorescence emission behavior with the variation of K+ concentration, demonstrating its promising properties for the development of a selective fluorescent method for potassium determination.
Cancer-targeted drug delivery systems (DDS) based on carbon nanostructures have shown great promise in cancer therapy due to their ability to selectively recognize specific receptors overexpressed in cancer cells. In this paper, we have explored a green route to synthesize nanobiochar (NBC) endowed with graphene structure from the hydrothermal carbonization (HTC) of orange peels and evaluated the suitability of this nanomaterial as a nanoplatform for cancer therapy. In order to compare the cancer-targeting ability of different widely used targeting ligands (TL), we have conjugated NBC with biotin, riboflavin, folic acid and hyaluronic acid and have tested, in vitro, their biocompatibility and uptake ability towards a human alveolar cancer cell line (A549 cells). The nanosystems which showed the best biological performances—namely, the biotin- and riboflavin- conjugated systems—have been loaded with the poorly water-soluble drug DHF (5,5-dimethyl-6a-phenyl-3-(trimethylsilyl)-6,6a-dihydrofuro[3,2-b]furan-2(5H)-one) and tested for their anticancer activity. The in vitro biological tests demonstrated the ability of both systems to internalize the drug in A549 cells. In particular, the biotin-functionalized NBC caused cell death percentages to more than double with respect to the drug alone. The reported results also highlight the positive effect of the presence of oxygen-containing functional groups, present on the NBC surface, to improve the water dispersion stability of the DDS and thus make the approach of using this nanomaterial as nanocarrier for poorly water-soluble drugs effective.