Graphene-Based Sensors for the Detection of Bioactive Compounds: A Review.

Over the last years, different nanomaterials have been investigated to design highly selective and sensitive sensors, reaching nano/picomolar concentrations of biomolecules, which is crucial for medical sciences and the healthcare industry in order to assess physiological and metabolic parameters. The discovery of graphene (G) has unexpectedly impulsed research on developing cost-effective electrode materials owed to its unique physical and chemical properties, including high specific surface area, elevated carrier mobility, exceptional electrical and thermal conductivity, strong stiffness and strength combined with flexibility and optical transparency. G and its derivatives, including graphene oxide (GO) and reduced graphene oxide (rGO), are becoming an important class of nanomaterials in the area of optical and electrochemical sensors. The presence of oxygenated functional groups makes GO nanosheets amphiphilic, facilitating chemical functionalization. G-based nanomaterials can be easily combined with different types of inorganic nanoparticles, including metals and metal oxides, quantum dots, organic polymers, and biomolecules, to yield a wide range of nanocomposites with enhanced sensitivity for sensor applications. This review provides an overview of recent research on G-based nanocomposites for the detection of bioactive compounds, providing insights on the unique advantages offered by G and its derivatives. Their synthesis process, functionalization routes, and main properties are summarized, and the main challenges are also discussed. The antioxidants selected for this review are melatonin, gallic acid, tannic acid, resveratrol, oleuropein, hydroxytyrosol, tocopherol, ascorbic acid, and curcumin. They were chosen owed to their beneficial properties for human health, including antibiotic, antiviral, cardiovascular protector, anticancer, anti-inflammatory, cytoprotective, neuroprotective, antiageing, antidegenerative, and antiallergic capacity. The sensitivity and selectivity of G-based electrochemical and fluorescent sensors are also examined. Finally, the future outlook for the development of G-based sensors for this type of biocompounds is outlined.

Fluorescence study of the influence of centrifugation on graphene oxide dispersions in water and in tannic acid.

Graphene oxide (GO) is acquiring a great interest in biomedicine, biotechnology and biochemistry due to its unique properties. However, GO layers are boundbyvan der Waals forces, which results in aggregation. An efficient dispersion of the aggregated nanostructures is crucial from an application viewpoint, hence eco-friendly procedures are pursued. In this work, the potential of tannic acid (TA) as a GO dispersant in water has been investigated for the first time. Transmission electronic microscopy (TEM) was used to visualize the degree of GO exfoliation in the dispersions. To further assess TA dispersant capability, a fluorescent biomolecule, riboflavin, has been selected. GO and TA cause a quenching effect on riboflavin fluorescence, which depends on the GO and TA concentration, the GO/TA weight ratio and the final centrifugation step that was found to be crucial. Multiple regression analysis has been used to determine the quenching constants for TA and GO simultaneously. The GO-riboflavin interaction weakens upon centrifugation. This step, traditionally used to remove the nanomaterial aggregates, should be avoided to obtain a high GO concentration in the dispersions. This study paves the way towards the use of environmentally friendly dispersant agents instead of conventional organic solvents or synthetic surfactants to attain high-quality dispersions of carbon nanomaterials in water.

Graphene Oxides Derivatives Prepared by an Electrochemical Approach: Correlation between Structure and Properties.

Graphene oxide (GO) can be defined as a single monolayer of graphite with oxygen-containing functionalities such as epoxides, alcohols, and carboxylic acids. It is an interesting alternative to graphene for many applications due to its exceptional properties and feasibility of functionalization. In this study, electrochemically exfoliated graphene oxides (EGOs) with different amounts of surface groups, hence level of oxidation, were prepared by an electrochemical two-stage approach using graphite as raw material. A complete characterization of the EGOs was carried out in order to correlate their surface topography, interlayer spacing, defect content, and specific surface area (SSA) with their electrical, thermal, and mechanical properties. It has been found that the SSA has a direct relationship with the d-spacing. The EGOs electrical resistance decreases with increasing SSA while rises with increasing the D/G band intensity ratio in the Raman spectra, hence the defect content. Their thermal stability under both nitrogen and dry air atmospheres depends on both their oxidation level and defect content. Their macroscopic mechanical properties, namely the Young's modulus and tensile strength, are influenced by the defect content, while no correlation was found with their SSA or interlayer spacing. Young moduli values as high as 54 GPa have been measured, which corroborates that the developed method preserves the integrity of the graphene flakes. Understanding the structure-property relationships in these materials is useful for the design of modified GOs with controllable morphologies and properties for a wide range of applications in electrical/electronic devices.

Physico-Chemically Distinct Nanomaterials Synthesized from Derivates of a Poly(Anhydride) Diversify the Spectrum of Loadable Antibiotics.

Recent advances in the field of nanotechnology such as nanoencapsulation offer new biomedical applications, potentially increasing the scope and efficacy of therapeutic drug delivery. In addition, the discovery and development of novel biocompatible polymers increases the versatility of these encapsulating nanostructures, enabling chemical properties of the cargo and vehicle to be adapted to specific physiological requirements. Here, we evaluate the capacity of various polymeric nanostructures to encapsulate various antibiotics of different classes, with differing chemical structure. Polymers were sourced from two separate derivatives of poly(methyl vinyl ether-alt-maleic anhydride) (PMVE/MA): an acid (PMVE/MA-Ac) and a monoethyl ester (PMVE/MA-Es). Nanoencapsulation of antibiotics was attempted through electrospinning, and nanoparticle synthesis through solvent displacement, for both polymers. Solvent incompatibilities prevented the nanoencapsulation of amikacin, neomycin and ciprofloxacin in PMVE/MA-Es nanofibers. However, all compounds were successfully loaded into PMVE/MA-Es nanoparticles. Encapsulation efficiencies in nanofibers reached approximately 100% in all compatible systems; however, efficiencies varied substantially in nanoparticles systems, depending on the tested compound (14%-69%). Finally, it was confirmed that both these encapsulation processes did not alter the antimicrobial activity of any tested antibiotic against Staphylococcus aureus and Escherichia coli, supporting the viability of these approaches for nanoscale delivery of antibiotics.

Tailorable Synthesis of Highly Oxidized Graphene Oxides via an Environmentally-Friendly Electrochemical Process.

Graphene oxide (GO) is an attractive alternative to graphene for many applications due to its captivating optical, chemical, and electrical characteristics. In this work, GO powders with a different amount of surface groups were synthesized from graphite via an electrochemical two-stage process. Many synthesis conditions were tried to maximize the oxidation level, and comprehensive characterization of the resulting samples was carried out via elemental analysis, microscopies (TEM, SEM, AFM), X-ray diffraction, FT-IR and Raman spectroscopies as well as electrical resistance measurements. SEM and TEM images corroborate that the electrochemical process used herein preserves the integrity of the graphene flakes, enabling to obtain large, uniform and well exfoliated GO sheets. The GOs display a wide range of C/O ratios, determined by the voltage and time of each stage as well as the electrolyte concentration, and an unprecedented minimum C/O value was obtained for the optimal conditions. FT-IR evidences strong intermolecular interactions between neighbouring oxygenated groups. The intensity ratio of D/G bands in the Raman spectra is high for samples prepared using concentrated H2SO4 as an electrolyte, indicative of many defects. Furthermore, these GOs exhibit smaller interlayer spacing than that expected according to their oxygen content, which suggests predominant oxidation on the flake edges. Results point out that the electrical resistance is conditioned mostly by the interlayer distance and not simply by the C/O ratio. The tuning of the oxidation level is useful for the design of GOs with tailorable structural, electrical, optical, mechanical, and thermal properties.