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.

Fluorescence Study of Riboflavin Interactions with Graphene Dispersed in Bioactive Tannic Acid.

The potential of tannic acid (TA) as a dispersing agent for graphene (G) in aqueous solutions and its interaction with riboflavin have been studied under different experimental conditions. TA induces quenching of riboflavin fluorescence, and the effect is stronger with increasing TA concentration, due to π-π interactions through the aromatic rings, and hydrogen bonding interactions between the hydroxyl moieties of both compounds. The influence of TA concentration, the pH, and the G/TA weight ratio on the quenching magnitude, have been studied. At a pH of 4.1, G dispersed in TA hardly influences the riboflavin fluorescence, while at a pH of 7.1, the nanomaterial interacts with riboflavin, causing an additional quenching to that produced by TA. When TA concentration is kept constant, quenching of G on riboflavin fluorescence depends on both the G/TA weight ratio and the TA concentration. The fluorescence attenuation is stronger for dispersions with the lowest G/TA ratios, since TA is the main contributor to the quenching effect. Data obey the Stern-Volmer relationship up to TA 2.0 g L-1 and G 20 mg L-1. Results demonstrate that TA is an effective dispersant for graphene-based nanomaterials in liquid medium and a green alternative to conventional surfactants and synthetic polymers for the determination of biomolecules.

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.

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.

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.

Impact of recovery correction or subjecting calibrators to sample preparation on measurement uncertainty: PAH determinations in waters.

The decision on the fitness of a measurement for its intended use and the interpretation of an analytical result requires the assessment of the measurement uncertainty. Frequently, the determination of analytes in complex matrices involves demanding sample preparations in which analyte losses are observed. These losses should be considered when reporting the results, which can be corrected for low recovery by taking the mean recovery observed in the analysis of reference items (e.g. spiked samples) or, alternatively, by subjecting calibrators to the same pre-treatment performed on the samples. In these cases, neat (NC) or adjusted (AC) calibrators are used, respectively. The way analyte losses are handled impacts on the measurement uncertainty. The top-down evaluation of the measurement uncertainty involves combining precision, trueness and additional uncertainty components. The trueness component is quantified by pooling various analyte recovery determinations. This work assesses and compares the uncertainty of polycyclic aromatic hydrocarbons (PAHs) measurements in water based on HPLC-FD calibrations with NC or AC. The trueness component is estimated by pooling mean recoveries observed from the analysis of different spiked samples to which mean recovery uncertainty and degrees of freedom are used to estimate a weighted mean recovery and respective uncertainty. The performance of measurements based on NC and AC are associated with equivalent uncertainty except when large analyte losses are observed, namely in the determination of Naphtalene. In this case, the processing of AC reduces the expanded relative uncertainty from 9.9% to 3.5%. The evaluated expanded uncertainty ranged from 3.5% to 12% of the measured value.

Graphene/sepiolite mixtures as dispersive solid-phase extraction sorbents for the anaysis of polycyclic aromatic hydrocarbons in wastewater using surfactant aqueous solutions for desorption.

Different graphene/sepiolite (G/Sep) solid mixtures have been prepared and tested as nanometric sorbents for the analysis of polycyclic aromatic hydrocarbons (PAHs) using dispersive solid phase extraction (dSPE) and aqueous solutions of surfactants as environmentally friendly agents for desorption. Quantification of the PAHs was carried out by reversed-phase liquid chromatography (RP-HPLC) with fluorescence detection. The adsorption of four PAHs with increasing number of benzene rings into a G/Sep mixture (2/98, w/w) was investigated. A 100% retention was attained for phenanthrene (Phe), pyrene (Pyr) and benzo(a)pyrene (BaP), while for naphthalene (Nap) the maximum retention was close to 75%. The G/Sep mixtures can be used to remove the PAHs from wastewater. The desorption step was carried out using an aqueous surfactant solution: 100 mM non-ionic polyoxiethylen-23-lauryl eter (Brij L23). Considering the whole extraction process, the highest PAH recoveries (50, 92, 83 and 76% for Nap, Phe, Pyr and BaP, respectively) were obtained using 100 mM Brij L23. The developed method shows very high sensitivity, robustness and precision, as well as low limits of detection and quantification, and has been successfully applied to the analysis of PAHs in wastewater samples.

Influence of surfactants of different nature and chain length on the morphology, thermal stability and sheet resistance of graphene.

The effects of surfactants of different nature (anionic, cationic and non-ionic) and chain length on the morphology, microstructure, thermal stability and electrical resistivity of liquid exfoliated graphene (G) were investigated. Microscopic (SEM and AFM) observations revealed that the thickness of G in the dispersions depended on the surfactant nature: non-ionic surfactants rendered the highest level of exfoliation, whilst dispersions in the cationic ones exhibited fully-covered thicker sheets; the flake thickness increased with increasing surfactant chain length. X-ray diffraction studies indicated an increased interlamellar G spacing with increasing surfactant content. Raman spectra showed an increase in the ID/IG ratio with decreasing G loading. Larger upshifts of the G, 2D and D + G bands were found with increasing surfactant concentration, particularly for dispersions in the cationic surfactants. For the same G/surfactant weight ratio, the electrical resistivity of the dispersions followed the order: cationic > non-ionic > anionic, consistent with the amount of surfactant adsorbed onto G calculated via TGA. It is demonstrated herein that the thermal and electrical properties of liquid exfoliated G can be tuned by varying the surfactant concentration, nature and chain length, which is of great importance for numerous applications like solar power harvesting, high-temperature devices and flexible nanoelectronics.

Effect of Graphene Flakes Modified by Dispersion in Surfactant Solutions on the Fluorescence Behaviour of Pyridoxine.

The influence of graphene (G) dispersions in different types of surfactants (anionic, non-ionic, and cationic) on the fluorescence of vitamin B6 (pyridoxine) was studied. Scanning electron microscopy (SEM) was used to evaluate the quality of the G dispersions via measuring their flake thickness. The effect of surfactant type and concentration on the fluorescence intensity was analyzed, and fluorescence quenching effects were found for all of the systems. These turn out to be more intense with increasing both surfactant and G concentrations, albeit they do not depend on the G/surfactant weight ratio. For the same G concentration, the magnitude of the quenching follows the order: cationic > non-ionic ≥ anionic. The cationic surfactants, which strongly adsorb onto G via electrostatic attraction, are the most effective dispersing agents and they enable a stronger interaction with the zwitterionic form of the vitamin; the dispersing power improves with increasing the surfactant chain length. The fit of the experimental data to the Stern-Volmer equation suggests either a static or dynamic quenching mechanism for the dispersions in non-ionic surfactants, while those in ionic surfactants show a combined mechanism. The results that were obtained herein have been compared to those that were reported earlier for the quenching of another vitamin, riboflavin, to elucidate how the change in the vitamin structure influences the interactions with G in the surfactant dispersions.