Dispersive Solid Phase Extraction of Melatonin with Graphene/Clay Mixtures and Fluorescence Analysis in Surfactant Aqueous Solutions.

In this work, the dispersive solid phase extraction (dSPE) of melatonin using graphene (G) mixtures with sepiolite (SEP) and bentonite (BEN) clays as sorbents combined with fluorescence detection has been investigated. The retention was found to be quantitative for both G/SEP and G/BEN 4/96 and 10/90 w/w mixtures. G/clay 4/96 w/w mixtures were selected to study the desorption process since the retention was weaker, thus leading to easier desorption. MeOH and aqueous solutions of the nonionic surfactant Brij L23 were tested as desorbents. For both clays and an initial sample volume of 25 mL, a percentage of melatonin recovery close to 100% was obtained using 10 or 25 mL of MeOH as desorbent. Further, using a G/SEP mixture, 25 mL as the initial sample volume and 5 mL of MeOH or 60 mM Brij L23 solution as the desorbent, recoveries of 98.3% and 90% were attained, respectively. The whole method was applied to herbal tea samples containing melatonin, and the percentage of agreement with the labeled value was 86.5%. It was also applied to herbal samples without melatonin by spiking them with two concentrations of this compound, leading to recoveries of 100 and 102%.

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.

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.

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.

Comparison of Anionic, Cationic and Nonionic Surfactants as Dispersing Agents for Graphene Based on the Fluorescence of Riboflavin.

Fluorescence quenching is a valuable tool to gain insight about dynamic changes of fluorophores in complex systems. Graphene (G), a single-layered 2D nanomaterial with unique properties, was dispersed in surfactant aqueous solutions of different nature: non-ionic polyoxyethylene-23-lauryl ether (Brij L23), anionic sodium dodecylsulphate (SDS), and cationic hexadecyltrimethylammonium bromide (CTAB) and dodecyltrimethylammonium bromide (DTAB). The influence of the surfactant type, chain length and concentration, G total concentration and G/surfactant weight ratio on the fluorescence intensity of vitamin B2 (riboflavin) was investigated. The quality of the different G dispersions was assessed by scanning and transmission electron microscopies (SEM and TEM). A quenching phenomenon of the fluorescence of riboflavin was found for G dispersions in all the surfactants, which generally becomes stronger with increasing G/surfactant weight ratio. For dispersions in the ionic surfactants, the quenching is more pronounced as the surfactant concentration raises, whilst the non-ionic one remains merely unchanged for the different G/Brij L23 weight ratios. More importantly, results indicate that DTAB solutions are the optimum media for dispersing G sheets, leading to an up to 16-fold drop in the fluorescence intensity. Understanding the mechanism in fluorescence quenching of G dispersions in surfactants could be useful for several optical applications.

Quenching of fluorene fluorescence by single-walled carbon nanotube dispersions with surfactants: application for fluorene quantification in wastewater.

The fluorescence of fluorene in aqueous solutions of surfactants of different natures, anionic sodium dodecylsulphate (SDS), cationic cetyltrimethyl ammonium chloride (CTAC) and non-ionic polyoxyethylene-23-lauryl ether (Brij 35), as well as in single-walled carbon nanotube (SWCNT) dispersions in these surfactants, has been studied and compared. A fluorescence quenching phenomenon has been observed in the presence of SWCNT, the effect being stronger for dispersions in CTAC, related to the improved dispersion capability of this surfactant as revealed by microscopic observations and its stronger adsorption onto the SWCNT surfaces as inferred from the Raman spectra. SWCNT interact with fluorene causing a fluorescence quenching. The fluorescence intensity ratio, calculated in the absence and in the presence of SWCNT, follows the Stern-Volmer equation. For the CTAC concentration that provides the highest quenching effect, the analytical characteristics of the fluorimetric method like sensitivity, detection and quantification limits, repeatability, reproducibility and robustness have been calculated. Results demonstrate that it is possible to determine fluorene in a fortified wastewater sample in aqueous solutions of CTAC and SWCNT/CTAC dispersions, showing recoveries close to 100 %. The quenching effect found in this work could be useful for the development of an optical device that uses SWCNT-based receptors for fluorene detection and quantification in aqueous surfactant solutions. Graphical abstract Distribution of fluorene between single-walled carbon nanotubes and micelles.

Antioxidant, antibacterial and ACE-inhibitory activity of four monofloral honeys in relation to their chemical composition.

Different monofloral honeys from Castilla-La Mancha (Spain) have been studied in order to determine their main functional and biological properties. Thyme honey and chestnut honey possess the highest antioxidant capacity, which is due to their high vitamin C (in thyme honey) and total polyphenolic content (in chestnut honey). On the other hand, chestnut honey showed high antimicrobial activity against Staphylococcus aureus and Escherichia coli, whilst others had no activity against S. aureus and showed very small activity against E. coli. Moreover it was found that the antimicrobial activity measured in chestnut honey was partly due to its lysozyme content. In addition the angiotensin I-converting enzyme (ACE) inhibitory activity was measured, and the ACE inhibition is one mechanism by which antihypertensive activity is exerted in vivo. All the types of honey showed some activity but chestnut honey had the highest ACE inhibitory activity.

Vitamin C and sugar levels as simple markers for discriminating Spanish honey sources.

UNLABELLED: In this work, 7 Spanish honeys with different botanical origins were studied. The honey origins were rosemary, chestnut, lavender, echium, thyme, multifloral, and honeydew. The chemical compounds determined were ascorbic acid (vitamin C), hydroxymethylfurfural, and major sugar contents (glucose and fructose). The physicochemical parameters, pH, conductivity, moisture, free acidity, and color, were also measured. Vitamin C is an important antioxidant in food, and the possibility to use it as discriminate parameter among different honeys was studied. The determination of vitamin C in honey samples was carried out by 2 different methods, volumetric and chromatographic comparing the results by both statistically. Vitamin C content was higher in thyme honeys than in the other types; however a wide dispersion in the values was found. Through a linear discriminant analysis (LDA), conductivity, glucose, fructose, and vitamin C content were the most important discriminant parameters. PRACTICAL APPLICATION: Vitamin C content in different honey sources has been determined by a simple and rapid chromatographic method (less than 3 min) in honeys from 6 botanical origins. The results together with glucose and fructose content and some physicochemical parameters have been studied in order to discriminate the botanical origin of honeys and in the future certified their quality. A statistical LDA was applied to the data, and differentiation of honey sources was possible with very good agreement. The vitamin C content found in thymus honeys was significantly higher than in other types. This fact makes vitamin C a special marker for thymus honeys that have a higher antioxidant effect than the others giving it special properties. The identification of honey sources is essential for beekeepers in order to certify honeys for consumers.