In Vitro Assessment of the Physiologically Relevant Oral Bioaccessibility of Metallic Elements in Edible Herbs Using the Unified Bioaccessibility Protocol.

In this work, the total content of seven metallic elements (Fe, Cu, Zn, Mg, Pb, Ni, and Co) in common edible herbs was determined and related to their bioaccessibility by an in vitro human digestion model. Specifically, the unified bioaccessibility protocol developed by the BioAccessibility Research Group of Europe (BARGE) was used to determine the release of each element during gastric and gastrointestinal digestion. The results show that Fe, Zn, and Mg are released during gastric digestion (34-57% Fe, 28-80% Zn, 79-95% Mg), but their overall bioaccessibility is reduced in the gastrointestinal tract (<30%). On the contrary, Cu is more bioaccessible during gastrointestinal digestion (38-60%). Pb, Ni, and Co exhibited similar bioaccessibility in both gastric and gastrointestinal fluids. Principle component analysis of the data shows that the classification of the nutritional value of herbs differs between the total and the gastrointestinal concentration, suggesting that the total concentration alone is not an adequate indicator for drawing secure conclusions concerning the nutritional benefits of edible plant species.

Development of a sequential extraction and speciation procedure for assessing the mobility and fractionation of metal nanoparticles in soils.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

Determination of silver nanoparticles by atomic absorption spectrometry after dispersive suspended microextraction followed by oxidative dissolution back-extraction.

This study presents a liquid phase microextraction method for the quantification of silver nanoparticles (AgNPs) in environmental samples by means of directly suspended microextraction and atomic absorption spectrometry. The method is based on the dispersion of octanol into fine droplets where AgNPs are partitioned and extracted from the bulk aqueous phase. Then octanol is re-dispersed again in a strongly acidic and oxidizing aqueous medium in order to selectively decompose AgNPs to silver ions. The aqueous extract is then analyzed by atomic absorption spectrometry. Under the working conditions, the method offers high selectivity for AgNPs since most nanoparticle species cannot be extracted into the octanol phase, while the selective back-extraction procedure ensures that only AgNPs are dissolved to the final extract medium. The method works equally well for AgNPs of different size and coatings, thus enabling the determination of the total concentration AgNPs in real samples. Method application in different water samples was used to evaluate the utility of the method in the analysis of real samples of variable complexity with satisfactory results in terms of detection limit (less than 100 femto-mole of AgNPs), recoveries (90-104%) and reproducibility (lower than 7%).

Intrinsic peroxidase-like activity of rhodium nanoparticles, and their application to the colorimetric determination of hydrogen peroxide and glucose.

The intrinsic peroxidase-like activity of rhodium nanoparticles (RhNPs) and their use as catalytic labels for sensitive colorimetric assays is presented. RhNPs catalyze the oxidation of the peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue reaction product with a maximum absorbance at 652 nm. Kinetic studies show catalysis to follow Michaelis-Menten kinetics and a "ping-pong" mechanism. The calculated kinetic parameters indicate high affinity of RhNPs for both the substrate TMB and H2O2. In fact, they are better than other peroxidase mimicking nanomaterials and even the natural enzyme horseradish peroxidase. On the other hand, RhNPs exhibit no reactivity towards saccharides, thiols, amino acids and ascorbic acid. Based on these findings, a sensitive and selective colorimetric method was worked out for the determination of H2O2 in real samples with a linear response in the 1-100 µM concentration range. By employing glucose oxidase, the glucose assay has a linear range that covers the 5 to 125 µM glucose concentration range. The detection limits are <0.75 µM for both species. The methods were applied to the determination of H2O2 in spiked pharmaceutical formulations, and of glucose in soft drinks and blood plasma. Figures of merit include (a) good accuracy (with errors of <6%), (b) high recoveries (96.5-103.7%), and (c) satisfactory reproducibility (<6.3%). Graphical abstract Rhodium nanoparticles catalyze the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue reaction product. The effect is exploited in photometric assays for hydrogen peroxide and glucose.

In-situ suspended aggregate microextraction of gold nanoparticles from water samples and determination by electrothermal atomic absorption spectrometry.

This work describes a new method for the extraction and determination of gold nanoparticles in environmental samples by means of in-situ suspended aggregate microextraction and electrothermal atomic absorption spectrometry. The method relies on the in-situ formation of a supramolecular aggregate phase through ion-association between a cationic surfactant and a benzene sulfonic acid derivative. Gold nanoparticles are physically entrapped into the aggregate phase which is separated from the bulk aqueous solution by vacuum filtration on the surface of a cellulose filter in the form of a thin film. The film is removed from the filter surface and is dissociated into an acidified methanolic solution which is used for analysis. Under the optimized experimental conditions, gold nanoparticles can be efficiently extracted from water samples with recovery rates between 81.0-93.3%, precision 5.4-12.0% and detection limits as low as 75femtomolL(-1) using only 20mL of sample volume. The satisfactory analytical features of the method along with the simplicity indicate the efficiency of this new approach to adequately collect and extract gold nanoparticle species from water samples.

Paper-based assay of antioxidant activity using analyte-mediated on-paper nucleation of gold nanoparticles as colorimetric probes.

With the increasing interest in the health benefits arising from the consumption of dietary products rich in antioxidants, there exists a clear demand for easy-to-use and cost-effective tests that can be used for the identification of the antioxidant power of food products. Paper-based analytical devices constitute a remarkable platform for such expedient and low-cost assays with minimal external resources but efforts in this direction are still scarce. In this work we introduce a new paper-based device in the form of a sensor patch that enables the determination of antioxidant activity through analyte-driven on-paper formation of gold nanoparticles. The principle of detection capitalizes, for the first time, on the on-paper nucleation of gold ions to its respective nanoparticles, upon reduction by antioxidant compounds present in an aqueous sample. The ensuing chromatic transitions, induced on the paper surface, are used as an optical "signature" of the antioxidant strength of the solution. The response of the paper-based sensor was evaluated against a large variety of antioxidant species and the respective dose response curves were constructed. On the basis of these data, the contribution of each species according to its chemical structure was elucidated. For the analysis of real samples, a concentration-dependent colorimetric response was established against Gallic acid equivalents over a linear range of 10 µM-1.0 mM, with detection limits at the low and ultra-low µM levels (i.e. <1.0 µM) and satisfactory precision (RSD=3.6-12.6%). The sensor has been tested for the assessment of antioxidant activity in real samples (teas and wines) and the results correlated well with commonly used antioxidant detection methods. Importantly, the sensor performed favorably for long periods of time when stored at moisture-free and low temperature conditions without losing its activity thus posing as an attractive alternative to the assessment of antioxidant activity without specialized equipment. The use of the sensor by non-experts for a rapid assessment of natural products in field testing is envisioned. Importantly, we demonstrate for the first time that analyte-mediated growth of nanomaterials directly on the paper surface could open new opportunities in paper-based analytical devices.