Nanofibrillar biochar from industrial waste as hosting network for transition metal dichalcogenides. Novel sustainable 1D/2D nanocomposites for electrochemical sensing.

Industrial wastes have become elective sustainable sources to obtain materials for electronic/electroanalytical purposes; on the other hand, easy and green strategies to include semiconductor 2D graphene-like materials in conductive networks are highly required. In this work, 1D/2D nanocomposites (NCs) based on nanofibrillar biochar (BH) from paper industry waste and transition metal dichalcogenides (TMDs: MoS2, WS2, MoSe2, and WSe2), were prepared in water via liquid phase exfoliation (LPE) using sodium cholate as bioderived surfactant. The TMD amount in the NCs has been carefully optimized, searching for the best compromise between electron transfer ability and electroanalytical performances. Four different water-dispersed BH-TMD NCs have been selected and comprehensively studied from the electrochemical point of view and morphologically characterized. The BH-TMDs potentiality have been demonstrated in model solutions and real samples towards different analytes of biological and agri-food interest. The most performing NCs have been selected and used for the simultaneous determination of the neurotransmitters dopamine (DP) and serotonin (SR), and the flavonoids quercetin (QR) and rutin (RT), obtaining good linearity (R2 ≥ 0.9956) with limits of detection ranging from 10 to 200 nM. Reproducible quantitative recovery values (90-112%, RSD ≤6%, n = 3) were obtained analyzing simultaneously DP and SR in synthetic biological fluid and drugs, and QR and RT in food supplements, proving the usability of the proposed materials for real analyses. This work proves that BH-nanofibers act as a sustainable conductive hosting network for 2D-TMDs, allowing full exploit their electroanalytical potential. The proposed BH-TMD NCs represent a sustainable, affordable, and captivating opportunity for the electrochemical and (bio)sensoristic field.

Metal nanoparticles based lab-on-paper for phenolic compounds evaluation with no sample pretreatment. Application to extra virgin olive oil samples.

In this work, a low-cost, disposable, and portable lab-on-paper device is proposed to simultaneously quantify total polyphenol content (TPC) and antioxidant capacity (AOC) in 15 min; the assay requires no pre-treatment of the samples. The lab-on-paper device fabrication has been carried out employing a xurography-based benchtop microfabrication technology using low-cost materials as chromatography paper and polymeric sheets. Extra virgin olive oil (EVOO) phenolic compounds' represents a nutritional added value, nevertheless, the high lipidic content hinders their direct and rapid analysis, resulting in an extremely challenging sample. The realized lab-on-paper allows to perform the dual TPC and AOC determination in three simple steps: (i) sample loading, (ii) analytes transport to the analysis spot, and (iii) double colorimetric analysis exploiting the growth of AuNPs and AgNPs on paper mediated by phenolic compounds. Signal acquisition is achieved using a standard digital camera. The dual colorimetric assay is able to detect phenolic compounds in the 25-500 mg L-1 range with limits of detection ≤6 mg L-1 and good reproducibility (RSDs ≤11%). Direct analysis of EVOO samples (n = 30) correlated well (r > 0.92) with conventional spectrophotometric methods for TPC and AOC determination.

Effect of phenolic compounds-capped AgNPs on growth inhibition of Aspergillus niger.

An exponential increase of scientific works dealing with the use of polyphenol-rich 'natural products' for the synthesis of bioactive AgNPs is in progress. However, a lack of fundamental studies on phytochemical compounds involved, and their role is evident. In this work, a comprehensive study of the antifungal performances of silver nanoparticles (AgNPs) synthesized exclusively with phenolic compounds (PCs) with different structures and different antioxidant capacity is presented. The experimental hypothesis is that AgNPs@PCs produced with different PCs can exert different toxicity. In particular, di-hydroxylic and tri-hydroxylic phenolic acids (caffeic acid and gallic acid) and flavonoids (catechin and myricetin) were compared. A room temperature rapid and simple AgNPs synthesis was carefully optimized, obtaining stable and reproducible colloids. AgNPs@PCs suspensions were characterized by UV-vis spectroscopy, ς-potential, dynamic light scattering and transmission electron microscopy. AgNPs@PCs radical scavenging capacity was also assessed. Finally, the AgNPs@PCs antifungal effect was tested against Aspergillus niger, particularly on spore germination and mycelial growth. The different antifungal activity was attributed to the different PCs' ability to generate/stabilize AgNPs with different shells, residual antioxidant capacity, and capacity to interact and aggregate during their 'attack' to A. niger hyphae. This work paves the way for the rational use of PCs and PCs rich-products for AgNPs-based applications.

Colorimetric determination of polyphenols via a gold nanoseeds-decorated polydopamine film.

A polystyrene ELISA plate (EP) modified with a thin film based on gold nanoseeds (AuSDs) assembled onto polydopamine (PDA) is proposed. The nanodecorated film (PDA@AuSD) allows to evaluate the polyphenols antioxidant capacity (AOC) through a colorimetric approach based on a seed-mediated growth strategy. Polyphenols, in the presence of the nanodecorated (PDA@AuSD) surfaces are able to drive an increase in size of the AuSDs according to their AOC; this produces an increase of the localized surface plasmon resonance (LSPR; maximum at λ ~ 550 nm) that is taken as analytical signal. The PDA@AuSD EP manufacturing shows good intraplates repeatability (RSD ≤ 6.6%, n = 96 wells) and interplates reproducibility (RSD ≤ 7.4%, n = 748 wells), resulting stable for 1 year. The AuSDs growth kinetic has been studied using 11 polyphenols belonging to different chemical classes and 4 different food samples. The PDA@AuSD film is able to return quantitative information on the AOC of food polyphenols. Good repeatability (RSD ≤ 5.7%, n = 12 EP wells) and reproducibility (RSD ≤ 8.1%, n = 12 EP wells) was achieved, with acceptable linear correlation coefficients (R2 ≥ 0.990) and useful limits of detection (LODs ≤ 2.5 10-5 mol L-1). The samples analyzed with the PDA@AuSD device have been successfully ordered according to their AOC in agreement with conventional optical methods. The PDA@AuSD plate allows multiple measurements (96 wells per EP) with a one-step strategy, overcoming the limitations related to the use of colloidal nanoparticles; in addition, since absorbance is measured after washing, it is not affected by sample color or turbidity. Graphical abstract Schematic representation of ELISA plate (EP) modified with polydopamine (PDA) film decorated with gold nanoseeds (AuSD). The colorimetric assay, to evaluate the antioxidant capacity, is based on the AuSD growth mediated by polyphenols, resulting in absorbance increase at 550 nm (ΔAbs550), which is employed as analytical signal.

Silver and gold nanoparticles based colorimetric assays for the determination of sugars and polyphenols in apples.

In this work, the exploitability of rapid and easy to use methods for the evaluation of the antioxidant capacity (AOC) and sugars content (SC), through metal nanoparticles (MNPs) formation, has been proved and applied to apples. In particular, an AgNPs-based sugar quantification assays and an AuNPs-based polyphenols antioxidant capacity assay have been used as tools for the evaluation of apple extracts composition. Both assays are based on the ability of the analytes (sugars and polyphenols) to reduce the source of metal (Au3+ and Ag+), stabilizing, at the same time, the resulting MNPs colloidal suspensions. The AuNPs and AgNPs formation depends on the analyte structure and concentration, resulting in red (AuNPs) and yellow (AgNPs) colored suspensions. Both assays require an initial mixing step, followed by MNPs formation under mild conditions (10 min, room temperature or 45 °C), and the colorimetric response is easily acquired at a fixed wavelength (AgNPs: 430 nm and AuNPs: 540 nm). The analytical performance of both assays has been proven, obtaining good reproducibility (RSD ≤ 6%,), sensitivity (LODs ≤8.7 µmol L-1) and recoveries (91% -113.7%). The produced MNPs (AgNPs and AuNPs) have been characterized using UV-Vis spectroscopy and TEM, and the cross-reactivity between assays, as well as the possible endogenous interferents, studied. The assays have been tested on 42 apple samples, and the data obtained compared with those obtained by conventional methods (i.e. FC, ABTS, and ion chromatography). The proposed AgNPs-sugars assay gives results comparable (R = 0.915) to those determined by ion chromatography in terms of total sugars, and the AuNPs-polyphenols assay results able to assess the polyphenols antioxidant capacity, being correlated with those obtained by the ABTS method (R = 0.922). This MNPs-based approach demonstrated to be an excellent tool for rapid and facile analysis of sugars and polyphenols in apple samples.

Simple and rapid silver nanoparticles based antioxidant capacity assays: Reactivity study for phenolic compounds.

A single-step, rapid (10 min), sensitive silver nanoparticles (AgNPs) based spectrophotometric method for antioxidant capacity (AOC) assay has been developed. The assay is based on the ability of natural polyphenols to reduce Ag(I) and stabilize the produced AgNPs(0) at room temperature. Localized surface plasmon resonance (LSPR) of AgNPs at ≈420 nm is then measured. Using different conditions of pH (8.4) and temperature (45 °C) a further assay based on the production of AgNPs with selectivity for flavonols was also developed. The reactivity of the two AgNPs based assays vs. 15 polyphenols belonging to different chemical classes and 9 different samples has been studied and compared with ABTS, Folin and AuNPs based methods for AOC. The proposed assays had good reproducibility (RSD ≤ 13) and are simple, sensitive and cost effective. Moreover, used in conjunction with the classical AOC assays, can improve the information on the polyphenolic pool of food samples.