Enhanced Electron Transfer Efficiency of Fructose Dehydrogenase onto Roll-to-Roll Thermal Stamped Laser-Patterned Reduced Graphene Oxide Films.

Herein, a strategy to stamp laser-produced reduced graphene oxide (rGO) onto flexible polymers using only office-grade tools, namely, roll-to-roll thermal stamping, is proposed, proving for the first time its effectiveness for direct bioelectrocatalysis. This straightforward, scalable, and low-cost approach allows us to overcome the limits of the integration of laser-induced rGO-films in bioanalytical devices. Laser-produced rGO has been thermally stamped (TS) onto different polymeric substrates (PET, PVC, and EVA) using a simple roll-laminator; the obtained TS-rGO films have been compared with the native rGO (untransferred) via morphochemical and electrochemical characterization. Particularly, the direct electron transfer (DET) reaction between fructose dehydrogenase (FDH) and TS-rGO transducers has been investigated, with respect to the influence of the amount of enzyme on the catalytic process. Remarkable differences have been observed among TS-rGO transducers; PET proved to be the elective substrate to support the transfer of the laser-induced rGO, allowing the preservation of the morphochemical features of the native material and returning a reduced capacitive current. Noteworthily, TS-rGOs ensure superior electrocatalysis using a very low amount of FDH units (15 mU). Eventually, TS-rGO-based third-generation complete enzymatic biosensors were fabricated via low-cost benchtop technologies. TS-rGOPET exhibited bioanalytical performances superior to the native rGO, allowing a sensitive (0.0289 µA cm-2 µM-1) and reproducible (RSD = 3%, n = 3) d-fructose determination at the nanomolar level (LOD = 0.2 µM). TS-rGO exploitability as a point-of-need device was proved via the monitoring of d-fructose during banana (Musa acuminata) postharvest ripening, returning accurate (recoveries 110-90%; relative error -13/+1%) and reproducible (RSD ≤ 7%; n = 3) data.

Ecotoxicological assessment of water phase exfoliated two-dimensional Group-VI transition metal dichalcogenides using zebrafish embryo model.

Among emerging layered materials, 2D transition metal dichalcogenides (TMDs) nanosheets (n-sheets) have received increasing attention for optoelectronics, energy storage, and, recently, for bioremediation and advanced biomedical applications; however, a lack of ecotoxicological in vivo studies is evident. Herein, for the first time, the potential nanotoxicity of liquid phase exfoliated Group VI TMDs n-sheets (MoS2, WS2, WSe2, and MoSe2) was comparatively investigated using zebrafish embryos (Z-EBs) as an in-vivo model. The 2D n-sheets were produced directly in aqueous-medium, the obtained n-sheets were characterized by scanning electron microscopy, Raman and visible spectroscopy, and their potential nanotoxicity was investigated by fish embryo test OECD TG 236. Chorionated and dechorionated embryos were used to assess the severity of TMD exposure. The survival rate, sublethal alteration during embryogenesis, hatching rate, and mortality were evaluated. TMDs n-sheets tend to adhere to the Z-EBs surface depending on their chemistry. Despite this, TMDs did not show lethal effects; weak sublethal effects were found for MoS2 and WSe2, while slight hatching delays were registered for MoSe2 and WSe2. The observed effects are attributable to the TMDs' tendency to interact with Z-EBs, because of the different chemistry. This work demonstrates how water-dispersed TMDs are potential eco/biocompatible materials.

Lab-made flexible third-generation fructose biosensors based on 0D-nanostructured transducers.

Herein, we report a scalable benchtop electrode fabrication method to produce highly sensitive and flexible third-generation fructose dehydrogenase amperometric biosensors based on water-dispersed 0D-nanomaterials. The electrochemical platform was fabricated via Stencil-Printing (StPE) and insulated via xurography. Carbon black (CB) and mesoporous carbon (MS) were employed as 0D-nanomaterials promoting an efficient direct electron transfer (DET) between fructose dehydrogenase (FDH) and the transducer. Both nanomaterials were prepared in water-phase via a sonochemical approach. The nano-StPE exhibited enhanced electrocatalytic currents compared to conventional commercial electrodes. The enzymatic sensors were exploited for the determination of D-fructose in model solutions and various food and biological samples. StPE-CB and StPE-MS integrated biosensors showed appreciable sensitivity (∼150 µA cm-2 mM-1) with µmolar limit of detection (0.35 and 0.16 µM, respectively) and extended linear range (2-500 and 1-250 µM, respectively); the selectivity of the biosensors, ensured by the low working overpotential (+0.15 V), has been also demonstrated. Good accuracy (recoveries between 95 and 116%) and reproducibility (RSD ≤8.6%) were achieved for food and urine samples. The proposed approach because of manufacturing versatility and the electro-catalytic features of the water-nanostructured 0D-NMs opens new paths for affordable and customizable FDH-based bioelectronics.

Freestanding laser-induced two dimensional heterostructures for self-contained paper-based sensors.

The production of 2D/2D heterostructures (HTs) with favorable electrochemical features is challenging, particularly for semiconductor transition metal dichalcogenides (TMDs). In this studies, we introduce a CO2 laser plotter-based technology for the realization of HT films comprising reduced graphene oxide (rGO) and 2D-TMDs (MoS2, WS2, MoSe2, and WSe2) produced via water phase exfoliation. The strategy relies on the Laser-Induced production of HeterosTructures (LIHTs), where after irradiation the nanomaterials exhibit changes in the morphological and chemical structure, becoming conductive easily transferable nanostructured films. The LIHTs were characterized in detail by SEM, XPS, Raman and electrochemical analysis. The laser treatment induces the conversion of GO into conductive highly exfoliated rGO decorated with homogeneously distributed small TMD/TM-oxide nanoflakes. The freestanding LIHT films obtained were employed to build self-contained sensors onto nitrocellulose, where the HT works both as a transducer and sensing surface. The proposed nitrocellulose-sensor manufacturing process is semi-automated and reproducible, multiple HT films may be produced in the same laser treatment and the stencil-printing allows customizable design. Excellent performance in the electroanalytical detection of different molecules such as dopamine (a neurotransmitter), catechin (a flavonol), and hydrogen peroxide was demonstrated, obtaining nanomolar limits of detection and satisfactory recovery rates in biological and agrifood samples, together with high fouling resistance. Considering the robust and rapid laser-induced production of HTs and the versatility of scribing desired patterns, the proposed approach appears as a disruptive technology for the development of electrochemical devices through sustainable and accessible strategies.

Rapid pretreatment-free evaluation of antioxidant capacity in extra virgin olive oil using a laser-nanodecorated electrochemical lab-on-strip.

An electroanalytical lab-on-a-strip device for the direct extra-virgin olive oil (EVOO) antioxidant capacity evaluation is proposed. The lab-made device is composed of a CO2 laser nanodecorated sensor combined with a cutter-plotter molded paper-strip designed for EVOOs sampling and extraction. Satisfactory performance towards the most representative o-diphenols of EVOOs i.e., hydroxytyrosol (HY) and oleuropein (OL) were achieved; good sensitivity (LODHY = 2 µM; LODOL = 0.6 µM), extended linear ranges (HY: 10-250 µM; OL: 2.5-50 µM) and outstanding reproducibility (RSD < 5%, n = 3) were obtained in rectified oil. The device was challenged for the extraction-free analysis of 15 different EVOO samples, with satisfactory recoveries (90-94%; RSD < 5%, n = 3) and correlation with classical photometric assays (r ≥ 0.91). The proposed device includes all analysis steps, needs 4 µL of sample, and returns reliable results in 2 min, resulting portable and usable with a smartphone.

Catechin versus MoS2 Nanoflakes Functionalized with Catechin: Improving the Sperm Fertilizing Ability-An In Vitro Study in a Swine Model.

Nowadays, the adoption of In Vitro Fertilization (IVF) techniques is undergoing an impressive increase. In light of this, one of the most promising strategies is the novel use of non-physiological materials and naturally derived compounds for advanced sperm preparation methods. Here, sperm cells were exposed during capacitation to MoS2/Catechin nanoflakes and catechin (CT), a flavonoid with antioxidant properties, at concentrations of 10, 1, 0.1 ppm. The results showed no significant differences in terms of sperm membrane modifications or biochemical pathways among the groups, allowing the hypothesis that MoS2/CT nanoflakes do not induce any negative effect on the parameters evaluated related to sperm capacitation. Moreover, the addition of CT alone at a specific concentration (0.1 ppm) increased the spermatozoa fertilizing ability in an IVF assay by increasing the number of fertilized oocytes with respect to the control group. Our findings open interesting new perspectives regarding the use of catechins and new materials obtained using natural or bio compounds, which could be used to implement the current strategies for sperm capacitation.

Nanoscale Surface-Enhanced Raman Spectroscopy Investigation of a Polyphenol-Based Plasmonic Nanovector.

The demand for next-generation multifunctional nanovectors, combining therapeutic effects with specific cellular targeting, has significantly grown during the last few years, pursuing less invasive therapy strategies. Polyphenol-conjugated silver nanoparticles (AgNPs) appear as potential multifunctional nanovectors, integrating the biorecognition capability and the antioxidant power of polyphenols, the antimicrobial activity of silver, and the drug delivery capability of NPs. We present a spectroscopic and microscopic investigation on polyphenol-synthesized AgNPs, selecting caffeic acid (CA) and catechol (CT) as model polyphenols and using them as reducing agents for the AgNP green synthesis, both in the presence and in the absence of a capping agent. We exploit the plasmonic properties of AgNPs to collect Surface-Enhanced Raman Scattering (SERS) spectra from the nanosized region next to the Ag surface and to characterize the molecular environment in the proximity of the NP, assessing the orientation and tunable deprotonation level of CA, depending on the synthesis conditions. Our results suggest that the SERS investigation of such nanovectors can provide crucial information for their perspective biomedical application.

One-Step Laser Nanostructuration of Reduced Graphene Oxide Films Embedding Metal Nanoparticles for Sensing Applications.

The combination of two-dimensional materials and metal nanoparticles (MNPs) allows the fabrication of novel nanocomposites with unique physical/chemical properties exploitable in high-performance smart devices and biosensing strategies. Current methods to obtain graphene-based films decorated with noble MNPs are cumbersome, poorly reproducible, and difficult to scale up. Herein, we propose a straightforward, versatile, surfactant-free, and single-step technique to produce reduced graphene oxide (rGO) conductive films integrating "naked" noble MNPs. This method relies on the instantaneous laser-induced co-reduction of graphene oxide and metal cations, resulting in highly exfoliated rGO nanosheets embedding gold, silver, and platinum NPs. The production procedure has been optimized, and the obtained nanomaterials are fully characterized; the hybrid nanosheets have been easily transferred onto lab-made screen-printed electrodes preserving their nanoarchitecture. The Au@rGO-, Ag@rGO-, and Pt@rGO-based electrodes have been challenged to detect caffeic acid, nitrite, and hydrogen peroxide in model solutions and real samples. The sensors yielded quantitative responses (R2 ≥ 0.997) with sub-micromolar limits of detections (LODs ≤ 0.6 µM) for all the analytes, allowing accurate quantification in samples (recoveries ≥ 90%; RSD ≤ 14.8%, n = 3). This single-step protocol which requires low cost and minimal equipment will allow the fabrication of free-standing, MNP-embedded rGO films integrable into a variety of scalable smart devices and biosensors.

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.

Optical plasmonic sensing based on nanomaterials integrated in solid supports. A critical review.

Noble metal nanoparticles (MNPs), have represented the keystone of a plethora of (bio)sensing analytical strategies because of their unique physicochemical features, becoming unique tools in the analytical scenario; in particular, MNPs localized surface plasmon resonance (LSPR) offers infinite analytical possibilities. In this work, the scaling-up from colloidal MNPs to their integration in solid substrates is overviewed, and the relative sensing and biosensing optical strategies based on LSPR changes are systematically treated in accordance with the supporting substrate employed. Recent literature and key papers reporting MNPs integration into solid substrates are considered, paying particular attention to the MNPs-based event into/onto the solid support and the related plasmonic change used as analytical signal. The review is organized in sections according to the solid support nature (glass, polymers, cellulose) and the papers are discussed according to the sensing strategy. The strategies have been classified in MNPs synthesis, growth, etching, displacement/aggregation directly or indirectly mediated by the analyte(s); only works that rely on plasmonic-transduction principles are taken into account, MNPs used as catalysts or in lateral flow systems are not considered. The review demonstrates that MNPs decorated/integrated substrates are now mature analytical tools, able to overcome the limitations of MNPs colloidal suspensions; this results in new analytical opportunities, particularly the realization of integrated systems, lab-on-chip/lab-on-strip and flexible devices, paving the way for a new generation of plasmonic (bio)sensors for point-of-need applications.

Carbon Black Functionalized with Naturally Occurring Compounds in Water Phase for Electrochemical Sensing of Antioxidant Compounds.

A new sustainable route to nanodispersed and functionalized carbon black in water phase (W-CB) is proposed. The sonochemical strategy exploits ultrasounds to disaggregate the CB, while two selected functional naturally derived compounds, sodium cholate (SC) and rosmarinic acid (RA), act as stabilizing agents ensuring dispersibility in water adhering onto the CB nanoparticles' surface. Strategically, the CB-RA compound is used to drive the AuNPs self-assembling at room temperature, resulting in a CB surface that is nanodecorated; further, this is achieved without the need for additional reagents. Electrochemical sensors based on the proposed nanomaterials are realized and characterized both morphologically and electrochemically. The W-CBs' electroanalytical potential is proved in the anodic and cathodic window using caffeic acid (CF) and hydroquinone (HQ), two antioxidant compounds that are significant for food and the environment. For both antioxidants, repeatable (RSD ≤ 3.3%; n = 10) and reproducible (RSD ≤ 3.8%; n = 3) electroanalysis results were obtained, achieving nanomolar detection limits (CF: 29 nM; HQ: 44 nM). CF and HQ are successfully determined in food and environmental samples (recoveries 97-113%), and also in the presence of other phenolic classes and HQ structural isomers. The water dispersibility of the proposed materials can be an opportunity for (bio) sensor fabrication and sustainable device realization.

An electronic nose based on 2D group VI transition metal dichalcogenides/organic compounds sensor array.

Rapid volatile organic compounds (VOCs) detection is a hot topic today; in this framework nanomaterials and their tailorable chemistry offer a plethora of compelling opportunities. In this work, Group VI transition metal dichalcogenides (TMDs, i.e., MoS2, WSe2, MoSe2, and WSe2) were functionalized with organic compounds (ellagic acid, tannic acid, catechin, and sodium cholate) able to assist their sonochemical exfoliation in water. The 16 resulting water-dispersed 2D hybrid inorganic/organic TMDs resulted in a few-layer nanoflakes conformation and were used to modify quartz crystal microbalances (QCMs) to equip an e-nose for VOCs determination. The ability of the sensors for the detection of VOCs was assessed on alcohols, terpenes, esters, and aldehydes; the responses were significatively different, confirming the synergic effect of TMD and the organic compound in the interaction with VOCs. The 16 sensors exhibited quantitative responses for VOCs (R2≥0.978) with fast signals recovery (<100 s) and repeatable (RSD ≤9.3%, n = 5), reproducible (RSD ≤12.8%, n = 3) and stable (RSD ≤14.6%, 3 months) signals. As proof of applicability, in an e-nose format, banana aroma evolution during post-harvest ripening was successfully monitored using the 2D TMDs-based sensors array. These data demonstrate that TMDs exfoliated in water with different organic compounds are sustainable functional nanomaterials, able to offer new opportunities in nano-bioelectronic applications.

Effect of Wheat Crop Nitrogen Fertilization Schedule on the Phenolic Content and Antioxidant Activity of Sprouts and Wheatgrass Obtained from Offspring Grains.

This work was aimed at investigating the effects of rate and timing of nitrogen fertilization applied to a maternal wheat crop on phytochemical content and antioxidant activity of edible sprouts and wheatgrass obtained from offspring grains. We hypothesized that imbalance in N nutrition experienced by the mother plants translates into transgenerational responses on seedlings obtained from the offspring seeds. To this purpose, we sprouted grains of two bread wheat cultivars (Bologna and Bora) grown in the field under four N fertilization schedules: constantly well N fed with a total of 300 kg N ha-1; N fed only very early, i.e., one month after sowing, with 60 kg N ha-1; N fed only late, i.e., at initial shoot elongation, with 120 kg N ha-1; and unfertilized control. We measured percent germination, seedling growth, vegetation indices (by reflectance spectroscopy), the phytochemical content (total phenols, phenolic acids, carotenoids, chlorophylls), and the antioxidant activity (by gold nanoparticles photometric assay) of extracts in sprout and wheatgrass obtained from the harvested seeds. Our main finding is that grains obtained from crops subjected to late N deficiency produced wheatgrass with much higher phenolic content (as compared to the other N treatments), and this was observed in both cultivars. Thus, we conclude that late N deficiency is a stressing condition which elicits the production of phenols. This may help counterbalance the loss of income related to lower grain yield in crops subjected to such an imbalance in N nutrition.

Modular graphene mediator film-based electrochemical pocket device for chlorpyrifos determination.

In this work, a redox-graphene (Rx-Gr) film with electron-mediating ability has been integrated into a modular flexible pocket device, giving rise to a reusable biosensing platform. The Rx-Gr has been obtained in water from graphite taking advantage of catechin, a redox-antioxidant, able to assist the sonochemical layered-material exfoliation, conferring electron mediating feature. A film composed exclusively of Rx-Gr has been transferred via thermal rolling onto a flexible PET-support that was used as the biosensor base. The biosensing platform, composed of office-grade materials, was then fabricated using a cutter-plotter and assembled by thermal lamination; an interchangeable paper-based strip was used to host the enzymatic reaction and drive the capillary flow. An acetylcholinesterase-based inhibition assay has been optimized onboard the pocket device to determine chlorpyriphos, a widespread environmental pesticide. The proposed set-up allows the determination of chlorpyriphos at low overpotential (0.2 V) with satisfactory sensitivity (LOD = 0.2 ppb), thanks to the straightforward electroactivity of the Rx-Gr film towards thiocholine (enzymatic product). The modular design allows 5 consecutive complete inhibition assays (control + inhibition measure) retaining the performance (RSD = 5.4%; n = 5). The coupling of bench-top technologies and a new functional graphene film resulted in the development of a cost-effective, reusable, transportable, and within everyone's reach biosensing platform.

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.

Plasmonic active film integrating gold/silver nanostructures for H2O2 readout.

A nanostructured Ag/Au adhesive film for H2O2 reagentless determination is here proposed. The film has been realised onto ELISA polystyrene microplates. Microwells surface has been initially modified with a gold nanoparticles (AuNPs)/polydopamine thin-film. The pristine AuNPs-decorated film was later functionalized with catechin (Au-CT) allowing a uniform formation of a plasmonic active nanostructured silver network in presence of Ag+. Changes in localized surface plasmon resonance (LSPR) of the silver network upon addition of H2O2 has been used as analytical signal, taking advantage of the etching phenomenon. The Ag/Au nanocomposite-film is characterized by a well-defined (LSPRmax = 405 ± 5 nm), reproducible (intraplate RSD ≤ 9.8%, n = 96; inter-plate RSD ≤ 11.4%, n = 480) and stable LSPR signal. The film's analytical features have been tested for H2O2 and glucose (bio)sensing. Satisfactory analytical performances were obtained both for H2O2 (linear range 1-200 µM, R2 = 0.9992, RSD ≤ 6.3%, LOD = 0.2 µM) and glucose (linear range 2-250 µM, R2 = 0.9998, RSD ≤ 8.9%, LOD = 0.4 µM). As proof of applicability, the determination of the two analytes in soft drinks has been carried out achieving good and reproducible recoveries (84-111%; RSD ≤ 9%). The developed nanostructured film overcomes analytical drawbacks associated with the use of colloidal dispersions in plasmonic assays carried out in solution; the low cost, robustness, ease of use and possibility of coupling enzymatic reactions appears very promising for (bio)sensors based on the detection of H2O2.

Class-selective voltammetric determination of hydroxycinnamic acids structural analogs using a WS2/catechin-capped AuNPs/carbon black-based nanocomposite sensor.

A high-performance screen-printed electrode (SPE) based nanocomposite sensor integrating tungsten disulfide (WS2) flakes decorated with catechin-capped gold nanoparticles (AuNP-CT) and carbon black (CB) has been developed. The excellent antifouling properties of WS2 decorated with AuNP-CT into a high conductivity network of CB results in high selectivity, sensitivity, and reproducibility for the simultaneous determination of hydroxycinnamic acid (hCN) structural analogs: caffeic (CF), sinapic (SP), and p-coumaric acids (CM). Using differential pulse voltammetry (DPV), the target hCNs resulted in three well-resolved oxidation peaks at SPE-CB-WS2/AuNP-CT sensor. Excellent antifouling performance (RSD ip,a ≤ 3%, n = 15 for three analytes' simultaneous measure) and low detection limits (CF 0.10 µmol L-1; SP, 0.40 µmol L-1; CM, 0.40 µmol L-1) are obtained despite the analyzed compounds having a high passivation tendency towards carbon-based sensors. The SPE-CB-WS2/AuNP-CT sensor was successfully applied to determine CF, SP, and CM in food samples with good precision (RSD ≤ 4%, n = 3) and recoveries (86-109%; RSD ≤ 5%, n = 3). The proposed sensor is the first example exploiting the simultaneous determination of these compounds in food samples. Given its excellent electrochemical performance, low cost, disposability, and ease of use, this SPE-CB-WS2/AuNP-CT nanocomposite sensor represents a powerful candidate for the realization of electrochemical devices for the determination of (bio)compounds with high passivation tendency. Graphical abstract.

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.