Selective dual sensing strategy for free and vitamin D3 micelles in food samples based on S,N-GQDs photoinduced electron transfer.

A reliable nanotechnological sensing strategy, based on an S,N-co-doped graphene quantum dot (GQD) platform, has been developed to distinctly detect two key variants of vitamin D3, specifically the free (VD3) and the nanoencapsulated form (VD3Ms). For this purpose, food-grade vitamin D3 micelles were self-assembled using a low-energy procedure (droplet size: 49.6 nm, polydispersity index: 0.34, ζ-potential: -33 mV, encapsulation efficiency: 90 %) with an innovative surfactant mixture (Tween 60 and quillaja saponin). Herein, four fluorescent nanoprobes were also synthesized and thoroughly characterized: S,N-co-doped GQDs, α-cyclodextrin-GQDs, ß-cyclodextrin-GQDs, and γ-cyclodextrin-GQDs. The goal was to achieve a selective dual sensing strategy for free VD3 and VD3Ms by exploiting their distinctive quenching behaviors. Thus, the four nanosensors allowed the individual sensing of both targets to be performed (except α-CD-GQD for VD3Ms), but S,N-GQDs were finally selected due to selectivity and sensitivity (quantum yield, QY= 0.76) criteria. This choice led to a photoinduced electron transfer (PET) mechanism associated with static quenching, where differentiation was evidenced through a displayed 13-nm hypsochromic (blue) shift when interacting with VD3Ms. The reliability of this dual approach was demonstrated through an extensive evaluation of analytical performance characteristics. The feasibility and accuracy were proven in commercial food preparations and nutritional supplements containing declared nanoencapsulated and raw VD3, whose results were validated by a paired Student's t-test comparison with a UV-Vis method. To the best of our knowledge, this represents the first non-destructive analytical approach addressing the groundbreaking foodomic trend to distinctly detect different bioactive forms of vitamin D3, while also preserving their native nanostructures as a chemical challenge, thus providing reliable information about their final stability and bioavailability.

γ-Cyclodextrin-graphene quantum dots-chitosan modified screen-printed electrode for sensing of fluoroquinolones.

An innovative electrochemical approach based on screen-printed carbon electrodes (SPCEs) modified with graphene quantum dots (GQDs) functionalized with γ-cyclodextrin (γ-CD) and assembled to chitosan (CHI) is designed for the assessment of the total content of fluoroquinolones (FQs) in animal source products. For the design of the bionanocomposite, carboxylated graphene quantum dots synthesized from uric acid as precursor were functionalized with γ-CD using succinic acid as a linker. Physic-chemical and nanostructural characterization of the ensuing nanoparticles was performed by high-resolution transmission scanning microscopy, dynamic light scattering, Z potential measurement, Fourier transformed infrared spectroscopy and X-ray diffraction. Electrochemical properties of assembled bionanocomposite like potential difference, kinetic electronic transfer constant and electroactive area among other parameters were assessed by cyclic voltammetry and differential pulse voltammetry using potassium ferricyanide as redox probe. The oxidation behaviour of four representative quinolones with distinctive structures was studied, obtaining in all cases the same number of involved e- (2) and H+ (2) in their oxidation. These results led us to propose a single and consistent oxidation mechanism for all the checked analytes. The γ-CD-GQDs-CHI/SPCE sensor displayed a boosted electroanalytical performance in terms of linear range (4-250 µM), sensibility (LOD = 1.2 µM) and selectivity. This electrochemical strategy allowed the determination of FQs total amount in complex processed food like broths, bouillon cubes and milkshakes at three concentration levels (150, 75 and 37.5 µM) for both equimolar and different ratio FQs mixtures with recovery values ranging from 90 to 106%.

Distinctive sensing nanotool for free and nanoencapsulated quercetin discrimination based on S,N co-doped graphene dots.

A selective and sensitive fluorescent nanoprobe (sulfur and nitrogen co-doped graphene quantum dots, S,N-GQDs) was designed for both detection and discrimination between free and quercetin-loaded nanoemulsion in food samples of diverse nature. Quercetin nanoemulsions (Q-NEs) were synthesized by a phase inversion temperature (PIT) procedure, while S,N-GQDs were synthesized using a bottom-up methodology by means of simple hydrothermal treatment of citric acid and cysteamine. Both synthetized nanomaterials (analyte and fluorescent probe), were carefully characterized through advanced spectroscopic and high-resolution microscopic techniques. It was observed that fluorescence intensity of S,N-GQDs could be markedly and distinctively quenched by the addition of both quercetin forms through inner filter effect (IFE) mechanisms, exhibiting static quenching events for free quercetin and Q-NEs but with a characteristic 13 nm red-shift spectra in presence of Q-NEs. Linear dynamic ranges between 0.05 and 10 mg L-1 and 0.025-70 mg L-1, with detection limits of 17 and 8 µg L-1 were revealed for free and nanoquercetin, respectively. After nanostructural and physic-chemical optimization, the discrimination strategy was metrologically validated and applied to nutraceutical supplements containing nanoencapsulated quercetin and on diverse free quercetin products such as onion peels and dietary supplements. Accuracy and reliability were proved by means of a statistical comparison with the results obtained by a µHPLC-DAD method (paired Student's t-test at 95% confidence level). The method provides the exciting prospect of analyzing new designed nanoencapsulated bioactives without altering their native nanostructure, as well as being able to accomplish the challenge to distinguish between both forms of quercetin.