Discrimination between nanocurcumin and free curcumin using graphene quantum dots as a selective fluorescence probe.

Accurate-controlled sized graphene quantum dots (GQDs) have been used as an analytical nanoprobe for detecting curcumin as a function of the photoluminescent quenching upon increasing concentrations of the analyte. Regarding the importance of curcumin nanoparticles in nutraceutical food, the analytical method described herein was also proven for the discrimination of curcumin remaining in free solution from that encapsulated into water-soluble nanomicelles of ca. 11 nm. This recognition is based on the displacement of GQD emission when interacting with both curcumin species. Maximum emission wavelength of GQDs suffers a gradual quenching as well as a red-shifting upon increasing concentrations of free curcumin (from 458 to 490 nm, exciting at 356 nm). On the other hand, in the presence of nanocurcumin, GQD photoluminescent response only displays a quenching effect (458/356 nm). The sensitivity of the described method in terms of detection limits was 0.3 and 0.1 µg mL-1 for curcumin and nanocurcumin, respectively. The applicability of the photoluminescent probe for the quantification and discrimination between both curcumin environments was demonstrated in nutraceutical formulations namely functional food capsules and fortified beverages such as ginger tea. Graphical abstract.

Determination of vanillin by using gold nanoparticle-modified screen-printed carbon electrode modified with graphene quantum dots and Nafion.

A voltammetric analytical assay for the selective quantification of vanillin is described. It is based on the use of a gold nanoparticle-modified screen-printed carbon electrode (SPCE) modified with graphene quantum dots (GQD) in a Nafion matrix. The GQD were synthesized by an acidic thermal method and characterized by UV-Vis, photoluminescence, and FTIR spectroscopy. The modified SPCE displays a strongly enhanced response to vanillin. Linear sweep voltammetry (LSV) and differential pulse voltammetry (DPV) were applied to optimize the methods. The analytical assay has linear responses in the 13 to 660 µM and 0.66 to 33 µM vanillin concentration ranges. The detection limits are 3.9 µM and 0.32 µM when using LSV and DPV, respectively. The analytical assay is selective and stable. It was applied to the determination of vanillin in several food samples with satisfactory results. Recoveries from spiked samples ranged between 92.1 and 113.0%. Graphical abstract The selective and sensitive quantification of vanillin is carried out by the use of a gold nanoparticle-modified screen-printed carbon electrode modified with graphene quantum dots in a Nafion matrix.

Direct determination of graphene quantum dots based on terbium-sensitized luminescence.

Graphene quantum dots (GQD) were determined in water samples using terbium-sensitized luminescence (TSL). Terbium ions complex with GQD due to the carboxylic groups that are usually present in these nanomaterials, increasing the luminescence signal of terbium. In Tb(III)-GQD complexes, GQD absorb energy at their characteristic excitation wavelength and transfer it to terbium ion, which emits at its particular emission wavelength. The analytical signal, measured at λexc=257nm and λem=545nm, increases proportionally to GQD concentration between 50 and 500µgL-1. Under optimum conditions, the proposed method presents a detection limit of 15µgL-1 and is selective to GQD in the presence of other nanomaterials of similar size. As GQD are highly water-soluble, they are potential contaminants in environmental or drinking waters water samples, and hence the method was applied to the analysis of different drinking waters which were the target samples for the application of the developed method.

Graphene quantum dots-terbium ions as novel sensitive and selective time-resolved luminescent probes.

We propose an alternative approach for the development of analytical methods based on terbium-sensitized luminescence (TSL). TSL is based on the complexation between Tb(III) ions and fluorescent organic compounds that have appropriate functional groups to complex with Tb(III). We report the use of graphene quantum dot (GQDs) nanoparticles to improve the sensitivity and selectivity of TSL detection. GQDs can react with terbium ions through the carboxylic groups present in their structure. These Tb(III)-GQD complexes, formed in situ in aqueous solution, can be used as time-resolved luminescent probes. Ascorbic acid was selected as a target analyte to demonstrate the suitability of the proposed method. The selectivity of the TSL method was highly improved for most of the interferences tested. Under the optimum conditions [Tb(III) concentration 5 × 10-4 mol L-1, GQD concentration 4 mg L-1], a minimum 100% increase in selectivity was observed for several vitamins and common cations that may be present in the samples to be analyzed. In addition, the analytical signal showed a 30% enhancement with the use of GQDs compared with the use of merely Tb(III) ions, with a detection limit of 0.12 µg mL-1. The repeatability and intermediate precision were lower than 3% and 5%, respectively. From the results obtained, the implementation of GQDs in TSL can lead to the development of novel time-resolved luminescent probes with high analytical potential. Graphical abstract Quenching of Tb(III)-graphene quantum dot (GQD) luminescence by ascorbic acid (AA). TBL terbium-sensitized luminescence.

Analysis of penicillamine using Cu-modified graphene quantum dots synthesized from uric acid as single precursor.

A simple methodology was developed to quantify penicillamine (PA) in pharmaceutical samples, using the selective interaction of the drug with Cu-modified graphene quantum dots (Cu-GQDs). The proposed strategy combines the advantages of carbon dots (over other nanoparticles) with the high affinity of PA for the proposed Cu-GQDs, resulting in a significant and selective quenching effect. Under the optimum conditions for the interaction, a linear response (in the 0.10-7.50 µmol/L PA concentration range) was observed. The highly fluorescent GQDs used were synthesized using uric acid as single precursor and then characterized by high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, fluorescence, and absorption spectroscopy. The proposed methodology could also be extended to other compounds, further expanding the applicability of GQDs.

Development and Characterization of Carbon Based Electrodes from Pyrolyzed Paper for Biosensing Applications.

This article details the study of electrochemical behavior of new carbon electrodes based on pyrolysis of different paper sources to be used in biosensor applications. The resistivity of the pyrolyzed papers was initially used as screening parameters to select the best three paper samples (imaging card paper, multipurpose printing paper, and 3MM chromatography paper) and assemble working electrodes that were further characterized by a combination of microscopy, electrochemistry, and spectroscopy. Although slight differences in performance were observed, all carbon substrates fabricated from pyrolysis of paper allowed the development of competitive biosensors for uric acid. The presented results demonstrate the potential of these electrodes for sensing applications and highlight the potential advantages of 3MM chromatography paper as a substrate to fabricate electrodes by pyrolysis.

Quantum Dot-Modified Paper-Based Assay for Glucose Screening.

A simple and inexpensive method to fabricate a colloidal CdSe/ZnS quantum dots-modified paper-based assay for glucose is herein reported. The circular paper sheets were uniformly loaded and displayed strong fluorescence under a conventional hand-held UV lamp (365 nm). The assay is based on the use of glucose oxidase enzyme (GOx), which impregnated the paper sheets, producing H2O2 upon the reaction with the glucose contained in the samples. After 20 min of exposure, the fluorescence intensity changed due to the quenching caused by H2O2. To obtain a reading, the paper sheets were photographed under 365 nm excitation using a digital camera. Several parameters, including the amount of QD, sample pH, and amount of GOx were optimized to maximize the response to glucose. The paper-based assay showed a sigmoidal-shaped response with respect to the glucose concentration in the 5-200 mg·dL-1 range (limit of detection of 5 µg·dL-1), demonstrating their potential use for biomedical applications.

Synthesis of CuNP-Modified Carbon Electrodes Obtained by Pyrolysis of Paper.

A one-step approach for the synthesis and integration of copper nanoparticles (CuNPs) onto paper-based carbon electrodes is herein reported. The method is based on the pyrolysis (1000 °C under a mixture of 95% Ar / 5% H2 for 1 hour) of paper strips modified with a saturated solution of CuSO4 and yields to the formation of abundant CuNPs on the surface of carbonized cellulose fibers. The resulting substrates were characterized by a combination of scanning electron microscopy, EDX, Raman spectroscopy as well as electrical and electrochemical techniques. Their potential application, as working electrodes for nonenzymatic amperometric determination of glucose, was then demonstrated (linear response up to 3 mM and a sensitivity of 460 ± 8 µA·cm-2·mM-1). Besides being a simple and inexpensive process for the development of electrochemically-active substrates, this approach opens new possibilities for the in-situ synthesis of metallic nanoparticles without the traditional requirements of solutions and adjuvants.

ß-Cyclodextrin coated CdSe/ZnS quantum dots for vanillin sensoring in food samples.

An optical sensor for vanillin in food samples using CdSe/ZnS quantum dots (QDs) modified with ß-cyclodextrin (ß-CD) was developed. This vanillin-sensor is based on the selective host-guest interaction between vanillin and ß-cyclodextrin. The procedure for the synthesis of ß-cyclodextrin-CdSe/ZnS (ß-CD-CdSe/ZnS-QDs) complex was optimized, and its fluorescent characteristics are reported. It was found that the interaction between vanillin and ß-CD-CdSe/ZnS-QDs complex produced the quenching of the original fluorescence of ß-CD-CdSe/ZnS-QDs according to the Stern-Volmer equation. The mechanism of the interaction is discussed. The analytical potential of this sensoring system was demonstrated by the determination of vanillin in synthetic and food samples. The method was selective for vanillin, with a limit of detection of 0.99 µg mL(-1), and a reproducibility of 4.1% in terms of relative standard deviation (1.2% under repeatability conditions). Recovery values were in the 90-105% range for food samples.

Microwave-assisted synthesis of water soluble thiol capped CdSe/ZnS quantum dots and its interaction with sulfonylurea herbicides.

A simple and fast procedure for water solubilization of CdSe/ZnS quantum dots (QDs) using microwave irradiation (MW) has been optimized. The CdSe/ZnS QDs were synthesized in organic media and water solubilization was achieved by replacing the initial hydrophobic ligands (TOPO and TOP) with hydrophilic heterobifunctional thiol ligands, such as L-cysteine (L-Cys), 3-mercaptopropionic acid (3-MPA) and cysteamine (CTAM). The use of MW irradiation allowed carrying out the modification of the surface thiol of QDs in a simple and fast way (only 40 s was required). Different optimization studies based on activation-time, irradiation-time, concentration of ligands, pH and lifetime fluorescent properties were carried out in order to obtain the best results for the solubilization of QDs. By the proposed method, the resulting water-soluble QDs exhibit a strong fluorescence emission at about 590 nm, with a high and reproducible photostability and acceptable yields. With the aim of contributing to exploiting the advantages of synthetized QDs from an analytical point of view, the different behavior with sulfonylurea herbicides (SUHs) were studied.

Use of Cdse/ZnS quantum dots for sensitive detection and quantification of paraquat in water samples.

Based on the highly sensitive fluorescence change of water-soluble CdSe/ZnS core-shell quantum dots (QD) by paraquat herbicide, a simple, rapid and reproducible methodology was developed to selectively determine paraquat (PQ) in water samples. The methodology enabled the use of simple pretreatment procedure based on the simple water solubilization of CdSe/ZnS QDs with hydrophilic heterobifunctional thiol ligands, such as 3-mercaptopropionic acid (3-MPA), using microwave irradiation. The resulting water-soluble QDs exhibit a strong fluorescence emission at 596 nm with a high and reproducible photostability. The proposed analytical method thus satisfies the need for a simple, sensible and rapid methodology to determine residues of paraquat in water samples, as required by the increasingly strict regulations for health protection introduced in recent years. The sensitivity of the method, expressed as detection limits, was as low as 3.0 ng L(-1). The lineal range was between 10-5×10(3) ng L(-1). RSD values in the range of 71-102% were obtained. The analytical applicability of proposed method was demonstrated by analyzing water samples from different procedence.