Ultrasensitive determination of mercury ions using a glassy carbon electrode modified with nanocomposites consisting of conductive polymer and amino-functionalized graphene quantum dots.

A one-pot method based on cyclic voltammetric scan was used to fabricate a glassy carbon electrode modified with nanocomposites consisting of poly(thionine) and amino-functionalized graphene quantum dots (afGQDs). Under near-neutral conditions, the dye polymer was effectively oxidized by hydroxyl radicals (·OH) that were derived from the copper-catalyzed Fenton-like reaction, and the cathodic peak current on the modified electrode greatly increased. The reaction of Cu2+ with thiourea (TU) and the generation of a complex, CuTU2+, led to the decrease of Cu2+/Cu+ species, which inhibited the Fenton-like reaction and reduced the electrochemical response change. Due to a displacement reaction, the addition of Hg2+ into the H2O2-Cu2+-TU system resulted in the release of cuprous ions that benefited the Fenton-like reaction. Under the following optimal conditions: 6 mg mL-1 afGQDs and the 25-cycle potential cycling for the fabrication of the modified electrode, pH 6.5, and the [Formula: see text] ratio of 1.0, the increasing extent of the cathodic peak current exhibited a good linear response to the logarithm of the Hg2+ concentration in the range of 1 pM-1 µM with a detection limit of 0.6 pM. Mercury ions in a water sample were determined with good recovery, ranging from 97 to 103%. The investigation on the uptake of Hg2+ into human vascular endothelial cells, HUVEC, shows that the cells incubated in the high-concentration glucose medium absorbed more mercury ions than HUVEC incubated in the normal medium. As a result, Hg2+ could lead to the greater damage to the former. Graphical abstract.

Fluorescence "on-off-on" Assay of Copper Ions and EDTA Using Amino-Functionalized Graphene Quantum Dots.

Copper is an important trace element involved in several physiological processes. The deficiency or excess of Cu in the human body may cause some serious diseases. EDTA has been widely employed in many industry fields owing to its excellent chelating ability. The poor biodegradability of EDTA makes itself a persistent substance in the natural environment. This work provided a fluorescence "on-off-on" strategy for the sequential determination of trace Cu2+ and EDTA. Amino-functionalized graphene quantum dots (afGQDs) were synthetized via the thermal pyrolysis of citric acid. Fluorescence resonance energy transfer (FRET) between afGQDs and 1-(2-pyridylazo)-2-naphthol (PAN) effectively quenched the fluorescence of this carbon-based nanomaterial. The generation of the Cu2+-PAN complex caused the increased FRET efficiency and the further fluorescence decline. The change of the fluorescence intensity sensitively responded to copper ions. The linear range and the limit of detection (LOD) were 1 nM-10 µM and 0.87 nM, respectively. EDTA could decompose the Cu2+-PAN complex and liberate PAN, which weakened the FRET efficiency and led to the fluorescence recovery. The increasing degree of the fluorescence intensity was closely related to EDTA within a concentration range from 10 nM to 10 µM with a LOD at 4 nM. Copper ions in the water and human serum samples and EDTA in the trypsin-EDTA sample were successfully detected based on the proposed fluorescence method.

Investigation of photo-induced electron transfer between amino-functionalized graphene quantum dots and selenium nanoparticle and it's application for sensitive fluorescent detection of copper ions.

Copper ions play an essential role in some biological processes. Currently, there is a need for the development of convenient and reliable analytical methods for the Cu2+ measurement. In the present work, a sensitive fluorescence method was developed for the determination of copper ions. Amino-functionalized graphene quantum dots (af-GQDs) and selenium nanoparticles (Se NPs) were synthetized, respectively, and they were characterized via transmission electron microscope, infrared spectrum analysis and X-ray photoelectron spectrum measurement. Photo-induced electron transfer (PET) between the prepared two nanomaterials could effectively quench the fluorescence of af-GQDs. Cu(II) was reduced to Cu(I) in the presence ascorbic acid and Cu2Se was finally generated on Se NPs surface, which led to the declined PET efficiency and inhibited the fluorescence quenching of af-GQDs. The change in fluorescence intensity was linearly correlated to the logarithm of the Cu2+ concentration from 1 nM to 10 µM, with a detection limit of 0.4 nM under the optimal conditions. The detections of copper ions in water samples were realized via standard addition method and the recovery values varied from 98.7% to 103%. The proposed fluorescence method was also employed to analyze the uptake of Cu2+ into human cervical carcinoma HeLa cells and cisplatin-resistant HeLa cells (HeLa/DDP cells). The experimental results indicate that the decreased hCTR1 expression level in HeLa/DDP cells weakened the uptake of copper ions into these drug-resistant tumor cells.

Voltammetric determination of reduced glutathione using poly(thionine) as a mediator in the presence of Fenton-type reaction.

An indirect and sensitive electrochemical method for the determination of reduced glutathione (GSH) was developed by using poly(thionine) (PTH) as a mediator in the presence of Fenton-type reaction on the electrode surface in this work. Cyclic voltammetry and the adsorption of Cu2+ were employed in sequence to fabricate a Cu-PTH modified electrode, which was characterized by scanning electron microscopy, XPS and electrochemical measurements. Hydroxyl radicals that were derived from the Fenton-type reaction between Cu2+ and H2O2 could effectively oxidize PTH, leading to the great enhancement of the cathodic peak current of the dye polymer in the cyclic voltammetric scan. The electroreduction of PTH on the electrode surface was found to be inhibited in the presence of GSH. Under the optimized conditions, the cathodic peak current change was found to be proportional to the logarithm of the GSH concentration from 10nM to 1mM with a detection limit of 2.5nM estimated at a signal-to-noise ratio of 3. The proposed electrochemical sensor was successfully employed for the determination of GSH in real samples with satisfactory results.