A novel synthesis of graphene quantum dots via thermal treatment of crude graphite oxide in a dry and alkaline condition, and their application in uranyl detection.

In this article, a novel method to synthesize graphene quantum dots was developed via thermal treatment of crude graphite oxide (GO) in a dry and alkaline condition to cut the crude GO sheets into small graphene quantum dots (named as aGQDs). The aGQDs are nano-scale reduced graphene oxide pieces with the sizes around 5-10 nm. The aGQDs could disperse in water for their richment of oxygen-containing groups. The fluorescence properties were carefully investigated. The aGQDS aqueous solution shows a bright yellow-green fluorescence under the UV illumination. Besides, the uranyl ions show a strong fluorescence quenching effect on the a aGQD aqueous solution even at a low concentration (~10-7 M) compared with other common ions in natural water-body, which makes that these aGQDs could be applied as a chemosensor for detection of uranyl ions with good sensitivity and selectivity.

Graphene quantum dot electrochemiluminescence increase by bio-generated H2O2 and its application in direct biosensing.

In this study, a novel signal-increase electrochemiluminescence (ECL) biosensor has been developed for the detection of glucose based on graphene quantum dot/glucose oxidase (GQD/GOx) on Ti foil. The proposed GQD with excellent ECL ability is synthesized through a green one-step strategy by the electrochemical reduction of graphene oxide quantum dot. Upon the addition of glucose, GOx can catalytically oxidize glucose and the direct electron transfer between the redox centre of GOx and the modified electrode also has been realized, which results in the bio-generated H2O2 for ECL signal increase in GQD and realizes the direct ECL detection of glucose. The signal-increase ECL biosensor enables glucose detection with high sensitivity reaching 5 × 10-6 mol l-1 in a wide linear range from 5 × 10-6 to 1.5 × 10-3 mol l-1. Additionally, the fabrication process of such GQD-based ECL biosensor is also suitable to other biologically produced H2O2 system, suggesting the possible applications in the sensitive detection of other biologically important targets (e.g. small molecules, protein, DNA and so on).

Flexible and adhesive tape decorated with silver nanorods for in-situ analysis of pesticides residues and colorants.

A flexible adhesive tape decorated with SERS-active silver nanorods (AgNRs) in the form of an array nanostructure is described. The tape was constructed by transferring the AgNRs nanostructures from silicon to the transparent tape by a "paste & peel off" procedure. The transparent, sticky, and flexible properties of commercial tapes allow almost any SERS-inactive irregular surface to be detected in-situ by pasting the SERS tape onto the position to be analyzed. Three examples for an analytical application are presented, viz. determination of (a) tetramethylthiuram disulfide and thiabendazole (two pesticides), (b) colorants in the gel of a writing pen, and (c) the fluorophore Rhodamine B. The tetramethylthiuram disulfide on apple surface was rapidly detected with a LOD of 28.8 ng·cm-2. The AgNRs effectively quenched the fluorescence of the matrix and fluorophores, this enabling the colorants and Rhodamine B to be identified. The results demonstrated that the SERS tape can be used for versatile in-situ detection. Conceivably, it may find applications in food analysis, non-invasive identification, environmental monitoring, and in other areas of daily life. Graphic abstract A flexible and adhesive SERS active tape decorated with silver nanorods (AgNRs) arrays was constructed through a "paste & peel off" method. It can be used as a versatile in situ analysis platform for various applications.

Assembly of porphyrin-based uranium organic frameworks with (3,4)-connected pto and tbo topologies.

Three (3,4)-connected uranyl-organic frameworks (UOFs) with pto and tbo topologies were synthesized. The UOF with a pto net possesses a 2-fold interpenetrating network and exhibits 2D interconnected channels. The UOF with a tbo net is constructed from two types of ultralarge nanocages. All these compounds can efficiently remove large cationic dye crystal violet (CV) through a cation exchange mechanism.

The contribution of photoinduced charge-transfer enhancement to the SERS of uranyl(VI) in a uranyl-Ag2O complex.

Charge-transfer (CT) is an important enhancement mechanism in the field of surface-enhanced Raman scattering (SERS) that typically increases the Raman intensity of molecules by as much as 10-100 times. Herein, a low-cost Ag2O aggregates substrate was prepared via a facile chemical precipitation method, and the calculated CT-based enhancement factor of the uranyl ions adsorbed on it reached as high as 105, a metal-comparable value. The efficient photoinduced CT process from the valence band of Ag2O to the LUMO of uranyl ions under appropriate excitation sources resulted in the repulsion of the axial oxygen atoms of the OUO bond, which enhanced its polarizability, creating a more intense Raman mode. To the best of our knowledge, this study firstly reports such a strong photoinduced CT enhancement of uranyl ions, with concentrations of 10-8 mol L-1 or lower being detected using this Ag2O substrate. Most importantly, this research has shown that the photoinduced CT enhancement also contributes to the SERS of uranyl ions on pure Ag substrates which have often been ascribed to the electromagnetic enhancement in previous studies. In addition, Ag2O can be used to selectively detect uranyl ions without interference from many other molecules or ions because of the energy matching rule of the photoinduced CT process, which was readily available for uranyl detection in the environmental aqueous solution.

Advances in the use of carbonaceous materials for the electrochemical determination of persistent organic pollutants. A review.

Persistent organic pollutants (POPs) are key pollutants due to their persistence, refractory biodegradation, high toxicity and bioaccumulation in the food chain. This review (with 93 refs.) covers the progress made in the past decades in the application of carbonaceous materials for electrochemical detection of POPs as listed in the Stockholm Convention. Following an introduction into the field, typical carbonaceous materials for use in electrodes are discussed, with subsection on carbon nanotubes, graphene, reduced graphene oxide, graphitic carbon nitride and carbon dots. This is followed by a section on application of carbonaceous materials in electrochemical detection, with subsections on the use of carbon nanotubes, of (doped-) graphene, of reduced graphene oxide, of graphitic carbon nitride, and of carbon dots. The review concludes with conclusions and future perspectives. The detection mechanisms of POPs are also discussed. Graphical abstract Advanced carbonaceous materials for the electrochemical determination of persistent organic pollutants.

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions.

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of OUO resulting from two kinds of adsorption of uranyl species ("strong" and "weak" adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of OUO shifted from 871cm-1 (normal Raman) to 720cm-1 and 826cm-1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at ~826cm-1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10-7 to 10-3molL-1 with an excellent linear relation (R2=0.998), and the detection limit was ~10-7molL-1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

Graphene oxide amplified electrochemiluminescence of graphitic carbon nitride and its application in ultrasensitive sensing for Cu(2+).

Here for the first time, we present a novel electrochemiluminescence (ECL) sensor based on graphitic carbon nitride/graphene oxide (g-C3N4/GO) hybrid for the ultrasensitive detection of Cu(2+), which is a common pollutant in environmental system. The g-C3N4/GO shows stable ECL signal in the presence of the self-produced coreactant from oxygen reduction, and the ECL signal could be effectively quenched by Cu(2+), the possible ECL detection mechanism has been proposed in detail. GO can not only significantly enhance the cathodic ECL signal of g-C3N4 (∼3.8 times), but also serve as immobilization platform for g-C3N4. After optimization of experimental conditions, the proposed protocol can offer an ultrasensitive, highly selective and recyclable method for the detection of Cu(2+) with a low detection limit of 1.0 × 10(-11) M and a wide linear range from 1.0 × 10(-11) to 1.0 × 10(-7) M. Moreover, the practicability of the ECL sensor in real wastewater samples is also tested, showing that the proposed ECL sensor could be a promising alternative method for the emergency and routine monitoring of Cu(2+) in real sample.