Graphene Aerogel-Metal-Organic Framework-Based Electrochemical Method for Simultaneous Detection of Multiple Heavy-Metal Ions.

The development of an effective method for detecting heavy-metal ions remains a serious task because of their high toxicity to public health and environments. Herein, a new electrochemical method based on a graphene aerogel (GA) and metal-organic framework (MOF) composites was developed for simultaneous detection of multiple heavy-metal ions in aqueous solutions. The GA-MOF composites were synthesized via the in situ growth of the MOF UiO-66-NH2 crystal on the GA matrix. GA not only serves as the backbone for UiO-66-NH2 but also enhances the conductivity of the composites by accelerating the electron transfer in the matrix. UiO-66-NH2 worked as a binding site for heavy-metal ions because of the interaction between hydrophilic groups and metal cations. The detection performance of the GA-UiO-66-NH2 composite-modified electrodes was determined. The developed electrochemical method can be successfully applied for individual and simultaneous detection of heavy-metal ions, namely, Cd2+, Pb2+, Cu2+,and Hg2+, in aqueous solutions with high sensitivity and selectivity. The method can also be used for simultaneous detection of Cd2+, Pb2+, Cu2+, and Hg2+ in river water and the leaching solutions of soil and vegetable with high accuracy and reliability. This work provides a new approach for simultaneous detection of multiple heavy-metal ions in practical applications.

3-D graphene-supported mesoporous SiO2 @Fe3 O4 composites for the analysis of pesticides in aqueous samples by magnetic solid-phase extraction with high-performance liquid chromatography.

Three-dimensional graphene-supported mesoporous silica@Fe3 O4 composites (mSiO2 @Fe3 O4 -G) were prepared by modifying mesoporous SiO2 -coated Fe3 O4 onto hydrophobic graphene nanosheets through a simple adsorption co-condensation method. The obtained composites possess unique properties of large surface area (332.9 m(2) /g), pore volume (0.68 cm(3) /g), highly open pore structure with uniform pore size (31.1 nm), as well as good magnetic separation properties. The adsorbent (mSiO2 @Fe3 O4 -G) was used for the magnetic solid-phase extraction of seven pesticides with benzene rings in different aqueous samples before high-performance liquid chromatography. The main parameters affecting the extraction such as adsorbent amount, volume of elution solvent, time of extraction and desorption, salt effect, oscillation rate were investigated. Under the optimal conditions, this method provided low limits of detection (S/N = 3, 0.525-3.30 µg/L) and good linearity (5.0-1000 µg/L, R(2) > 0.9954). Method validation proved the feasibility of the developed adsorbent, which has a high extraction efficiency and excellent enhancement performance for pesticides in this study. The proposed method was successfully applied to real aqueous samples, and satisfactory recoveries ranging from 77.5 to 113.6% with relative standard deviations within 9.7% were obtained.

Core-shell MOF@MOF composites for sensitive nonenzymatic glucose sensing in human serum.

The detection of blood glucose level receives much attention, because diabetes has become one of the significant threats to human health worldwide. In this paper, we described a novel core-shell MOF@MOF composite-based electrochemical sensor for nonenzymatic glucose sensing in alkaline media. The core-shell UiO-67@Ni-MOF composites were synthesized by internal extended growth of shell Ni-MOF on the core UiO-67 under polyvinylpyrrolidone (PVP) regulation. In the sensor system, UiO-67 with large specific surface area and good conductivity was used to accelerate the rate of electron transfer of UiO-67@Ni-MOF. Ni-MOF served as an electrocatalytic material due to excellent electrochemical activity toward glucose oxidation. The morphology, structure, and electrochemical performance of UiO-67@Ni-MOF composites were characterized. To demonstrate the detection performance of the UiO-67@Ni-MOF composite-based sensor, it was successfully used for nonenzymatic glucose sensing. The results indicated that UiO-67@Ni-MOF composites exhibited high electrocatalytic activity toward glucose oxidation compared with individual UiO-67 and Ni-MOF. Moreover, the sensor possessed high sensitivity and selectivity for real-time amperometric detection of glucose. It performed glucose level detection in human serum samples with acceptable reliability and accuracy. The present work suggested that the as-fabricated sensor is promising for nonenzymatic glucose sensing in real samples and holds great potential as an alternative tool for the rapid diagnosis of diabetes and for monitoring blood glucose levels daily.

Carboxyl hydrogel particle film as a local pH buffer for voltammetric determination of luteolin and baicalein.

Electrochemical determination of luteolin and baicalein always needs acidic supporting electrolyte to guarantee good sensitivity. Therefore, most of the reported electrochemical sensors of luteolin and baicalein are unsuitable for detection of neutral actual samples. It is necessary to design a highly sensitive sensor for direct determination of them in neutral conditions. In this study, poly(N-isopropylacrylamide-acrylic acid) hydrogel particles (NIPA/AA) and multiwall carbon nanotubes (MWCNTs) composite modified glassy carbon electrode (GCE) was fabricated by a simple casting method. The voltammetric results showed that the NIPA/AA particle film provided acidic environment for proton-electron coupled reaction in neutral mediums. The near-surface pH of the electrode was related on the loaded amount of the NIPA/AA particles in pH range from 4.2 to 5.9. The voltammetric behaviors of luteolin and baicalein at the NIPA/AA-MWCNTs-GCE were studied by cyclic voltammetry. The peak separations between cathodic and anodic peaks were decreased and peak currents were increased because of decrease in pH and increase in ion conductivity at the local electrode surface. The sensitivity of the electrode was investigated by differential pulse voltammetry. Even under neutral conditions, the plots of the oxidation currents of luteolin and baicalein were dependent linearly on their concentration with detection limit of 14.5 pM and 44.4 pM, respectively. Moreover, the proposed NIPA/AA-MWCNTs-GCE was also successfully applied for determination of luteolin and baicalein in peanut shell, Huang-qin and tomato samples.