Xinhong Song

Preparation and evaluation of graphene-coated solid-phase microextraction fiber

In this paper, a novel graphene (G) based solid-phase microextraction (SPME) fiber was firstly prepared by immobilizing the synthesized G on stainless steel wire as coating. The new fiber possessed a homogeneous, porous and wrinkled surface and showed excellent thermal (over 330°C), chemical and mechanical stability, and long lifespan (over 250 extractions). The SPME performance of the G-coated fiber was evaluated in detail through extraction of six pyrethroid pesticides. Although the thickness of G-coated fiber was only 6-8 μm, its extraction efficiencies were higher than those of two commercial fibers (PDMS, 100 μm; PDMS/DVB, 65 μm). This high extraction efficiency may be mainly attributed to huge delocalized π-electron system of G, which shows strong π-stacking interaction with pyrethroid pesticide. The G-coated fiber was applied in the gas chromatographic determination of six pyrethroids, and their limits of detection were found to be ranged from 3.69 to 69.4 ng L(-1). The reproducibility for each single fiber was evaluated and the relative standard deviations (RSDs) were calculated to be in the range from 1.9% to 6.5%. The repeatability of fiber-to-fiber and batch-to-batch was 4.3-9.2% and 4.1-9.9%. The method developed was successfully applied to three pond water samples, and the recoveries were 83-110% at a spiking of 1 μg L(-1).

A Label-Free Fluorescence Sensing Approach for Selective and Sensitive Detection of 2,4,6-Trinitrophenol (TNP) in Aqueous Solution Using Graphitic Carbon Nitride Nanosheets

An effective and facile fluorescence sensing approach for the determination of 2,4,6-trinitrophenol (TNP) using the chemically oxidized and liquid exfoliated graphitic carbon nitride (g-C3N4) nanosheets was developed. The strong inner filter effect and molecular interactions (electrostatic, π-π, and hydrogen bonding interactions) between TNP and the g-C3N4 nanosheets led to the fluorescence quenching of the g-C3N4 nanosheets with efficient selectivity and sensitivity. Under optimal conditions, the limit of detection for TNP was found to be 8.2 nM. The proposed approach has potential application for visual detection of TNP in natural water samples for public safety and security.

Non-enzymatic electrochemical glucose sensor based on platinum nanoflowers supported on graphene oxide

A non-enzymatic electrochemical method was developed for glucose detection using a glassy carbon electrode modified with platinum nanoflowers supported on graphene oxide (PtNFs-GO). PtNFs-GO was synthesized using a nontoxic, rapid, one-pot and template-free method. Low-cost, green solvent ethanol acted as the reductant, and the advanced and effective 2D carbon material-GO nanosheet acted as the stabilizing material. Their morphologies were characterized using transmission electron microscopy. Cyclic voltammetry and amperometric methods were used to evaluate the electrocatalytic activity towards glucose in neutral media. The modified electrode exhibited strong and sensitive amperometric responses to glucose even in the presence of a high concentration of chloride ions. The response time was within 5s. The interference effects from ascorbic acid and uric acid were comparatively small when operated at suitable potential. Under optimal detection potential (0.47 V with a saturated calomel reference electrode) the PtNFs-GO modified electrode performed a current response towards glucose at a broad concentration range from 2 μM to 20.3mM. Two linear regions could be observed at 2 μM to 10.3mM with a sensitivity of 1.26 μA mM(-1)cm(-2) (correlation coefficient 0.9968), and at 10.3mM to 20.3mM with a sensitivity of 0.64 μA mM(-1)cm(-2)(correlation coefficient 0.9969). The LOD of 2 μM was lower than many non-enzymatic electrochemical glucose sensors. The modified electrode was also applied to the determination of glucose in glucose injection solutions, and the satisfactory results obtained indicated that it was promising for the development of a novel non-enzymatic electrochemical glucose sensor.

Polypyrrole/graphene composite‐coated fiber for the solid‐phase microextraction of phenols

A polypyrrole (Ppy)/graphene (G) composite was developed and applied as a novel coating for use in solid-phase microextraction (SPME) coupled with gas chromatography (GC). The Ppy/G-coated fiber was prepared by electrochemically polymerizing pyrrole and G on a stainless-steel wire. The extraction efficiency of Ppy/G-coated fiber for five phenols was the highest compared with the fibers coated with either Ppy or Ppy/graphene oxide (GO) using the same method preparation. Significantly, compared with various commercial fibers, the extraction efficiency of Ppy/G-coated fiber is better than or comparable to 85 μm CAR/PDMS fiber (best extraction efficiency of phenol, o-cresol, and m-cresol in commercial fibers) and 85 μm polyacrylate (PA) fiber (best extraction efficiency of 2,4-dichlorophenol and p-bromophenol in commercial fibers). The effects of extraction and desorption parameters such as extraction time, stirring rate, and desorption temperature and time on the extraction/desorption efficiency were investigated and optimized. The calibration curves were linear from 10 to 1000 μg/L for o-cresol, m-cresol, p-bromophenol, and 2,4-dichlorophenol, and from 50 to 1000 μg/L for phenol. The detection limits were within the range 0.34-3.4 μg/L. The single fiber and fiber-to-fiber reproducibilities were <8.3 (n=7) and 13.3% (n=4), respectively. The recovery of the phenols spiked in natural water samples at 200 μg/L ranged from 74.1 to 103.9% and the relative standard deviations were <3.7%.

Intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots and their application in the colorimetric detection of H2O2 and glucose

In this paper, the highly intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots (N-GQDs) is revealed. This activity was greatly dependent on pH, temperature and H2O2 concentration. The experimental results showed that the stable N-GQDs could be used for the detection of H2O2 and glucose over a wide range of pH and temperature, offering a simple, highly selective and sensitive approach for their colorimetric sensing. The linearity between the analyte concentration and absorption ranged from 20 to 1170 μM for H2O2 and 25 to 375 μM for glucose with a detection limit of 5.3 μM for H2O2 and 16 μM for glucose. This assay was also successfully applied to the detection of glucose concentrations in diluted serum and fruit juice samples.

A Phytic Acid Induced Super-Amphiphilic Multifunctional 3D Graphene-Based Foam.

Surfaces with super-amphiphilicity have attracted tremendous interest for fundamental and applied research owing to their special affinity to both oil and water. It is generally believed that 3D graphenes are monoliths with strongly hydrophobic surfaces. Herein, we demonstrate the preparation of a 3D super-amphiphilic (that is, highly hydrophilic and oleophilic) graphene-based assembly in a single-step using phytic acid acting as both a gelator and as a dopant. The product shows both hydrophilic and oleophilic intelligence, and this overcomes the drawbacks of presently known hydrophobic 3D graphene assemblies. It can absorb water and oils alike. The utility of the new material was demonstrated by designing a heterogeneous catalytic system through incorporation of a zeolite into its amphiphilic 3D scaffold. The resulting bulk network was shown to enable efficient epoxidation of alkenes without prior addition of a co-solvent or stirring. This catalyst also can be recovered and re-used, thereby providing a clean catalytic process with simplified work-up.

An electrochemically enhanced solid-phase microextraction approach based on a multi-walled carbon nanotubes/Nafion composite coating.

In this paper, we proposed an approach using a multi-walled carbon nanotubes (MWCNTs)/Nafion composite coating as a working electrode for the electrochemically enhanced solid-phase microextraction (EE-SPME) of charged compounds. Suitable negative and positive potentials were applied to enhance the extraction of cationic (protonated amines) and anionic compounds (deprotonated carboxylic acids) in aqueous solutions, respectively. Compared to the direct SPME mode (DI-SPME) (without applying potential), the EE-SPME presented more effective and selective extraction of charged analytes primarily via electrophoresis and complementary charge interaction. The experimental parameters relating to extraction efficiency of the EE-SPME such as applied potentials, extraction time, ionic strength, sample pH were studied and optimized. The linear dynamic range of developed EE-SPME-GC for the selected amines spanned three orders of magnitude (0.005-1mugmL(-1)) with R(2) larger than 0.9933, and the limits of detection were in the range of 0.048-0.070ngmL(-1). All of these characteristics demonstrate that the proposed MWCNTs/Nafion EE-SPME is an efficient, flexible and versatile sampling and extraction tool which is ideally suited for use with chromatographic methods.

A new strategy for basic drug extraction in aqueous medium using electrochemically enhanced solid-phase microextraction.

This work describes an electrochemically enhanced solid-phase microextraction (EE-SPME) method using a mild negative potential (-0.6 V) for the enhanced extraction of the selected basic drugs in a pure aqueous matrix and urine samples. The EE-SPME method gave a more effective extraction of drugs (primarily via electrophoresis and complementary charge interaction) compared to that obtained with SPME (without applying a potential, and which is based on passive partitioning). The EE-SPME method eliminated the need for alkalizing, derivatizing the drugs, or modifying the fiber coating before extraction. The analysis of methamphetamine (MA) and amphetamine (AM) was selected as a typical example to demonstrate in detail the advantages of EE-SPME over SPME. Based on the results obtained, 3-min extraction efficiency for both the amphetamines using EE-SPME was better than that of 30-min using SPME. The developed EE-SPME-GC method exhibited wide linear ranges (2-1000 ng mL(-1)) for both the amphetamines with R(2) larger than 0.99, and the method detection limits (MDLs) for AM and MA were 0.26 and 0.12 ng mL(-1), respectively. In addition, the EE-SPME method developed was also successfully applied to enhance the extraction of several other basic drugs (ephedrine, 3,4-methylenedioxyamphetamine (MDA), atropine, methadone, cocaine, codeine, acetylcodeine and papaverine) with preconcentration factors from 157 to 2199, indicating the potential applicability of this method in the field of forensic, clinical and pharmaceutical analysis.

Preparation of Reversible Colorimetric Temperature Nanosensors and Their Application in Quantitative Two-Dimensional Thermo-Imaging

Reversible colorimetric temperature nanosensors were prepared using a very simple precipitation method to encapsulate two color luminescent dyes. These nanosensors presented obvious reversible temperature response and enabled both rapid colorimetric temperature estimation using the eyes and quantitative two-dimensional thermo-imaging. Heat-exchange induced fluid motion was, for the first time, rapidly, precisely, and quantitatively imaged by just taking color pictures, and this presented good temporal and spatial resolution for studying heat-driven hydrodynamics. These nanosensors should have great application in micro/nanoscale research and also fabrication into films for macroscopic study.

Synthesis of highly fluorescent P,O-g-C3N4 nanodots for the label-free detection of Cu2+ and acetylcholinesterase activity

Highly fluorescent phosphorus, oxygen-doped graphitic carbon nitride nanodots (P,O-g-C3N4 nanodots) were synthesized using chemical oxidation and hydrothermal etching of bulk P-g-C3N4 obtained via pyrolysis of phytic acid and melamine. The P,O-g-C3N4 nanodots emitted strong blue fluorescence with a high quantum yield of 90.2%, and displayed high resistance to photobleaching and high ionic strength. A sensitive and facile fluorescence sensing approach for Cu2+ was developed through fluorescence quenching based on the static fluorescence quenching and photoinduced electron transfer. Under optimal conditions, a rapid detection of Cu2+ could be completed in 5 min with a detection limit of 2 nM, and a linearity ranging from 0 to 1 μM. Using acetylthiocholine (ATCh) as the substrate, the fluorescence of the P,O-g-C3N4 nanodots–Cu2+ system could be sensitively turned on in the presence of acetylcholinesterase (AChE) through the reaction between Cu2+ and thiocholine, the hydrolysis product of ATCh by AChE. A linearity ranging from 0.01 to 3 mU mL−1 could be obtained with a detection limit of 0.01 mU mL−1. In addition, the proposed approach showed potential application for the detection of Cu2+ in natural water samples and AChE activity in human plasma.