Guosheng Chen

Carbon Nanotubes Act as Contaminant Carriers and Translocate within Plants

Nanotechnology permits broad advances in agriculture. However, as it is still at a relatively early stage of development, the potential risks remain unclear. Herein, for the first time, we reveal the following: 1) the impact of multi-walled carbon nanotubes (MWCNTs) on the accumulation/depuration behaviors of contaminants in crop, mustard (Brassica juncea), and 2) the permeability and transportability of MWCNTs in intact mature mustard plants. Using an in vivo sampling technique, the kinetic accumulation/depuration processes of several contaminants in mustard plans exposed to MWCNTs were traced, and an enhancement of contaminant accumulation in living plants was observed. Meanwhile, we observed that the MWCNTs permeated into the roots of intact living plants (three months old) and were then transported to the upper organs under the force of transpiration steam. This study demonstrated that MWCNTs can act as contaminant carriers and be transported to the edible parts of crops.

Hollow fiber based liquid phase microextraction for the determination of organochlorine pesticides in ecological textiles by gas chromatography–mass spectrometry

In this study, the hollow fiber-liquid phase microextraction (HF-LPME) coupled gas chromatograph/mass spectrometry (GC/MS) was firstly developed to determine 10 organochlorine pesticides (OCPs) in ecological textiles. The present method can offer high separation efficiencies with minimal sample and solvent consumption. The extraction conditions were optimized, including the types of hollow fiber and organic solvent, the extraction time, the stirring and the salinity. Under the optimized conditions, the linear ranges of OCPs in cotton, terylene and fur samples were 5-1000 ng/g, 10-1000 ng/g and 10-800 ng/g, respectively, and the detection limit of the three samples were 0.07-2.30 ng/g, 0.89-1.66 ng/g and 0.06-1.04 ng/g, respectively. The optimized method was then successfully used to determine the OCPs in 3 kinds of spiked real samples, including cotton, terylene and fur. The good recoveries and RSDs of the quantification in real textile samples were obtained and the results were confirmed by the traditional liquid extraction method (GB/T 18412-2006). This study proved that the HF-LPME method, which was simple, low-cost and virtually solvent-free, was reliable for the qualitative and quantitative analysis of the harmful OCP residues in ecological textiles.

Environmental fates of synthetic musks in animal and plant: An in vivo study.

As emerging contaminants, synthetic musks (SMs) cause worldwide concern due to their bioaccumulation in biota. However, the environmental fates of SMs in biota are poorly understood. Here, for the first time, the uptake and elimination behaviors, as well as the transferable capacities, of SMs in living edible biota (fish and aloe) were revealed. Fish muscle was approximately 100-2000 times more efficient in accumulating SMs than was aloe leaf, and nitro musks showed a higher bioaccumulation potential than did polycyclic musks in biota. In addition, the transferable capabilities of SMs by root uptake in aloe were poor. This investigation also showed that both nitro musks and polycyclic musks that accumulated in biota exhibited excellent elimination rates in clean water, and the elimination rates were greater than 78% and 80% in fish (3 d) and aloe (2 d), respectively. Furthermore, the calculated results suggest that SMs might act as chemosensitizers and enhance the accumulation of normally excluded toxicants in biota in a real aquatic environment.

Bioinspired Polyelectrolyte-Assembled Graphene-Oxide-Coated C18 Composite Solid-Phase Microextraction Fibers for In Vivo Monitoring of Acidic Pharmaceuticals in Fish

A novel solid-phase microextraction (SPME) fiber was prepared by gluing poly(diallyldimethylammonium chloride) (PDDA) assembled graphene oxide (GO)-coated C18 composite particles (C18@GO@PDDA) onto a quartz fiber with polyaniline (PANI). The fiber surface coating was sequentially modified with bioinspired polynorepinephrine, which provided a smooth biointerface and makes the coating suitable for in vivo sampling. The novel custom-made coating was used to extract acidic pharmaceuticals, and high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was employed for analysis. The custom-made coating exhibited a much higher extraction efficiency than the previously used commercial polydimethylsiloxane (PDMS) and polyacrylate (PA) coatings. The custom-made coating also possessed satisfactory stability (the relative standard deviations (RSDs) ranged from 1.60% to 10.3% for six sampling-desorption cycles), interfiber reproducibility (the RSDs ranged from 2.61% to 11.5%), and resistance to matrix effects. The custom-made fibers were used to monitor the presence of acid pharmaceuticals in dorsal-epaxial muscle of living fish, and satisfactory sensitivities (limits of detection ranged from 0.13 ng/g to 7.56 ng/g) were achieved. The accuracies were verified by the comparison with liquid extraction. Moreover, the novel fibers were successfully used to monitor the presence of acidic pharmaceuticals in living fish, which demonstrated that the custom-made fibers were feasible for possible long-term in vivo continuous pharmaceutical monitoring.

In Situ Hydrothermally Grown TiO2@C Core-Shell Nanowire Coating for Highly Sensitive Solid Phase Microextraction of Polycyclic Aromatic Hydrocarbons

Nanostructured materials have great potential for solid phase microextraction (SPME) on account of their tiny size, distinct architectures and superior physical and chemical properties. Herein, a core-shell TiO2@C fiber for SPME was successfully fabricated by the simple hydrothermal reaction of a titanium wire and subsequent amorphous carbon coating. The readily hydrothermal procedure afforded in situ synthesis of TiO2 nanowires on a titanium wire and provided a desirable substrate for further coating of amorphous carbon. Benefiting from the much larger surface area of subsequent TiO2 and good adsorption property of the amorphous carbon coating, the core-shell TiO2@C fiber was utilized for the SPME device for the first time and proved to have better performance in extraction of polycyclic aromatic hydrocarbons. In comparison to the polydimethylsiloxane (PDMS) and PDMS/divinylbenzene (DVB) fiber for commercial use, the TiO2@C fiber obtained gas chromatography responses 3-8 times higher than those obtained by the commercial 100 μm PDMS and 1-9 times higher than those obtained by the 65 μm PDMS/DVB fiber. Under the optimized extraction conditions, the low detection limits were obtained in the range of 0.4-7.1 ng L-1 with wider linearity in the range of 10-2000 ng L-1. Moreover, the fiber was successfully used for the determination of polycyclic aromatic hydrocarbons in Pearl River water, which demonstrated the applicability of the core-shell TiO2@C fiber.

In vivo tracing of organochloride and organophosphorus pesticides in different organs of hydroponically grown malabar spinach (Basella alba L.)

An in vivo uptake and elimination tracing study based on solid phase microextraction (SPME) was conducted to investigate the accumulation, persistence and distribution of organochloride pesticides (OCPs) and organophosphorus pesticides (OPPs) in malabar spinach (Basella alba L.) plants. Uptake and elimination of the pesticides were traced in leaves, stems and roots of living malabar spinach plants. Root concentration factor (RCF), distribution concentration factor (DCF) and transpiration stream concentration factor (TSCF) were calculated based on the in vivo tracing data. The tracing data showed that the OCPs were much more accumulative and persistent than the OPPs in roots, while they were similarly accumulative and persistent in leaves and stems. RCF values of the OPPs or OCPs were likely to increase with the increase in LogKow values except fenthion. Obtained DCF values indicated that OPPs and OCPs were more accumulative in the organs containing more lipids. TSCF values showed that the translocation of OPPs and OCPs from roots to foliage was firstly dependent on the hydrophobicity of the compounds, but also significantly affected by the water solubility. This is the first study of generating RCF, DCF and TSCF data in living plants by in vivo sampling method, which provides a foundation to promote the application of in vivo SPME and improve understanding of contaminant behaviors in living plants.

Boronate Affinity-Molecularly Imprinted Biocompatible Probe: An Alternative for Specific Glucose Monitoring.

A biocompatible probe for specific glucose recognition is based on photoinitiated boronate affinity-molecular imprinted polymers (BA-MIPs). The unique pre-self-assembly between glucose and boronic acids creates glucose-specific memory cavities in the BA-MIPs coating. As a result, the binding constant toward glucose was enhanced by three orders of magnitude. The BA-MIPs probe was applied to glucose determination in serum and urine and implanted into plant tissues for low-destructive and long-term in vivo continuous glucose monitoring.

In vivo tracing of organophosphorus pesticides in cabbage (Brassica parachinensis) and aloe (Barbadensis)

In vivo solid-phase microextraction (SPME) sampling method coupled with gas chromatography-mass spectrometry (GC-MS) analysis was employed to trace the uptake and elimination of organophosphorus pesticides (OPPs) in two kinds of edible plants, cabbage (Brassica parachinensis) and aloe (Barbadensis). The metabolism of fenthion in aloe was also investigated by the liquid chromatography tandem mass spectrometry analysis (LC-MS/MS) to understand the fate of OPPs in living plants better. Transpiration stream concentration factor (TSCF) and depuration rate constants of the OPPs in living plants were obtained therein. The health risk of the OPPs treated aloe was estimated by the maximum residue limit (MRL) approach, and it revealed that the OPPs were rather safe for their fast degradable property. However, peak concentration of fenthion-sulfoxide was found to exceed the MRL and was higher than that of the parent fenthion, which indicated the potential risk of pesticide metabolites. This study highlighted the application of in vivo SPME for contaminant tracing in different living edible plants. The in vivo tracing method is very convenient and can provide more data to evaluate the risk of different pesticides, which are very important for the safety of agriculture production.

Sulfonated nanoparticles doped electrospun fibers with bioinspired polynorepinephrine sheath for in vivo solid-phase microextraction of pharmaceuticals in fish and vegetable.

In this study, the biocompatible copolymer Poly(lactic acid-co-caprolactone) (PLCL) doped with sulfonated γ-Al2O3 nanoparticles was used for electrospun on stainless wires. The electrospun fibers were further sheathed by the self-polymerization of norepinephrine, a catecholamine found both in neurotransmitters and mussel adhesive proteins, to improve the surface hydrophilicity and provide a smooth bio-interface. The modified electrospun fibers on stainless wires were developed as novel custom-made solid-phase microextraction (SPME) fibers. These fibers exhibited much higher extraction efficiency compared to the polydimethylsiloxane (PDMS) fibers, especially to the sulfonamides. The custom-made SPME fibers also showed excellent stability with the relative standard deviations (RSDs) of intra-fiber ranged from 1.98% to 9.86% and RSDs of inter-fiber ranged from 4.36% to 15.6%. Moreover, these fibers were also demonstrated to be anti-biofouling and suitable for in vivo sampling. The custom-made SPME fibers were successfully applied to determine the Pharmaceutical concentrations in living fishes and vegetables. The accuracies were verified by the comparison with liquid extraction and the sensitivities were demonstrated to be satisfying with the limits of detection (LODs) ranged from 0.16ng/g to 5.35ng/g in fish muscle and 0.02ng/g to 8.02ng/g in vegetable stem.

Rapid detection of five anesthetics in tilapias by in vivo solid phase microextraction coupling with gas chromatography-mass spectrometry

The concentration of five rapidly metabolized anesthetics in living tilapias was determined in this study, by the presented method coupling in vivo solid phase microextraction (SPME) to gas chromatography-mass spectrometry (GC-MS), which was the first time that in vivo sampling method was adapted in detecting the anesthetic residue in the living aquatic product. The analytical performance of the developed method was evaluated in homogenized tilapia dorsal muscle, and the results demonstrated that the present method possessed low detection limits 1.7-9.4ngg-1), wide linear ranges (10 or 30-5000ngg-1), and satisfactory reproducibility (relative standard deviations no more than 8.1% and 10.8% for inter-fiber and intra-fiber assays, respectively). Standard curves were established in homogenized tilapia dorsal muscle for calibrating in vivo SPME in living tilapias. And the concentrations determined by in vivo SPME were close to those determined by the liquid extraction. By using the present method, one anesthetic residue was detected above the detection limit in tilapias from the local markets. Comparing to traditional methods, the present one exhibited superior time-efficiency and cost performance, as the extraction time was only ten minutes, which was short to successfully avoid the possible loss of analytes caused by elimination and sample storage. In addition, owing to the time-efficiency of the present method, the elimination of the anesthetics in tilapias was traced successfully in the laboratory.