Rimao Hua

The occurrence and distribution of antibiotics in Lake Chaohu, China: Seasonal variation, potential source and risk assessment

The distribution and seasonal variation of fifteen antibiotics belonging to three classes (sulfonamides, fluoroquinolones and tetracyclines) were investigated in Lake Chaohu, China. The concentrations of the selected antibiotics in the surface water, eight major inflowing rivers and sewage treatment plant (STP) samples were analyzed by UPLC-MS/MS. The results indicated that sulfamethoxazole and ofloxacin were the predominant antibiotics, with maximum concentrations of 95.6 and 383.4ngL(-1), respectively, in the river samples. In Lake Chaohu, the western inflowing rivers (the Nanfei and Shiwuli Rivers) were the primary import routes for the antibiotics, and the domestic effluent from four STPs were considered the primary source of the antibiotics. The level of antibiotics in Lake Chaohu clearly varied with seasonal changes, and the highest detectable frequencies and mean concentrations were found during the winter. The quality of water downstream of Lake Chaohu was influenced by the lake, and the results of risk assessment of the antibiotics on aquatic organisms suggested that sulfamethoxazole, ofloxacin, ciprofloxacin and enrofloxacin in the surface water of Lake Chaohu and inflowing rivers might pose a high risk to algae and plants.

Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1

Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation.

Insecticidal Activity of Melaleuca alternifolia Essential Oil and RNA-Seq Analysis of Sitophilus zeamais Transcriptome in Response to Oil Fumigation.

Background The cereal weevil, Sitophilus zeamais is one of the most destructive pests of stored cereals worldwide. Frequent use of fumigants for managing stored-product insects has led to the development of resistance in insects. Essential oils from aromatic plants including the tea oil plant, Melaleuca alternifolia may provide environmentally friendly alternatives to currently used pest control agents. However, little is known about molecular events involved in stored-product insects in response to plant essential oil fumigation. Results M. alternifolia essential oil was shown to possess the fumigant toxicity against S. zeamais. The constituent, terpinen-4-ol was the most effective compound for fumigant toxicity. M. alternifolia essential oil significantly inhibited the activity of three enzymes in S. zeamais, including two detoxifying enzymes, glutathione S-transferase (GST), and carboxylesterase (CarE), as well as a nerve conduction enzyme, acetylcholinesterase (AChE). Comparative transcriptome analysis of S. zeamais through RNA-Seq identified a total of 3,562 differentially expressed genes (DEGs), of which 2,836 and 726 were up-regulated and down-regulated in response to M. alternifolia essential oil fumigation, respectively. Based on gene ontology (GO) analysis, the majority of DEGs were involved in insecticide detoxification and mitochondrial function. Furthermore, an abundance of DEGs mapped into the metabolism pathway in the Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway database were associated with respiration and metabolism of xenobiotics, including cytochrome P450s, CarEs, GSTs, and ATP-binding cassette transporters (ABC transporters). Some DEGs mapped into the proteasome and phagosome pathway were found to be significantly enriched. These results led us to propose a model of insecticide action that M. alternifolia essential oil likely directly affects the hydrogen carrier to block the electron flow and interfere energy synthesis in mitochondrial respiratory chain. Conclusion This is the first study to perform a comparative transcriptome analysis of S. zeamais in response to M. alternifolia essential oil fumigation. Our results provide new insights into the insecticidal mechanism of M. alternifolia essential oil fumigation against S. zeamais and eventually contribute to the management of this important agricultural pest.

Separation of Fenoxaprop-p-ethyl Biodegradation Products by HPTLC

Fenoxaprop-p-ethyl (Figure 1) is widely used in China as an active broad-spectrum herbicide for control of most grassy weeds. Several methods for determination of fenoxaprop-pethyl have been reported, including GC–ECD [1] and HPLC [2]. Ingelse et al. [3] separated fenoxaprop-p-ethyl and its enantiomers from ergot alkaloids by use of a capillary electrophoretic method. Although substantial research has been performed on the behavior of fenoxaprop-p-ethyl, there are no reports on the biodegradation or biodegradation products of fenoxaprop-p-ethyl.

A Simple and Effective Ratiometric Fluorescent Probe for the Selective Detection of Cysteine and Homocysteine in Aqueous Media.

Biothiols such as cysteine (Cys) and homocysteine (Hcy) are essential biomolecules participating in molecular and physiological processes in an organism. However, their selective detection remains challenging. In this study, ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate (NL) was synthesized as a ratiometric fluorescent probe for the rapid and selective detection of Cys and Hcy over glutathione (GSH) and other amino acids. The fluorescence intensity of the probe in the presence of Cys/Hcy increased about 3-fold at a concentration of 20 equiv. of the probe, compared with that in the absence of these chemicals in aqueous media. The limits of detection of the fluorescent assay were 0.911 μM and 0.828 μM of Cys and Hcy, respectively. 1H-NMR and MS analyses indicated that an excited-state intramolecular proton transfer is the mechanism of fluorescence sensing. This ratiometric probe is structurally simple and highly selective. The results suggest that it has useful applications in analytical chemistry and diagnostics.

HPTLC determination of imidacloprid, fenitrothion and parathion in Chinese cabbage

A simple, rapid, and sensitive high-performance thin-layer chromatographic method has been developed and validated for analysis of residues of imidacloprid, fenitrothion, and parathion in Chinese cabbage. The sample was extracted by sonication in an ultrasonic water bath with acetone—petroleum ether, 5:3 (v/v), and the extract was directly applied, as bands, to glass-backed silica gel 60F254 HPTLC plates. The plates were developed with hexane—acetone, 7 + 3 (v/v), in an unsaturated glass twin-trough Camag chamber. Evaluation of the developed HPTLC plates was performed densito-metrically with a Camag TLC Scanner 3 controlled by an external PC running Wincats software (Version 1.1.2). The results indicated that the detection limits of imidacloprid (RF = 0.10), fenitrothion (RF = 0.59), and parathion (RF = 0.70) were 5.0 × 10−9 g, 2.0 × 10−8 g, 1.0 × 10−8 g, respectively. Recoveries of the pesticides from Chinese cabbage by use of this analytical method were 80.04–85.22%, and RSD were 4.18–13.15%. The precision and accuracy of the method were generally fit for analysis of pesticide residues in Chinese cabbage.

A Simple and Rapid Turn On ESIPT Fluorescent Probe for Colorimetric and Ratiometric Detection of Biothiols in Living Cells

Biothiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), play a key role in an extensive range of physiological processes and biological functions. Therefore, the selective and sensitive detection of intracellular thiols is important for revealing cellular function. In this study, ethyl 2-(4-(acryloyloxy)-3-formylphenyl)-4-methylthiazole-5-carboxylate (NL-AC) was designed and synthesized as a colorimetric and ratiometric fluorescent probe that can be utilized to rapidly, sensitively and selectively detect biothiols in physiological media. The fluorescence intensity of this probe using the three target biothiols at a concentration of 20 equiv. of the probe increased by approximately 6~10-fold in comparison to that without the biothiols in aqueous solution. The limits of detection (LOD) for Cys, Hcy and GSH were 0.156, 0.185, and 1.838 μM, respectively. In addition, both 1H-NMR and MS analyses suggested the mechanism of fluorescence sensing to be excited-state intramolecular proton transfer (ESIPT). The novel colorimetric and ratiometric probe is structurally simple and offers detection within 20 min. Furthermore, this probe can be successfully applied in bioimaging. The results indicate high application potential in analytical chemistry and diagnostics.

Comparative Studies of Interactions between Fluorodihydroquinazolin Derivatives and Human Serum Albumin with Fluorescence Spectroscopy

In the present study, 3-(fluorobenzylideneamino)-6-chloro-1-(3,3-dimethylbutanoyl)-phenyl-2,3-dihydroquinazolin-4(1H)-one (FDQL) derivatives have been designed and synthesized to study the interaction between fluorine substituted dihydroquinazoline derivatives with human serum albumin (HSA) using fluorescence, circular dichroism and Fourier transform infrared spectroscopy. The results indicated that the FDQL could bind to HSA, induce conformation and the secondary structure changes of HSA, and quench the intrinsic fluorescence of HSA through a static quenching mechanism. The thermodynamic parameters, ΔH, ΔS, and ΔG, calculated at different temperatures, revealed that the binding was through spontaneous and hydrophobic forces and thus played major roles in the association. Based on the number of binding sites, it was considered that one molecule of FDQL could bind to a single site of HSA. Site marker competition experiments indicated that the reactive site of HSA to FDQL mainly located in site II (subdomain IIIA). The substitution by fluorine in the benzene ring could increase the interactions between FDQL and HSA to some extent in the proper temperature range through hydrophobic effect, and the substitution at meta-position enhanced the affinity greater than that at para- and ortho-positions.

High-performance thin-layer chromatographic determination of carbamate residues in vegetables

A high-performance thin-layer chromatographic method has been developed for determination of four carbamate residues in vegetables. The method uses two mobile phases on silica gel 60 F254 GLP HPTLC layers, and detection at λ = 243 nm and 207 nm, the average wavelengths of maximum adsorption of pirimicarb and methomyl, and carbaryl and carbofuran, respectively. Recovery of 1.0–5.0 mg kg−1 of the four mixed carbamates from wax gourd and potatoes was 70.05–103.7%. The accuracy and precision of the method were confirmed by means of fortification experiments.

Enhanced degradation of prometryn and other s-triazine herbicides in pure cultures and wastewater by polyvinyl alcohol-sodium alginate immobilized Leucobacter sp. JW-1

The s-triazine herbicides, such as prometryn, have been widely used in agriculture and have raised much public concern over their contamination of water and soil. Leucobacter sp. JW-1 cells were immobilized in polyvinyl alcohol‑sodium alginate (PVA-SA) beads and then used to degrade prometryn. Orthogonal array experiments showed that the optimal immobilization conditions of PVA-SA immobilized Leucobacter sp. JW-1 beads (PSLBs) were 3% JW-1 cells (w/v, wet weight), 10-12% (w/v) PVA, 2-3% (w/v) calcium chloride, and an immobilization time of 24-36h. The PSLBs were more tolerance to pH, temperature and salinity changes than free JW-1 cells and were stable and effective for degrading prometryn through six reuse cycles without losing their degradation capacity. The half-life of prometryn degradation by PSLBs at 100mgL-1 in pesticide plant wastewaters were 1.1-6.9h. The rate constants of prometryn degradation by PSLBs in wastewaters ranged from 304 to 576mgL-1day-1, which were approximately 1.25-118 times those of degradation by free JW-1 cells. The PSLBs degraded 99.9% of atrazine, 99.9% of ametryn, 97.8% of propazine, 100.0% of simetryn, 77.9% of simazine, 98.9% of terbuthylazine, 95.2% of prometon, 98.9% of atraton, and 31.6% of terbumeton at an initial concentration of 50mgL-1 of each herbicide in 2days. This study indicates that PSLBs persistently biodegrade s-triazine herbicides better than JW-1 free cells, and can be an efficient, safe and reusable biomaterial for the removal of s-triazine herbicides from contaminated sites.