Yuezhong Wen

Highly efficient detoxification of Cr(VI) by chitosan-Fe(III) complex: process and mechanism studies.

Metal-biopolymer complexes has recently gained significant attention as an effective adsorbent used for the removal of Cr(VI) from water. Unfortunately, despite increasing research efforts in the field of removal efficiency, whether this kind of complex can reduce Cr(VI) to less-toxic Cr(III) and what are the mechanisms of detoxification processes are still unknown. In this study, despite the highly adsorption efficiency (maximum adsorption capacity of 173.1 mg/g in 10 min), the significant improvement of Cr(VI) reduction by chitosan-Fe(III) complex compared with normal crosslinked chitoan has been demonstrated. In addition, the structure of chitosan-Fe(III) complex and its functional groups concerned with Cr(VI) detoxification have been characterized by the powerful spectroscopic techniques X-ray absorption fine structure (XAFS) and X-ray photoelectron spectroscopy (XPS). The XPS spectra indicated that the primary alcoholic function on C-6 served as an electron donor during Cr(VI) reduction and was oxidized to a carbonyl group. The X-ray adsorption near edge spectra (XANES) of the Cr(VI)-treated chitosan-Fe(III) complex revealed the similar geometrical arrangement of Cr species as that in Cr(III)-bound chitosan-Fe(III). Overall, a possible process and mechanism for highly efficient detoxification of Cr(VI) by chitosan-Fe(III) complex has been elucidate.

Enantioselectivity Tuning of Chiral Herbicide Dichlorprop by Copper: Roles of Reactive Oxygen Species

Reactive oxygen species (ROS) are considered to be the key players in cell toxicity. However, cross talk between the enantioselective toxicity of pesticides, heavy metals, and ROS is poorly understood. To decipher the puzzle, the effects of copper (Cu) on the enantioselective ecotoxicity of the chiral pesticide dichlorprop (DCPP) to Scenedesmus obliquus were investigated. The results showed that the presence of DCPP and Cu, both individually and in combination, caused a sudden increase of ROS. This in turn stimulated the response of antioxidant defenses, impaired subcellular structure and physiological function, and finally resulted in cell growth inhibition. In the absence of Cu, ROS production after exposure to the herbicidally active (R)-enantiomer was higher than that of the (S)-enantiomer, suggesting a preference for an (R)-enantiomer-induced production of ROS. When DCPP and Cu were both added to algae simultaneously, (R)-DCPP preferentially induced production of ROS was observed. However, the enantioselective induced production of ROS was reversed when DCPP was mixed with Cu for 24 h prior to addition to the algae solution. It was also found that the generation of ROS, antioxidant response, and growth inhibition rate in Scenedesmus obliquus were all (R)-enantiomer preferentially induced. These findings implied that ROS play a primary role in chemical contaminant toxicity, and interactions between contaminants can tune the enantioselectivity of chiral herbicides, which should be considered in future risk assessment.

Antioxidant defense system responses and DNA damage of earthworms exposed to Perfluorooctane sulfonate (PFOS)

The use of earthworms as a sublethal endpoint has significantly contributed to the ecological risk assessment of contaminated soils. Few studies have focused on the potential toxicity of PFOS to earthworms in the soil. In this work, artificial soils were tested, and contact filter paper studies were used. The results showed that earthworm growth was generally inhibited. The antioxidant activities of the enzymes superoxide dismutase, peroxidase, catalase and glutathione peroxidase were initially activated and then inhibited. Reduced glutathione content was observed, and malondialdehyde content was elevated over the duration of the exposure. These results suggested that PFOS induced oxidative stress in earthworms. In addition, the values of olive tail moment, tail DNA% and tail length using SCGE showed similar frequency distributions and increased with increases in the PFOS concentration. These results suggest that all concentrations of PFOS cause DNA damage.

Effect of Chitosan on the Enantioselective Bioavailability of the Herbicide Dichlorprop to Chlorella pyrenoidosa

Chitosan, a natural polysaccharide, is widely regarded as a biocompatible and potential carrier for controlled-release drug formulations. However, the potential effect of chitosan on the environmental behavior of contaminants is poorly understood, especially on chiral chemicals. In this study, the changes in bioavailability of the chiral herbicide dichlorprop to Chlorella pyrenoidosa by chitosan were investigated. The dissipation of (S)-enantiomer in Chlorella pyrenoidosa culture media without chitosan was faster than that of the herbicidally active (R)-enantiomer, whereas it was inversed to (R)-enantiomer being faster than (S)-enantiomer when chitosan was added into the media. In the absence of chitosan, the toxicity of (R)-enantiomer to Chlorella pyrenoidosa was more potent than that of the (S)-enantiomer. On the contrary, in the presence of chitosan, (R)-enantiomer was less toxic than (S)-enantiomer. These observations clearly suggest that chitosan changed the enantioselective bioavailability of dichlorprop. Fluorescence spectroscopic analysis showed that the interaction between chitosan and dichlorprop enantiomers depended greatly on the steric structure of dichlorprop, which offers a possible explanation as to why the addition of chitosan changed the enantioselective dissipation of dichlorprop by Chlorella pyrenoidosa. This work suggests that the enantioselective behaviors of chiral compounds in the environment might be shifted when interactions with other chiral receptors coexist.

Efficient removal of dyes in water using chitosan microsphere supported cobalt (II) tetrasulfophthalocyanine with H2O2.

A new efficient catalyst, CoTSPc@chitosan, was developed by immobilizing water soluble cobalt (II) tetrasulfophthalocyanine onto adsorbent chitosan microspheres covalently for the heterogeneous catalytic oxidation of C. I. Acid Red 73 with H(2)O(2). The result indicated that the COD removal and discoloration of C. I. Acid Red 73 made 55 and 95% respectively in the presence of CoTSPc@chitosan with H(2)O(2) in 4h. In addition, CoTSPc@chitosan-H(2)O(2) system could proceed efficiently in a relatively wide pH range and remain high catalytic activity after 6 reuse cycles. Furthermore, the adsorption study of CoTSPc@chitosan confirmed that chitosan was an outstanding support which contributed a lot to the removal reaction. In conclusion, the combination of adsorption process and catalytic oxidation made the CoTSPc@chitosan-H(2)O(2) system achieve a simple, efficiently and environmentally friendly water treatment.

Glow discharge plasma in water: A green approach to enhancing ability of chitosan for dye removal

There is a need to explore effective and green approaches to enhancing the ability to use chitosan for contaminant removal for practical implementation of this technology. In the present study, glow discharge plasma (GDP), which has thus far been studied for degradation of contaminants, was used for the first time to pre-treat chitosan for dye removal in aqueous solution. The results show that the GDP treatment changed the morphology and crystallinity of chitosan particles, and the number of -CH(2) and -CH(3) groups in the chitosan samples increased. Various pretreatment parameters, including discharge current and time, played significant roles in the chitosan modification. It is observed that dye uptake in GDP-modified chitosan was faster than adsorption in untreated chitosan. The maximum adsorption by chitosan followed the order of untreated chitosan<modified chitosan (GDP current: 50 mA)<modified chitosan (GDP current: 120 mA), implying that the chitosan modified by GDP had a higher maximum adsorption capacity in comparison with the untreated chitosan. A possible mechanism is proposed. These results show that GDP may be an attractive pretreatment technology for environmental adsorption materials.

Facile, green encapsulation of cobalt tetrasulfophthalocyanine monomers in mesoporous silicas for the degradative hydrogen peroxide oxidation of azo dyes

A facile and green approach that improves the catalytic lifetime of cobalt tetrasulfophthalocyanine (CoTSPc) for the degradation of dyes is presented. Structurally ordered mesoporous silicas (MCM-41, MCM-48 and SBA-15), microporous aluminosilicates (ZSM-5) and macroporous alumina (γ-Al(2)O(3)) with different pore sizes were selected for the immobilization of CoTSPc, and a wide range of pH conditions (pH values from 4 to 12) were tested with the CoTSPc immobilization procedure. In the catalytic oxidation study, CoTSPc that was immobilized to MCM-41 silica (CoTSPc@MCM-41) prepared at a pH of 12 showed the longest catalytic lifetime. The TOC removal and discoloration of C. I. Acid Red 73 was approximately 60% and 82%, respectively, in the presence of CoTSPc@MCM-41 with H(2)O(2) after 3h. These results indicate that MCM-41, which has a matching size between its mesopores (30 Å) and CoTSPc molecules (25 Å), can prevent CoTSPc molecules from aggregating and improve its catalytic lifetime. In addition, the ability of CoTSPc@MCM-41 to degrade other dyes, and the reuse studies, demonstrated that CoTSPc@MCM-41 could be reused for the degradation of most common dyes.

Spectroscopic investigations of the chiral interactions between lipase and the herbicide dichlorprop

The enantioselective interaction between penicillium expansum alkaline lipase and chiral phenoxypropionic acid herbicide dichlorprop was studied by using UV differential spectrophotometry and fluorescence spectrophotometry in the presence of a pH 8, phosphate buffer solution. Chiral differences in the UV absorption and fluorescence spectra of lipase with dichlorprop were detected. (R)-Dichlorprop interacted the strongest with lipase as measured by both UV absorption and fluorescence spectrophotometry, followed by (Rac)-dichlorprop, while (S)-dichlorprop had the weakest interaction. The hydrophobic interaction seem to play the dominant role in the interactions and the (R)-enantiomer needed the minimum put of energy to drive the endothermic reaction, while the Rac-type and S-type compounds needed more for the reaction to take place. In the meantime, the catalytic hydrolysis of FDA with lipase show that (R)-DCPP could inhibit lipase the most strongly relatively at the same condition, perhaps because (R)-DCPP had a stronger combining effect and high enantiomeric selectivity on lipase than (Rac)-DCPP and (S)-DCPP.

Evaluation of the role of the glutathione redox cycle in Cu(II) toxicity to green algae by a chiral perturbation approach

The effect of heavy metal toxicity on the environment is usually linked to changes in the glutathione redox cycle and oxidative damage as causative events. However, it is unknown whether changes in the glutathione redox cycle are a cause or result of Cu(II) toxicity. Herein, a new chiral perturbation strategy involving a chiral herbicide, dichlorprop (DCPP), as a perturbation factor was used. According to the dose-response fitting curve of DCPP and the combination with Cu(II), 40 μM (R)-DCPP and (S)-DCPP, whose toxicities were low enough to not significantly perturb the Cu(II) toxicity, were selected as the chiral perturbation factor. When Scenedesmus obliquus was incubated with the chiral perturbation factor and 10 μM Cu(II), chiral perturbation was observed in the chlorophyll content and the PAM chlorophyll fluorescence. Then, the role of the glutathione redox cycle in the toxicity of Cu(II) was evaluated with the chiral perturbation approach. The results revealed that the GSH differences in algae cells exposed to (R)-DCPP or (S)-DCPP were well correlated with the differences in the production of reactive oxygen species (ROS) after exposure to the two enantiomers. When (R)-DCPP or (S)-DCPP was added with Cu(II) to the algae culture, treatment with (R)-DCPP-Cu resulted in a decrease in the GSH content in algae cells compared to the control, whereas treatment with (S)-DCPP-Cu resulted in an increase in the GSH. The GSH/GSSG ratio and GR activity also showed similar enantioselectivities. The enantioselectivities would not exist if the changes of in glutathione redox cycle were the cause. Therefore, these data provide indirect evidence that ROS induced cell toxicity of Cu is a causative event, which results in the response of the glutathione redox cycle. These results also provided an implication that before sustainable detoxification strategies for heavy metal pollutants were proposed, it is better that the roles of ROS production and glutathione redox cycle are elucidated. In this case, the chiral perturbation strategy may be a good choice.

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.