链状高分子金属配合物催化氧化苯乙烯

利用链状Salen型高分子希夫碱金属配合物PLSBM(M:CoⅡ,MnⅡ,ZnⅡ,CuⅡ)作为催化剂,催化分子氧氧化苯乙烯.结果表明,在不添加任何助剂和共还原剂的条件下,氧化产物以苯甲醛(Ⅰ)和环氧苯乙烷(Ⅱ)为主,PLSBCuⅡ具有最佳的催化活性和产物选择性.考察了影响氧化反应的因素,发现在反应温度为90℃、反应时间为9h和催化剂与苯乙烯用量比为1mg∶2mL时,苯乙烯具有最优的转化率(61％)和产物选择性(Ⅰ:57％,Ⅱ:36％).     

日光/H2O2/草酸铁络合物光解水溶液中的直接耐酸大红

以H2O2/草酸铁络合物作光氧化剂,利用太阳光对水溶液中的直接耐酸大红进行了光氧化降解试验研究。结果表明,在日光照射下,H2O2/草酸铁络合物能使溶液中直接耐酸大红迅速光解,晴天光照15min或阴天光照30-40min,溶液（直接耐酸大红的质量浓度为50mg/L）可褪至无色;溶液的初始pH对染料光解有显著影响;pH为2-4时光解效果最佳;提高H2O2浓度可以提高光解速率,但H2O2的利用率会降低。     

Effects of lindane on the photosynthetic apparatus of the cyanobacterium<Emphasis Type="Italic">anabaena</Emphasis>

INTENTION, GOAL, SCOPE, BACKGROUND: Cyanobacteria have the natural ability to degrade moderate amounts of organic pollutants. However, when pollutant concentration exceeds the level of tolerance, bleaching of the cells and death occur within 24 hours. Under stress conditions, cyanobacterial response includes the short-term adaptation of the photosynthetic apparatus to light quality, named state transitions. Moreover, prolonged stresses produce changes in the functional organization of phycobilisomes and in the core-complexes of both photosystems, which can result in large changes in the PS II fluorescence yield. The localization of ferredoxin-NADP+ reductase (FNR) at the ends of some peripheral rods of the cyanobacterial phycobilisomes, makes this protein a useful marker to check phycobilisome integrity. OBJECTIVE: The goal of this work is to improve the knowledge of the mechanism of action of a very potent pesticide, lindane (gamma-hexaclorociclohexane), in the cyanobacterium Anabaena sp., which can be considered a potential candidate for bioremediation of pesticides. We have studied the effect of lindane on the photosynthetic apparatus of Anabaena using fluorescence induction studies. As ferredoxin-NADP+ reductase plays a key role in the response to oxidative stress in several systems, changes in synthesis, degradation and activity of FNR were analyzed. Immunolocalization of this enzyme was used as a marker of phycobilisome integrity. The knowledge of the changes caused by lindane in the photosynthetic apparatus is essential for rational further design of genetically-modified cyanobacteria with improved biorremediation abilities. METHODS: Polyphasic chlorophyll a fluorescence rise measurements (OJIP) have been used to evaluate the vitality and stress adaptation of the nitrogen-fixing cyanobacterium Anabaena PCC 7119 in the presence of increasing concentrations of lindane. Effects of the pesticide on the ultrastructure have been investigated by electron microscopy, and FNR has been used as a marker of phycobilisome integrity. RESULTS AND DISCUSSION: Cultures of Anabaena sp. treated with moderate amounts of lindane showed a decrease in growth rate followed by a recovery after 72 hours of pesticide treatment. Concentrations of lindane below 5 ppm increased the photosynthetic performance and activity of the cells. Higher amounts of pesticide caused a decrease in these activities which seems to be due to a non-competitive inhibition of PS II. Active PS II units are converted into non-QA reducing, so called heat sink centers. Specific activity and amount of FNR in lindane-treated cells were similar to the values measured in control cultures. Release of FNR from the thylakoid after 48 hours of exposure to 5 ppm of lindane towards the cytoplasm was detected by immunogold labeling and electron microscopy. CONCLUSIONS: From these results, we conclude that the photosynthetic performance and activity of the cells are slightly increased in the presence of lindane up to 5 ppm. Moreover, in those conditions, lindane did not produce significant changes in the synthesis, degradation or activity of FNR. The high capability of Anabaena to tolerate lindane makes this cyanobacterium a good candidate for phytoremediation of polluted areas. RECOMMENDATION AND OUTLOOK: The results of this study show that cultures of Anabaena PCC 7119 tolerate lindane up to 5 ppm, without significant changes in the photosynthetic vitality index of the cells. However, a slight increase in phycobiliprotein synthesis is observed, which is related to total protein content. This change might be due to degradation of proteins less stable than phycobiliproteins. An identification of the proteins with altered expression pattern in the presence of the pesticide remains the subject of further work and will provide valuable information for the preparation of strains which are highly tolerant to lindane.     

几种草酸铁络合物体系光降解酞酸酯比较研究

文章在比较研究了几种草酸铁络合物体系对两种酞酸酯DBP和DEHP的光催化降解情况.结果表明:草酸铁络合物和草酸铁络合物/H2O2体系在遮光条件下对DBP和DEHP没有降解作用.在中性pH值条件下,DBP和DEHP在几种反应体系中的降解速率依次为:UV/草酸铁络合物/H2O2＞UV/H2O2＞UV/草酸铁络合物＞UV＞太阳光/草酸铁络合物.UV与草酸铁络合物对DBP和DEHP光降解的协同作用不强,增强因子f分别为1.20和1.07.UV、草酸铁络合物与H2O2的对DBP光降解协同作用也不明显,增强因子f=1.18. UV与H2O2对DBP光降解存在明显的协同作用,增强因子f=8.78.     

Speciation analysis of aluminium in plant parts of Betula pendula and in soil

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection(HPIC-DAD). The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium–fluoride complexes: AlF_((x = 2,3,4))~((3-x))(first analytical signal), AlF~(2+)(second analytical signal) and Al~(3+)(third analytical signal) in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact:contaminated site of the Chemical Plant in Luboń and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF_((x = 2,3,4))~((3-x))had the largest contribution, followed by Al~(3+)and AlF~(2+). Significant differences in concentration and contribution of Al–F complexes and Al~(3+)form, depending on the place of sampling(different anthropogenic pressure) and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is "blocked" by lateral roots, and is closely related to Al content of soil.     

Sorption behavior of bensulfuron-methyl on andisols and ultisols volcanic ash-derived soils: Contribution of humic fractions and mineral-organic complexes

Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R² 0.969-0.998). K_f for soils (8.3-20.7 μg^1−1/n mL^1/n g⁻¹) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest K_f for HA, FA and HUM were 539.5, 82.9, and 98.7 μg^1−1/n mL^1/n g⁻¹. Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH₂⁺ and SO⁻ sites of sorbents.     

Effects of fluoride on the removal of cadmium and phosphate by aluminum coagulation

This study focuses on the effects of pH and fluoride at different molar ratios of fluoride to Al (R_F:Al) on the removal of cadmium (Cd²⁺) and phosphate by Al coagulation. Fluoride at R_F:Al ≥ 3:1 inhibits the removal of Cd over wide Al dose ranges from 5 to 10 mg/L as Al. The removal of phosphate decreases significantly at high R_F:Al of 10:1 whereas at lowered R_F:Al (i.e., ≤ 6:1), an adverse effect is observed only at insufficient Al doses below 2 mg/L. Fluoride shows inhibitive effects towards the removal of Cd at pH 7 and 8 and that of phosphate at pH 6. Fluoride decreases the ζ-potential in both systems, and the decreasing extent is positively correlated to the elevated R_F:Al. The Al fluoride interactions include the formation of Al–F complexes and the adsorption of fluoride onto Al(OH)₃ precipitates, i.e., the formation of Al(OH)_nF_m. Al–F complex formation inhibits Al hydrolysis and increases residual Al levels, and a more significant increase was observed at lower pH. Al–F complexes at high R_F:Al complicate the coagulation behavior of Al towards both negative and positive ionic species. Moreover, fluoride at low R_F:Al shows little effect on Al coagulation behavior towards Cd^2 + and phosphate, and the spent defluoridation adsorbent, i.e., aluminum (Al) hydro(oxide) with adsorbed fluoride at R_F:Al of below 0.1:1, may be reclaimed as a coagulant after being dissolved.     

Adsorption of picloram on clays nontronite,illite and kaolinite: equilibrium and herbicide-clays surface complexes

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite?<?illite?<?nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.     

Preliminary Studies on Converting Agricultural Waste into Biodegradable Plastics,Part I: Corn Distillers’ Dry Grain

Distillers dry grain (DDG) was derivatized either by carboxymethylation, glutaration, maleiation, phthallation, or succination in order to produce anionic materials suitable for complexation with soy protein isolate. Infrared spectroscopy confirmed that derivatization of DDG by all reagents was successful. Blending of derivatized anionic products with soy protein resulted in instant precipitation of gels. The gels were centrifuged, molded, and dried into solid pellets with tensile strengths as high as 1.67MPa, suggesting that these materials could be promising as biodegradable structural materials. Infrared spectroscopy suggested the possibility of complexes forming between soy protein isolate and each of the derivatized DDG samples.     

UV/草酸铁络合物光解对硫磷的研究

研究了紫外光（UV）/草酸铁络合物对对硫磷的光解作用,结果表明,UV/草酸铁络合物能快速有效地光解对硫磷,且较UV/TiO2的光解效果好。对硫磷光解率随着其初始浓度的增加而降低;pH为3-5时其光解速率最快;[Fe(Ⅲ）]与[OX^2-]之比（OX^2-代表草酸根）和溶液中的溶解氧对其光解有显著影响。