有机磷农药生物降解技术研究进展

有机磷农药是目前国内外使用较多的化学农药,对人、畜均有毒性。长期以来,人们努力寻找降解有机磷农药的方法,以去除其对人类生活的不利影响。对现有的有机磷农药种类、毒性、生物降解技术以及现有成果进行了系统的归纳和总结,并对有机磷农药生物降解的进一步研究提出了建议。     

七株有机磷农药降解菌的降解特性比较

对分离自同一有机磷农药污染土壤的7株有机磷农药降解菌的降解特性进行了比较,7株降解菌都能利用甲基对硫磷为唯一碳源生长,并生成中间代谢产物对硝基苯酚.对硝基苯酚的降解经过一段延滞期,不同菌株降解对硝基苯酚的能力和延滞期有很大差异.降解菌株对多种有机磷类农药和芳香族化合物具有降解能力,其降解谱表现了一定的差异.用PCR方法从7株降解菌中克隆了有机磷农药水解酶基因.     

气相色谱法测定蔬菜中有机磷农药残留的前处理方法比较

采用液-液萃取、索氏提取和基质固相分散3种不同的方法对青椒样品进行前处理，用毛细管气相色谱法对处理后样品中的DDV、甲拌磷、甲基-对硫磷和马拉硫磷等农药残留进行测定，并对不同前处理方法的回收率和精密度进行比较。结果：3种方法的回收率和RSD相当，但基质固相分散操作较为方便简单、溶剂消耗量少。     

蔬菜中有机磷农药残留的分光光度法快速检测

以鸡脑为酶源提取乙酰胆碱酯酶,利用酶抑制分光光度法检测蔬菜中有机磷农药残留量.用此方法测定了对硫磷、辛硫磷、氧化乐果三种农药,结果满意,回收率分别达到97%,101%和99%.     

海水中溶解有机磷化合物的生态效应

介绍了海水中溶解有机磷的生物效应及其分析方法。有机磷农药在农业中得到广泛应用并被雨水冲刷进入海水中。农药生产企业排放的污染物已经严重污染近海水体。讨论了有机磷农药的毒性机理和有效利用的方法。     

瘤胃微生物强化醋糟厌氧消化及其机制

针对醋糟中木质纤维素利用效率低的问题,通过接种瘤胃微生物可强化木质纤维素水解.采用逐步提升体系有机负荷的方式,考察瘤胃微生物生物强化对醋糟厌氧消化性能的提升效果,并运用绝对定量实时聚合酶链锁反应（Q-PCR）技术探究其微生物学强化机制.结果表明:长期连续运行成功塑造了高效的木质纤维素瘤胃强化体系.该体系的最高有机负荷达8.90 g/（L·d）（以VS计）,是强化前的1.53倍,该有机负荷下半纤维素和纤维素降解率分别达73.9%和40.1%,单位质量底物沼气和甲烷产量相应地分别达到451和261 mL/g（以VS计）,半纤维素和纤维素较高的降解率是该体系维持高产气性能的主要原因.生物相机制研究表明,瘤胃微生物强化体系中与木质纤维素水解密切相关的GH5（糖苷水解酶家族5）水解菌逐步富集,其基因拷贝数从初始的964×1010 copies/g升至最高有机负荷下的6.83×1011 copies/g,这是底物在高有机负荷下仍能被高效生物转化的根本原因.研究显示,瘤胃微生物的介入可有效强化体系底物的降解能力,促进醋糟产甲烷性能的提升.      

气相色谱法测定土壤和沉积物中12种有机磷农药

建立了索氏提取-固相萃取（SPE）小柱净化-GC-NPD测定土壤和沉积物中的12种有机磷农药的方法。用正己烷-丙酮（9：1）进行索氏提取，SPE硅胶小柱净化，15 mL乙酸乙酯洗脱。适用于土壤和沉积物的干样和湿样中12种有机磷农药的测定，取样量为10 g时，方法检出限为0.304~1.469 μg/kg，样品加标平均回收率为67.10%~109.8%，相对标准偏差为3.39%~14.7%。     

Insights into the structure of urea-like compounds as inhibitors of the juvenile hormone epoxide hydrolase (JHEH) of the tobacco hornworm Manduca sexta: analysis of the binding modes and structure-activity relationships of the inhibitors by docking and CoMFA calculations

Substituted urea compounds are well-known as potent inhibitors of juvenile hormone epoxide hydrolase (JHEH) of the tobacco hornworm Manduca sexta. Docking simulations of 47 derivatives inside JHEH were performed to gain insight into the structural characteristics of these complexes. The obtained orientations show a strong similitude with the observed in the known X-ray crystal structures of human soluble epoxide hydrolase (sEH) complexed with dialkylurea inhibitors. In addition, the predicted inhibitor concentration (IC₅₀) of the above-mentioned compounds as JHEH inhibitors were obtained by a quantitative structure-activity relationship (QSAR) method by using comparative molecular field analysis (CoMFA) applied to aligned dataset. The best models included steric and electrostatic fields and had adequate predictive abilities. In addition, these models were used to predict the activity of an external test set of compounds that was not used for building the model. Furthermore, plots of the CoMFA fields allowed conclusions to be drawn for the choice of suitable inhibitors.     

有机磷降解酶的固定化及其工业化应用初探

采用一种新型的酶固定化方法，在大孔微球中对有机磷降解酶（OPHC2）固定化，制备固相载体化的交联酶聚集体固定化酶。对具有实际应用意义的参数：热稳定性、牢固度和连续反应批次进行了重点研究。结果表明，有机磷降解酶固定化酶的半衰期在70℃时比游离酶提高了2.1倍。固定化酶分别在37℃的摇床中经14 h高速振荡，以及在pH 8、37℃条件下循环反应49个批次降解甲基对硫磷后，均未发现固定化酶酶活力下降。在37℃，有机磷降解酶固定化酶柱以每小时3倍柱床体积的速率对甲基对硫磷农药乳油的稀释液（甲基对硫磷含量为216 mg/L）进行降解处理，系统连续工作156 h，甲基对硫磷的降解率保持在98.4%～99.9%。     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.