酞酸二丁酯表面印迹聚合物的合成及其吸附性能

以酞酸二丁酯(DBP)作为模板分子,甲基丙烯酸作为功能单体,乙二醇二甲基丙烯酸酯(EDMA)作为交联剂,在硅胶表面合成分子印迹聚合物(MIPs)。通过红外、热重分析、比表面积测定等对聚合物进行分析和表征;采用静态吸附法对水相中的印迹聚合物的吸附性能进行考察.红外结果表明硅胶表面存在对模板分子具有识别功能的官能团;热重分析证明其良好的热稳定性;通过测定计算印迹膜厚度;静态吸附实验说明印迹聚合物具有良好的吸附性能.     

Removal of bis(2-ethylhexyl) phthalate at a sewage treatment plant

Bis(2-ethylhexyl) phthalate (DEHP) concentrations were measured at different stages in a full-scale sewage treatment plant (STP) and mass balances were calculated. The DEHP load to treatment process coming from the sewer system and the internal load comprising returned supernatants and filtrate from sludge treatment and excess secondary sludge were at the same level. The DEHP removal efficiency from the water phase at the STP was on average 94% of sewage DEHP, the main removal process being sorption to primary and secondary sludges. On average 29% of DEHP was calculated to be removed in the biological nitrifying-denitrifying activated sludge process, which was much less than expected from laboratory biodegradation studies described in literature. Monoethylhexyl phthalate, the primary biotransformation product of DEHP, was not detected at any treatment stage. Approximately 32% of DEHP in sewage was removed during anaerobic digestion of the sludge, while 32% remained in the digested and dewatered sludge.     

二乙基羟胺-臭氧体系降解邻苯二甲酸二甲酯的机理学研究

本研究采用二乙基羟胺（DEHA）促进臭氧（O3）降解水中邻苯二甲酸二甲酯（DMP）,并建立了强化O3氧化能力的O3/DEHA体系。主要探索了在O3/DEHA体系中pH、DEHA投量、臭氧通量和DMP投量对该体系的影响及体系的氧化机理,并通过气相色谱/质谱（GC/MS）对DMP的降解产物进行了分析。结果表明：DEHA能够有效促进臭氧的分解且在酸性条件下（pH=3）明显提高DMP的降解率,DEHA投量为25μΜ时促进效果最佳;DMP降解速率随臭氧通量的增加而增加,随DMP浓度的增加而减小,通过动力学计算,该反应符合拟一级动力学反应;投加叔丁醇（TBA）能够明显抑制DMP的降解,验证了在酸性条件下,·OH对DMP的降解起主要作用;通过产物分析可推导出O3/DEHA体系中DMP 的降解途径主要从苯环上碳链的断裂开始,中间生成酸类和脂类化合物,最终矿化为水和二氧化碳。     

新型阴离子表面活性剂PS的室内研究

根据油田泡沫驱的需要,研制出了新型阴离子表面活性剂PS(邻苯二甲酸单月桂醇酯钠盐)。对PS进行了定量、定性分析和红外光谱分析。测定了PS的表面张力和临界胶束浓度(cmc)值,用Rose-Mile法考察了PS的起泡性能。结果表明,70℃时PS溶液的临界胶束浓度为0.20％,此时表面张力为2.5×10-4N／cm;PS的起泡性能优于常用的SDS和ABS表面活性剂,70℃下PS含量为0.20％时,溶液起泡高度可达180 mm以上。这说明PS是一种综合性能优良的高效起泡剂,在油田三次采油中具有广阔的应用前景。     

用苯酐下脚料合成邻苯二甲酸二甲酯

苯酐下脚料经研碎后,在固体超强酸SO42-/MoO3-TiO2催化下,与甲醇直接酯化,经过滤、减压蒸馏可制得邻苯二甲酸二甲酯(DMP)。较佳反应条件为:在搅拌下,w(催化剂)=1.0%,甲醇/苯酐(摩尔比)=2.7:1,反应温度140℃,反应时间3h;减压蒸馏压力≤10.0kPa(绝对压力)。苯酐转化率可达95%以上,催化剂易分离并可重复使用。     

Adsorption of Acidic Impurities From Organic Esters Using Basic Ion Exchange Resins as Functionalized Polymers

Abstract

Sorption of acidic impurities from diethyl phthalate and butyl acetate using basic resins, bearing tertiary amino groups on a styrene‐divinylbenzene macroporous matrix, has been investigated for purification of the esters. The equilibrium studies show selective sorption of the acidic impurities and a high loading capacity (in the range of 2.2–5.3 mol/kg of dry resin) even at millimolar acid concentrations. The uptake of the acids is assisted by specific Lewis acid‐base interaction with the functional group of the resins. The interaction leads to formation of a hydrogen bonded complex between the acidic proton and the lone pair of electrons on the nitrogen of the amino group. The sorption studies have also been performed in ethanol and butyl alcohol to evaluate their use for the regeneration of the resins and recovery of the acids. The sorption data have also been analyzed using extended Flory‐Huggin theory of polymer solutions to determine the interaction parameters between different components.     

A facile method for preparation of high performance Pt catalyst supported on multi-wall carbon nanotubes for methanol electrooxidation

Due to the inherent inertness of multi-wall carbon nanotubes (MWCNTs), complicated procedures are involved in the preparation of MWCNT-supported catalysts. In this paper, a facile and effective method is introduced to prepare Pt nanoparticles dispersed on the surface of purified MWCNTs. In this method, sodium phthalate (SP) is used as a special additive to function as an effective cross linker between MWCNTs and Pt ions, and ethylene glycol (EG) aqueous solution is used as an effective solvent. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses reveal that the prepared face-centered cubic Pt nanoparticles with the average diameter of 2.2 nm are well dispersed on the surface of the MWCNTs. Cyclic voltammetry and chronoamperometry tests demonstrate that the Pt/MWCNTs catalyst obtained from typical experiment exhibits better catalytic activity and stability for methanol electrooxidation than the Pt catalyst supported on conventional acid-treated MWCNTs (AO-MWCNTs) and JM commercial 20% Pt/C catalyst.     

气相色谱-三重四级杆串联质谱同时测定香精中22种邻苯二甲酸酯

建立了固相萃取法结合气相色谱-三重四级杆串联质谱同时检测香精中22种邻苯二甲酸酯(PAEs)残留量的方法。样品经乙腈和正己烷混合溶液提取,固相萃取小柱净化,然后进行测定,内标法定量。结果表明,22种邻苯二甲酸酯在3~1000 μg/L范围内呈线性相关关系,判定系数R² ≥ 0.9922。方法检出限为0.3~1.0 μg/kg,方法定量限为1.0~3.0 μg/kg。添加20、40和200 μg/kg三个不同浓度水平,香精中22种邻苯二甲酸酯加标回收率为82.4%~107.1%,相对标准偏差为≤ 9.1%(n=6)。用此建立的方法测定了实际香精样品中的22种邻苯二甲酸酯,检出率为45.0%。此方法操作简单,灵敏度高和准确度高,适用范围广,适合香精中22种邻苯二甲酸酯残留量的检测。     

气相色谱质谱法(GC/MS)检测饲料中的20种塑化剂残留

建立气相色谱-质谱（GC/MS）法测定和确证饲料中塑化剂的残留量。试样用正己烷提取,气相色谱分离、质谱选择离子方式（SIM）对20种邻苯二甲酸酯进行定性,内标法定量分析。该方法操作简单、准确可靠、重现性良好,各种邻苯二甲酸酯化合物的方法检出限为10.2⁷01μg/kg,加标回收率为80%¹09%,相对标准偏差为1.0%⁵.9%,能够满足饲料中邻苯二甲酸酯类化合物含量的测定。      

First Identification of a Large Set of Serine Hydrolases by Activity-Based Protein Profiling in Dibutyl Phthalate-Exposed Zebrafish Larvae

Despite the involvement of several serine hydrolases (SHs) in the metabolism of xenobiotics such as dibutyl phthalate (DBP), no study has focused on mapping this enzyme class in zebrafish, a model organism frequently used in ecotoxicology. Here, we survey and identify active SHs in zebrafish larvae and search for biological markers of SH type after exposure to DBP. Zebrafish were exposed to 0, 5, and 100 µg/L DBP from 4 to 120 h post-fertilization. A significant decrease in vitellogenin expression level of about 2-fold compared to the control was found in larvae exposed to 100 µg/L DBP for 120 h. The first comprehensive profiling of active SHs in zebrafish proteome was achieved with an activity-based protein profiling (ABPP) approach. Among 49 SHs identified with high confidence, one was the carboxypeptidase ctsa overexpressed in larvae exposed to 100 µg/L DBP for 120 h. To the best of our knowledge, this is the first time that a carboxypeptidase has been identified as deregulated following exposure to DBP. The overall results indicate that targeted proteomics approaches, such as ABPP, can, therefore, be an asset for understanding the mechanism of action related to xenobiotics in ecotoxicology.