影响邻苯二甲酸二甲酯在黄河水体颗粒物上吸附行为的主要因素

研究了邻苯二甲酸二甲酯 ( DMP)在黄河水体颗粒物上吸附行为的影响因素。结果表明 ,酸度、器壁对酯吸附的影响可以忽略 ,吸附平衡时间以

邻苯二甲酸单甲酯双核铜配合物的强反铁磁性和磁构关联研究

以邻苯二甲酸单甲酯(mMP)为配体合成了一个新的双核铜配位化合物[Cu_2(mMP)_2(H_2O)_2]_2·2H_2O(1),并通过元素分析、红外光谱和X射线单晶衍射等方法对化合物晶体结构进行了表征.化合物1通过四羧酸桥联的方式形成了桨轮状双金属笼结构.每个Cu(Ⅱ)离子采用四方单锥的五配位构型,其中四个氧原子来自于四个不同的邻苯二甲酸单甲酯配体,轴向位置上的氧原子则来自于水分子.配化水分子和溶剂水分子与配体中未配位的氧原子形成了分子间氢键,并进一步形成三维网络结构.磁性数据显求双核铜内为强的反铁磁交换作用,磁耦合作用常数2J=-324 cm^(-1).通过与相关双核铜化合物的对比,详细分析了化合物的磁构关联并讨论了羧酸类双核铜中强反铁磁性作用的结构因素.研究表明,影响羧酸类双核铜强反铁磁性作用的主要结构因素是配体中桥联双核铜的O-C-O部分的电子结构.

邻苯二甲酸单甲酯对大鼠血液生化指标的影响及毒理研究

随着塑化剂邻苯二甲酸酯的大量使用,其代谢产物邻苯二甲酸单酯普遍存在于环境中。目前,邻苯二甲酸酯类代谢物(mPAEs)对生物体的危害已引起广泛关注,然而其对血液的毒性效应还不明确。本研究以邻苯二甲酸单甲酯(MMP)为对象,选用Sprague-Dawley(SD)大鼠为实验动物,通过检测大鼠血液中血细胞数量和血液生化指标考察MMP(低剂量50 mg·kg^(-1)、中剂量250 mg·kg^(-1)、高剂量500 mg·kg^(-1))的血液毒性,并从氧化应激的角度探究机制。结果表明:(1)染毒3 h后,3个剂量染毒组SD大鼠血液中的红细胞和白细胞数量均低于对照组。其中,高剂量组二者数量较对照组分别下降9.13%和43.56%。对于淋巴细胞和中性粒细胞数目,高剂量组二者分别比对照组低26.4%和30.7%。这说明MMP会使血细胞减少,进而会损害血液的携氧和免疫等功能。(2)染毒24 h(禁食12 h)和连续染毒7 d后,3个剂量MMP均使大鼠血清中总胆固醇和总蛋白含量较对照组有所下降;染毒24 h后,高剂量MMP使二者分别降低36.67%和18.25%;连续染毒7 d后,高剂量组二者分别降低43.97%和26.35%。与对照组相比,3个剂量MMP染毒组的大鼠血浆中尿素氮含量及血清中酸性磷酸酶活性在染毒24 h后均降低,高剂量MMP使二者分别下降34.33%和41.37%;连续染毒7 d后,高剂量组二者分别比对照组降低28%和31.43%。这说明MMP会对血脂的新陈代谢以及肾、肝功能产生影响。(3)染毒3 h后,随着MMP剂量的增加,大鼠血液中超氧化物歧化酶(SOD)和过氧化氢酶(CAT)活性均呈现下降趋势,高剂量组二者活性较对照组分别下降17.5%和58%。3个剂量MMP使丙二醛(MDA)含量均高于对照组,其中低剂量组MDA含量比对照组高70%。这说明MMP会破坏机体氧化抗氧化平衡,引发氧化应激反应。

气相色谱法测定2-乙基己基氯甲酸酯含量

建立2-乙基己基氯甲酸酯的测定方法,采用气相色谱内标法,在AC-1石英毛细管上,利用FID检测分离,测定2-乙基己基氯甲酸酯含量。其标准偏差在0.1%~0.17%,回收率在97.9%~100%,样品与内标的质量比在0.7~2.1之间有较好的线性,结果表明,待测物在所建立的色谱条件下有良好的分离,该方法简单快速,灵敏度高,满足定量分析的要求。

邻苯二甲酸二甲酯免疫层析快速检测试纸的研制

邻苯二甲酸酯类塑化剂是一类具有生殖毒性的环境激素类物质,通过违规添加或迁移而造成食品污染问题颇为严峻,开发适合现场的塑化剂快速监测方法非常重要。本研究以邻苯二甲酸二甲酯(DMP)为对象,建立了DMP的胶体金标记免疫层析检测试纸方法。采用柠檬酸三钠还原氯金酸制备了胶体金,将其标记DMP多克隆抗体,制备了金标抗体;采用棋盘法和单因素试验确定最佳包被浓度和二抗浓度分别为3000μg/mL和1600μg/mL,抗体浓度为稀释1.4倍,基于此建立了DMP免疫层析快速检测方法,其检测限为0.4μg/mL,5 min内肉眼可观察到检测结果,与其它结构功能类似物无明显交叉反应,特异性良好,白酒样品添加检测结果与GC-MS法相符。本法快速简单,稳定可靠,适用于实际样品中DMP的现场快速检测。

邻苯二甲酸单甲酯桥联双核铜(Ⅱ)配合物磁性的理论研究

采用对称性破损态方法结合密度泛函理论,选用典型的强反铁磁双核配合物作为研究对象,通过与实验数据相比较,探讨了不同密度泛函方法与基组对计算铜配合物[Cu2(mMP)4(H2O)2]·H2O交换耦合常数的准确度.结果表明,4种混合密度泛函DFT(B3LYP,B3P86,B3PW91和PBE0)的计算结果都能和实验所观察到的值-324cm-1符号一致,但B3PW91方法得到的结果和实验结果吻合程度最好,同时采用方法B3PW91方法计算所得的交换耦合常数Jab对基组的依赖性较大.研究表明,2个Cu(Ⅱ)离子之间的反铁磁相互作用主要源于单占据分子轨道SOMOs大的能量劈裂和桥联配体O-C-O轨道的重叠.

MIP-MSPD-UPLC法测定塑料玩具中的邻苯二甲酸单甲酯

以对模板分子具有较强识别特性的分子印迹聚合物为基质固相分散吸附剂,提取塑料玩具中邻苯二甲酸单甲酯,用UPLC法测定。研究了邻苯二甲酸单甲酯分子印迹聚合物对样品中邻苯二甲酸单甲酯的提取和净化效果,在优化条件下,方法的检出限为0.19ng/mL,定量限为0.51ng/mL,不同邻苯二甲酸单甲酯添加量的回收率>94.9%,RSD<3.6%。方法适用于塑料玩具中邻苯二甲酸单甲酯的测定。

邻苯二甲酸酯类首批化学对照品的标定及其色谱检测方法的建立

目的：对供含量测定用的6种邻苯二甲酸酯类首批化学对照品进行标定,同时建立检测该类物质的色谱方法。方法：结合文献,应用UV、IR、NMR和ESI-MS等谱学技术对邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二正丁酯（DBP）、邻苯二甲酸二正戊酯（DAP）、邻苯二甲酸二异戊酯（DIAP）、邻苯二甲酸二环己酯（DCHP）和邻苯二甲酸二（2-甲氧乙基）酯（DMEP）6种邻苯二甲酸酯类化学对照品的结构进行鉴定,采用高效液相色谱法（HPLC）和气相色谱法（GC）进行纯度分析,利用质量平衡法进行定值;利用HPLC和GC同时检测多种邻苯二甲酸酯类化合物。结果：HPLC法测得DMP、DBP、DAP、DIAP、DCHP、DMEP的纯度分别为99.4%、99.9%、99.5%、99.9%、99.9%、99.2%,GC法测得其纯度分别为99.6%、100.0%、99.4%、99.9%、100.0%、99.1%。在选定的HPLC色谱条件下,12种邻苯二甲酸酯类化合物的检测限为0.05-0.40μg·m L^-1,定量限为0.20-1.20μg·m L^-1,RSD为0.6%-0.9%;在选定的GC色谱条件下,其检测限为0.12-1.28μg·m L^-1,定量限为0.47-4.28μg·m L^-1,RSD为2.2%-2.7%。结论：建立了6种邻苯二甲酸酯类首批化学对照品;初步建立检测12种邻苯二甲酸酯类化学成分的HPLC和GC的方法,为该类化学成分的检测提供一定的参考依据。

C10重芳烃二乙苯的分离研究

本文以C10重芳烃为原料,先采用精馏的方法获得间二乙苯、对二乙苯的富液,然后采用萃取精馏的方法,选择一种有效的萃取剂,将间二乙苯和对二乙苯的分离系数增大,以提高分离效率,减少能耗,获得较高的纯度和收率。

壳聚糖接枝物改性胶原蛋白海绵状敷料的制备与表征

以胶原蛋白(Col)为载体,壳聚糖(CS)和羟丙甲纤维素邻苯二甲酸酯(HPMCP)的接枝共聚物CS-gHPMCP为性能改良剂,采用冷冻干燥工艺制备不同CS-g-HPMCP含量的Col/CS-g-HPMCP复合海绵状敷料,并利用扫描电子显微镜对其多孔结构进行表征,探讨不同CS-g-HPMCP含量对复合海绵状敷料的溶胀率、溶失率、透湿量以及力学性能的影响。结果表明,随着CS-g-HPMCP含量的增加,复合海绵状敷料的溶胀率总体上增大,溶失率总体上降低,透湿量、拉伸强度和断裂伸长率先升高后降低。当CS-g-HPMCP质量分数为60%时,复合海绵状敷料的溶胀率为313.7%,溶失率为27.4%,透湿量为5 282.3g/(m2·d),拉伸强度和断裂伸长率最高,分别为45.6MPa和23.9%,其各项性能优异,是具有应用潜力的海绵状医用敷料。

Analysis of the major components of root exudates released from several economic forest tree using GC-MS

In 2000 and 2001, 1-year-old seedlings of 7 economic tree species including chestnut, apricot, persimmon, peach, walnut, pear and apple were cultured in garden pots that had a diameter of 40 cm and were filled with clean sand. The major components of exudates released from their roots were isolated and analysed by GC-MS. Totally 200 kinds of organic chemicals were isolated, of which 3 kinds i.e. naphthalene, dimethylbenzene and dibutyl phthalate were principally controlled pollutants according to 'Blacklist of Principal Environment Pollutants in China' and the standard of U.S. Environmental Protection Agency (EPA). The research result provided theoretical evidence for selecting low-pollution economic forest crops in the water source protection area in Miyun Reservoir.

CS-HPMCP接枝共聚物的制备

以壳聚糖(CS)和羟丙甲纤维素邻苯二甲酸酯(HPMCP)为原料,通过1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDC)/N-羟基琥珀酰亚胺(NHS)偶联剂制备CS-HPMCP接枝共聚物,利用傅里叶变换-红外光谱仪,紫外可见分光光度计,接触角测量仪,差式扫描量热仪,X射线衍射仪对该接枝共聚物进行表征,判断接枝是否成功,测量接枝率并考察了接枝后亲水性、热稳定性、结晶性的变化。结果表明:通过接枝,改善了HPMCP与CS作为单体的性能,当CS分子量为50 000、HPMCP用量为1 g、EDC/NHS质量比为2∶1时,接枝共聚物中HPMCP的接枝率达到最大值73.42%。通过接枝改性使CS与HPMCP在各项性能上相互改善相互促进,从而获得性能更优异的生物医用材料。

Characterization of V_2O_5/MoO_3 composite photocatalysts prepared via electrospinning and their photodegradation activity for dimethyl phthalate

Vanadium pentoxide（V2O5）/molybdenum trioxide（MoO 3） composites with different molar ratios of vanadium（V） to molybdenum（Mo） were synthesized via a simple electrospinning technique. The photocatalytic activity of the composites were evaluated by their ability to photodegrade methylene blue and dimethyl phthalate（DMP） under visible-light irradiation. Compared with pure V2O5 and MoO 3,the V2O5/MoO 3 composites showed enhanced visible-light photocatalytic activity because of a V 3d impurity energy level and the formation of heterostructures at the interface between V2O5 and MoO 3. The optimal molar ratio of V to Mo in the V2O5/MoO 3 composites was found to be around 1/2. Furthermore,high-performance liquid chromatographic monitoring revealed that phthalic acid was the main intermediate in the photocatalytic degradation process of DMP.

Toxic effects of several phthalate esters on the embryos and larvae of abalone Haliotis diversicolor supertexta

As the most widely used plasticizers in the world, phthalate esters （PAEs） are potential endocrine disruption compounds （EDCs）. In the present study, the toxicity of dimethyl phthalate （DMP）, diethyl phthalate （DEP）, dibutyl phthalate （DBP）, di （2-ethylhexyl） phthalate （DEHP） on embryogenesis and larvae development of the marine univalve Haliotis diversicolor supertexta was examined in laboratory. The results show that the malformation of embryos appeared during the experiment, such as embryos died or lysed, small transparent flocculent rings studded on the periphery of the embryo, and the larvae could failed to hatch. In embryo toxic test, embryos incubated at the highest concentration of DMR DEP and DBP solutions showed significantly high abnormal rate compared with the control, while DEHP solutions displayed no significant difference. In larval toxic test, in all concentrations of DMP, DEP and DBP solutions, larval settlement rates were low significantly than that of the control. Similarly, DEHP solutions show nearly no effect on the larval settlement. The order of toxicity on embryos and larvae is DBP〉DEP〉DMP〉DEHE Being a simple and easy stimulation to indoor spawn, sensitive to environmental factors, and short culture time, the embryos of H. diversicolor supertexta can be used to indicate toxicity of the PAEs.

Isolation and characteristics of Arthrobacter sp.strain CW-1 for biodegradation of PAEs

Isolation of new bacterial strains and recognition of their metabolic activities are highly desirable for sustainability of natural ecosystems. Biodegradation of dimethyl phthalate （DMP） under anoxic conditions has been shown to occur as a series of sequential steps using strain CW-1 isolated from digested sludge of Sibao Wastewater Treatment Plant in Hangzhou, China. The microbial colony on LB medium was yellowish, 3-5 mm in diameter, convex in the center, and embedded in mucous externally. The individual cells of strain CW-1 are irregular rods, measuring （0.6-0.7）×（0.9-1.0） pm, V-shaped, with clubbed ends, Gram positive and without any filaments. 16S rDNA （ 1438 bp） sequence analysis showed that the strain was related to Arthrobacter sp. CW-1 and can degrade PAEs utilizing nitrate as electron acceptor, but cannot mineralize DMP completely. The degradation pathway was recommended as： dimethyl phthalate （DMP）→monomethyl phthalate （MMP）--,phthalic acid （PA）. DMP biodegradation was a first order reaction with degradation rate constant of 0.3033 d 1 and half-life 2.25 d. The DMP conversion to PA by CW-1 could be described by using sequential kinetic model.

Mechanistic studies on peroxymonosulfate activation by g-C3N4 under visible light for enhanced oxidation of light-inert dimethyl phthalate

Excitation of metal-free graphitic carbon nitride(g-C3N4) under visible light can successfully achieve efficient activation of peroxymonosulfate(PMS). Synergistic effects and involved mechanism were systematically investigated using a light-inert endocrine disrupting compound, dimethyl phthalate(DMP), as the target pollutant. Under visible light irradiation, DMP could not be degraded by direct g-C3 N4-mediated photocatalysis, while in the presence of PMS, the dominant radicals were converted from ·O2 to SO4·– and ·OH, resulting in effective DMP degradation and mineralization. Results showed that higher dosage of PMS or g-C3 N4 could increase the activation amount of PMS and corresponding DMP degradation efficiency, but the latter approach was more productive in terms of making the most of PMS. High DMP concentration hindered effective contact between PMS and g-C3 N4, but could provide efficient use of PMS. Higher DMP degradation efficiency was achieved at p H lower than the point of zero charge(5.4). Based on intermediates identification, the DMP degradation was found mainly through radical attack(·OH and SO4·–) of the benzene ring and oxidation of the aliphatic chains.

Aerobic biodegradation of diethyl phthalate by Acinetobacter sp. JDC-16 isolated from river sludge

A gram negative bacterium,named JDC-16,which can grow well on the substrate of phthalic acid esters(PAEs) as the sole source of carbon and energy,was isolated from river sludge.Based on the morphology,physiological and biochemical properties and analysis of 16S rRNA gene sequence,it was preliminarily identified belonging to the genus Acinetobacter.The result of substrates utilization range indicates that strain JDC-16 can utilize a variety of phthalates except for diisononyl phthalate(DINP) .The degradation tests using diethyl phthalate(DEP) as the model compound show that the optimal pH and temperature for DEP degradation by Acinetobacter sp.JDC-16 is 8.0 and 35℃,respectively.Meanwhile,degradation kinetics under various initial concentrations of DEP reveals that substrate depletion curves fit well with the modified Gompertz model with high correlation coefficient(R 2 >0.99) .Furthermore,the substrate induction test indicates that DEP-induction can apparently shorten the lag phase and enhance the degradation rate.This work highlights the potential of this isolate for bioremediation of phthalates-contaminated environments.

A preliminary study on total removal efficiency of organic pollutants in sewage by Harbin municipal sewage treatment plant

To evaluate the removal efficiency of organic pollutants in the sewage by Harbin municipal sewage treatment plant, the influent and effluent samples from the plant were pretreated by liquid-liquid extraction （LLE） under conditions of acidity, neutrality and alkaleseence in sequence, and then were analyzed by gas chromatograph-mass spectrum （GC-MS） procedures. Results indicate that there are 70 species of organic pollutants in the influent sample of the plant, which mainly consist of alkyls, benzene series, esters, and heteroeyclic compounds. Some of these organic pollutants are biotoxie and belong to persistent organic pollutants （POPs）. Four species among them are on the list of Prior Pollutants of Environmental Protection Agency of USA （USEPA）. However, 7 species of organic pollutants appearing in the effluent sample mainly include alkyls of multi-carbons and phthalate esters. The removal efficiency of phthalates is poor because of their poor biodegradability. The sewage treatment technique is effective in removing most＋of organics pollutants.

Study on Modification of Octyl-α-Cyanoacrylate Medical Adhesive

Objective:In order that the adhesive character could be improved to modify the octyl-α-cyanoacrylate(OCA) medical adhesive.Methods:Suitable modifiers involving polycaprolactone(PCL),dibutyl phthalate (DBP),dioctyl phthalate(DOP) and poly octyl methacrylat(POMA) have been chosen to modify the OCA adhesive,then tensile shear strength and adhesive strength are tested to evaluate the bond character of adhesives.Results:The PCL group's tensile shear strength and adhesive strength in normal temperature are descended while the other groups'are all enhanced.Conclusion:The modification of properties of the other groups is effectively promoted in the aspect of the bond character,except the PCL group treated in normal temperature and the PCL modified group treated by rectification get a best improvement in the agglutinate intention, while the stability is expected to be improved.

花生四烯酸甘油酯双重微胶囊化及性质表征

利用喷雾干燥法,以花生四烯酸甘油酯为原料制备微胶囊化产品;应用肠溶性壁材羟丙甲纤维素邻苯二甲酸酯(HPMCP)对所得一次微胶囊产品进行二次微胶囊化,得到肠溶性微胶囊。对两种微胶囊化产品性质进行测定、对比。结果表明:一次微胶囊化产品表面含油率低(1.79%)、包埋效果良好(94.03%),性能稳定;二次微胶囊化产品经长达4h人工胃液处理,油脂释放率仅为5.81%,耐人工胃液性能良好。所得肠溶性花生四烯酸甘油酯微胶囊的耐胃液性质有效地减少了花生四烯酸甘油酯少量变质引起的摄入后不适现象。