溶剂萃取-GC-MS/MS测定水中邻苯二甲酸二（2-乙基己基）酯

目的 建立简便快速检测生活饮用水及水源水中邻苯二甲酸二（2-乙基己基）酯（DEHP）的GC-MS/MS测定方法。方法 取100.0 mL水,加入2.00 mL正己烷,充分振荡提取,静置分层后,取正己烷层1.00 μL于GC-MS/MS定性定量测定。结果 该方法的检出限为0.000 02 mg/L,相对标准偏差＜3%,回收率在85.0%~103.3%之间。结论 该方法简便快速、准确可靠,适合于水样中DEHP的定量测定。     

不同烹调油样品中邻苯二甲酸二丁酯与邻苯二甲酸二（2-乙基己基）酯的分析

[目的]了解不同烹调油样品中邻苯二甲酸二丁酯（di-n—butyl phthalate,DBP）与邻苯二甲酸二（2-乙基己基）酯[di（2-ethylhexyl）phthalate,DEHP]的污染情况。[方法]采用气相色谱-质谱联用仪的选择离子检测（SIR）方式,测定取自居民家中未加热食用油、烹调剩油和厨房抽油烟机内油盒中的烹调油烟冷凝物,食堂中未加热食用油、烹调剩油和烹调油烟冷凝物;小摊贩所用的未加热食用油及其锅内剩油;快餐店未加热过的固体起酥油及烹调剩油等样品中DBP与DEHP的含量。[结果]9户居民家庭厨房和食堂不同烹调油样品中DBP和DEHP均为阳性,且烹调油烟冷凝物中的含量明显高于未加热食用油和烹调剩油中的含量;DBP和DEHP含量：前者分别为2．29～597．01μg／g和38．96～4774．72μg／g;后者分别为3．22～42．81μg／g和15．61～112．64μg／g。小摊贩和快餐店不同烹调油样品中,仅1例炸面食剩油检出DBP和DEHP。[结论]大部分烹调油样品被DBP、DEHP污染,且烹调油烟冷凝物中的含量大大增加。     

邻苯二甲酸二(2-乙基己基)酯毒性作用

邻苯二甲酸二(2 乙基己基)酯(DEHP)作为聚氯乙烯(PVC)等塑料制品的增塑剂,可增加塑料的弹性和韧性,被广泛应用于塑料工业。DEHP在塑料中是以游离的形式存在的,在重量上可达 30%~50%[1],很容易进入环境。作为环境污染物,可以在地表水、地下水、饮用水、空气、土壤及动、植物体内广泛检测到。目前的研究发现其毒性作用主要是作为内分泌干扰物,表现为生殖生长毒性、肝肾毒性及血液和生化方面的改变。随着DEHP产量的逐年增加,其在环境中的浓度也逐渐升高,对人体的毒性作用也越来越受到人们的关注[2]。目前对其健康效应方面的评价尚处…     

邻苯二甲酸二（２ 乙基己基）酯对小鼠肾脏损害及氧化应激机制的研究

摘要：目的　研究邻苯二甲酸二（２ 乙基己基） 酯（ＤＥＨＰ） 的肾脏毒性及氧化应激损伤作用机制;探讨
相关影响因素。方法　建立小鼠ＤＥＨＰ肾损伤模型：选择昆明４ 周龄小鼠６０ 只,体重（２０±２）ｇ,雌雄
各半,随机分为６ 组, 每组１０ 只。Ｏ 组为空白对照组,Ａ 组给予ＤＥＨＰ７５０ ｍｇ／ｋｇ,Ｂ 组给予ＤＥＨＰ
１５００ｍｇ／ｋｇ ,Ｃ 组给予３０００ ｍｇ／ｋｇＤＥＨＰ＋１０％ 维生素Ｃ,Ｄ 组给予ＤＥＨＰ３０００ ｍｇ／ｋｇ,Ｅ 组给予
３０００ｍｇ／ｋｇＤＥＨＰ＋０．５％ 尼古丁;经食饵和饮水连续自然给食染毒,于染毒第４周末处死。测量小鼠肾
脏和体质量的变化,检测不同ＤＥＨＰ染毒剂量组小鼠的血液、肾脏中谷胱甘肽过氧化物酶（ＧＰＸ）、过氧
化氢（Ｈ２Ｏ２）,丙二醛（ＭＤＡ）等变化。将实验数据进行单因素方差分析（ＡＮＯＶＡ）。结果　随着ＤＥＨＰ
染毒剂量的增加,小鼠体质量逐渐降低（犘＜０．０５）,高剂量组肾脏脏器系数呈现增加趋势。ＤＥＨＰ 高剂量
组ＨＥ 染色可见肾脏组织出现以明显充血和水肿为主的损伤,尼古丁干扰组最为严重。维生素Ｃ 呈现良好
的肾脏保护作用。氧化应激相关物质的改变：血液中的ＧＰＸ 活性由对照组的（４７１．３２±１２０．２４ ）Ｕ／ｍｌ降
低至Ｅ 组的（２０８．７５±５２．９２）Ｕ／ｍｌ （犘＜０．０５）,且有剂量 反应关系;肾脏中ＧＰＸ 活性降低（犘＜０．０５）,
同时肾组织中Ｈ２Ｏ２ 含量由（４０７．７４±３２８．８３）ｍｍｏｌ／ｍｇ蛋白增加到（１６７４．９８±３７６．０７）ｍｍｏｌ／ｍｇ蛋白
（犘＜０．０５）,血液中Ｈ２Ｏ２ 含量也随着ＤＥＨＰ 的剂量增加而增加（犘＜０．０５）;肾组织中ＭＤＡ 含量增加（犘
＜０．０５）;同时维生素Ｃ 的保护作用和尼古丁的协同作用也有体现。结论　ＤＥＨＰ 具有小鼠肾脏毒性,其
作用机制可能与氧化应激有关,抗氧化剂维生素Ｃ 对ＤＥＨＰ所致肾脏损伤具有抑制作用。
关键词：邻苯二甲酸二（２ 乙基己基）酯（ＤＥＨＰ）;肾脏毒性;氧化应激
中图分类号：Ｒ１２　　文献标识码：Ａ　　文章编号：１００９ ６６３９ （２０１４）０１ ０００８ ０５     

邻苯二甲酸二(2-乙基己基)酯生物降解研究进展

邻苯二甲酸二 (2 乙基己基 )酯是一种污染严重的有毒难降解有机物 ,自然降解能力很弱 ,降解过程主要为生物降解。运用微生物对其进行生物降解有着十分广阔的前景     

邻苯二甲酸（2—乙基己基）酯的致突变实验

邻苯二甲酸(2-乙基己基)酯(DEHP)作为一种增塑剂被广泛应用塑料制品、医疗器材、合成橡胶和工业涂料中,有所道认为对人类有潜在的致癌性。我们选择了Ames试验、小鼠骨髓嗜多染红细胞微核试验、小鼠骨髓细胞染色体畸变试验对其     

邻苯二甲酸二 -(2-乙基己基)酯对小鼠胚胎心肌细胞的毒性作用

邻苯二甲酸二 - ( 2 -乙基己基 )酯 [Di ( 2 - ethylhexyl)phthalate,DEHP]在全球被广泛用作 PVC ( polyvinylchloride)产品增塑剂 ,大量的动物实验表明 ,它是可能的致癌物、内分泌干扰物 ,同时具有生殖和发育毒性 [1 ,2 ] 。本课题组在植入后体外全胚胎培养实验中发现低剂量的 DEHP可通过胎盘直接影响器官形成期的小鼠胚胎发育 ,而心脏发育异常是最早出现的畸形。而先天性心脏病 (简称先心病 )是常见的出生缺陷之一 [3] ,鉴于母亲孕期接触外源性雌激素是先心病的一个危险因素 [4 ] ,推测内分泌干扰物 DEHP可能是先心病发生的危险因…     

邻苯二甲酸二（2-乙基己基）酯对雄性小鼠大脑皮质氧化损伤及Bcl-2、Bax蛋白表达的影响

选用ICR初断乳雄性小鼠40只,随机分为对照组(玉米油)和邻苯二甲酸二(2-乙基己基)酯(DEHP)(250、500、 1 000 mg/kg)染毒组,经口灌胃,6次/周,连续8周。于末次染毒24 h后处死动物,称取大脑质量并计算脏器系数;检测大脑皮质超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GSH-Px)的活性及丙二醛(MDA)的含量;Western Blot法检测Bcl-2和Bax蛋白表达水平。结果显示,1 000 mg/kg染毒组小鼠染毒1周时体重增长缓慢,与对照组差异有统计学意义(P005);染毒8周后其大脑系数高于对照组,差异有统计学意义(P005)。随着DEHP染毒剂量增加,大脑皮质组织匀浆中MDA含量增高,1 000 mg/kg染毒组与对照组差异有统计学意义(P005); 500、 1 000 mg/kg染毒组SOD活力高于对照组,差异有统计学意义(P005);各组GSH-Px活力与对照组差异无统计学意义(P005); DEHP各染毒组大脑皮质Bcl-2蛋白表达减少,500、 1 000 mg/kg剂量组Bax蛋白表达增高,与对照组比较差异均有统计学意义(P005)。提示DEHP可致小鼠大脑皮质氧化损伤及凋亡相关蛋白的改变。     

高效液相色谱法测定化妆品中邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基己基)酯的含量

目的：建立了高效液相色谱法测定化妆品中邻苯二甲酸二丁酯（DBP）和邻苯二甲酸二（2-乙基己基）酯（DE-HP）含量的方法。方法：采用固相萃取法处理样品，淋洗试剂为甲醇：乙醚=1：19。甲醇和水作为流动相，二极管阵列检测器测定DBP和DEHP。结果：DBP测定的线性范围为5．0～200μg／ml，线性相关系数为0．9993，DEHP测定的线性范围为5．5～220μg／ml，线性相关系数为0．9997。DBP的回收率范围在84％～93％，相对标准偏差为3．2％～4．8％。DE-HP的回收率范围在98％～105％，相对标准偏差为2．8％～4．7％。结论：该方法灵敏度高，结果准确而且稳定。     

生活饮用水中14种农药残留的全自动固相萃取-气相色谱质谱联用测定法

目的探索并建立生活饮用水中14种农药残留的固相萃取-气相色谱质谱联用(GC-MS)检测方法。方法通过全自动固相萃取提取水中农药残留,对固相萃取柱、水样pH值、洗脱溶剂种类与体积等进行优化。对比气相色谱-质谱-选择离子扫描模式(GC-MS-SIM)和气相色谱-质谱-多离子扫描模式(GC-MS-MRM)的检出限和灵敏度。结果采用C18固相萃取柱、水样pH调节在1～2之间进行萃取,用10 mL乙酸乙酯-二氯甲烷(V/V=1∶1)以0.5 m L/min的速度进行洗脱,所得的效果较佳。GC-MS-MRM检出限更低灵敏度更高。通过3个浓度水平的加标回收实验,在GC-MS-MRM扫描模式下,方法的回收率为70.9%～116.3%,相对标准偏差(RSD)为2.16%～6.39%,方法的检出限范围为0.000 1～0.050 0μg/L,定量限为0.000 3～0.150 0μg/L。结论本方法在样品前处理中有机溶剂使用量少,便于自动操作,检测结果准确,灵敏度高,能够应用于饮用水中多种农药检测。在优化条件下,GC-MS-MRM检测方法能有效满足水中痕量有机氯检测的要求。     

Determination of four metabolites of the plasticizer di (2-ethylhexyl) phthalate in human urine samples

Summary A method for biological monitoring of exposure to the plasticizer di(2-ethylhexyl)phthalate (DEHP) is described. In this method the four main metabolites of DEHP [i.e., mono (2-ethylhexyl) phthalate (MEHP), mono (5-carboxy-2-ethylpentyl)phthalate, mono(2-ethyl-5-oxohexyl)phthalate, and mono(2-ethyl-5-hydroxyhexyl)-phthalate] are determined in urine samples. The procedure includes enzymatic hydrolysis, ether extraction, and derivatization with triethyloxonium tetrafluoroborate. Analysis is performed by gas chromatography electron impact mass spectrometry. The detection limit for all four metabolites is less than 25 g/l urine. The coefficient of variation based on duplicate determinations of urine samples of workers occupationally exposed to DEHP was 16% for MEHP (mean concentration 0.157 mg/l) and 6% -9% for the other three metabolites (mean concentrations 0.130-0.175 mg/1). The method described here was used to study DEHP metabolism in man. Most persons excrete mono(2-ethyl-5-oxohexyl)-phthalate and mono (2-ethyl-5-hydroxyhexyl)phthalate as a (glucuronide) conjugate. Mono (5-carboxy-2-ethyl-pentyl)phthalate is mainly excreted in free form, while for MEHP a large interindividual variation in conjugation status was observed. Of the four metabolites quantified, 52% are products of a ((-l)-hydroxylation reaction of MEHP [i.e., mono (2-ethyl-5-oxohexyl)phthalate and mono (2-ethyl-5-hydroxyhexyl)phthalate], 22% is the product of a -hydroxylation reaction of MEHP [i.e., mono (5-carboxy-2-ethylpentyl)phthalate], and 26% is not oxidized further (i.e., MEHP). A good correlation is obtained when the amount of MEHP -hydroxylation products is compared with the amount of MEHP (-1)hydroxylation products in urine samples. When the internal dose of DEHP has to be established we recommend that the levels of all four metabolites of DEHP be studied in urine samples.     

Metabolites of the plasticizer di (2-ethylhexyl) phthalate in urine samples of workers in polyvinylchloride processing industries

Summary Little is known about occupational exposure to the plasticizer di(2-ethylhexyl)phthalate (CAS number 117-81-7), a compound widely used in polyvinylchloride (PVC) plastics. We have studied the uptake of DEHP in workers by determining the concentrations of four metabolites of DEHP in urine samples, i.e., mono(2-ethylhexyl)phthalate (MEHP), mono (5-carboxy-2-ethylpentyl)phthalate, mono(2-ethyl-5-oxohexyl)phthalate, and mono(2-ethyl-5-hydroxyhexyl)phthalate. In addition DEHP concentrations in the air were determined by personal air sampling. Nine workers in a PVC boot factory exposed to a maximum of 1.2 mg/m³ DEHP showed an increase in the urinary concentrations of all four metabolites over the workshift. These results were obtained on both the first and the last day of the workweek. With the exception of MEHP, the increases in the concentrations of the metabolites during a workday were statistically significant. Six workers from a PVC cable factory exposed to a maximum of 1.2 mg/m³ DEHP showed a one-to fourfold increase in the concentrations of the four metabolites over the workshift, but these increases were not statistically significant. These results indicate that measurement of DEHP metabolites in urine samples may be of use for monitoring the occupational exposure to DEHP.     

液液萃取-气相色谱质谱法测定饮用水中19种有机磷农药

目的:建立测定饮用水中19种有机磷农药(治螟磷,甲拌磷,内吸磷,二嗪磷,乙拌磷,异稻瘟净,氧化乐果,甲基对硫磷,皮蝇磷,甲基嘧啶磷,杀螟硫磷,马拉硫磷,毒死蜱,倍硫磷,对硫磷,久效磷,溴硫磷,甲基异柳磷,稻丰散)液液萃取-气相色谱质谱(GC-MS)检测方法。方法:二氯甲烷液液萃取(LLE)水样后,浓缩提取液至1 ml后,采用气相色谱-质谱(GC-MS)的选择离子监测(SIM)模式同时定性定量分析。结果:19种有机磷农药的峰面积与其浓度均有良好的线性关系,相关系数均大于0.998;最小检测量为0.14μg/L～0.64μg/L;样品加标回收率为85.2%～97.9%,相对标准偏差为1.9%～9.8%。结论:该方法可对饮用水中有机磷农药同时定量与定性,具有方法简便、准确、可靠等优点。     

饮用水中多种有机磷农药残留的气相色谱-三重四极杆质谱测定法

目的建立一种同时测定饮用水中7种有机磷农药残留量的气相色谱-三重四极杆质谱（GC-MS/MS）方法。方法采用液-液萃取方法,用二氯甲烷对水样中7种有机磷农药进行提取,无水硫酸钠脱水,滤液在40℃水浴中旋转蒸发近干,用二氯甲烷定容,GC-MS/MS测定,外标法定量。结果 7种有机磷农药在21 min内分离,在0.01-10 mg/L范围内相关系数r2均在0.99以上,在0.05、0.25和0.45 mg/L 3个水平加标回收率在78.9%-99.3%之间,相对标准偏差均小于10%,检出限为0.02-0.06μg/L。结论该方法操作简单,准确度和精密度高,消除了其他有机磷农药的干扰,避免假阳性的出现,适用于饮用水中7种有机磷农药残留量的检测和确证。     

饮用水中9种卤代烃的吹扫捕集-气相色谱-质谱联用测定法

目的建立了同时测定生活饮用水中二溴乙烷、二溴乙烯、三氯甲烷、四氯化碳、三氯乙烯、四氯乙烯、一溴二氯甲烷、二溴一氯甲烷、三溴甲烷等9种卤代烃的吹扫捕集-气相色谱-质谱联用方法。方法采用吹扫捕集的方法对水中的卤代烃进行富集,解吸后进入气相色谱-质谱联用仪,经色谱柱分离后,以质谱检测器测定。结果方法的线性范围分别为0.01~0.93μg/L(1,2-二溴乙烯)和0.01~0.80μg/L(其它8种卤代烃),检出限为0.002~0.004μg/L,回收率为84.4%~106%,RSD为1.0%~8.9%。结论该方法灵敏度高、重现性好、操作简单、无需有机溶剂,适用于水中二溴乙烷、二溴乙烯等9种卤代烃的测定。     

Species and inter-individual differences in metabolic capacity of di(2-ethylhexyl)phthalate (DEHP) between human and mouse livers

Objectives

This study was conducted to assess inter-species and inter-individual differences in the metabolism of di(2-ethylhexyl)phthalate (DEHP) in humans and mice.

Methods

The activities of four DEHP-metabolizing enzymes [lipase, UDP-glucuronocyltransferase (UGT), alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH)] were measured in the livers of 38 human subjects of various ages and in eight 129/Sv male mice.

Results

Microsomal lipase activity was significantly lower in humans than in mice. The V _max/K _m value in humans was one-seventh of that in mice, microsomal UGT activity in humans was a sixth of that in mice, and cytosolic ALDH activity for 2-ethylhexanal in humans was one-half of that in mice. In contrast, ADH activity for 2-ethylhexanol was twofold higher in humans than in mice. The total amount of DEHP urinary metabolites and the concentration of mono(2-ethylhexyl)phthalate (MEHP) were much higher in intact mice than in the U.S. general population based on data reported elsewhere, regardless of the similar estimated DEHP intake between these mice and the human reference population. However, mono(2-ethyl-5-oxo-hexyl)phthalate (5oxo-MEHP) and mono(2-ethyl-5-carboxypentyl)phthalate (5cx-MEPP) levels were higher in the latter than in the former. Of note, inter-subject variability in the activities of all enzymes measured was 10–26-fold.

Conclusion

The inter-individual variation in the metabolism of DEHP in humans may be greater than the difference between mice and humans (inter-species variation), and both may affects the risk assessment of DEHP.     

GC-MS检测蔬菜有机磷农药残留的效果分析

目的:用比较法对气相色谱-质谱法检测蔬菜农药残留的效果进行综合分析。方法:用气相色谱-质谱法对已知的5种农药标准品连续稀释计算出检出限,并随机抽取本地菜农种植的四种蔬菜进行农药残留量检测。同时用气相色谱法同步进行比较试验。结果:两种方法比较,气相色谱-质谱法具有更高的灵敏度和准确度,差异有统计学意义(P<0.05)。对蔬菜残留农药的检测结果表明GC-MS在蔬菜农残检测中具有更广泛的用途。结论:GC-MS在检测蔬菜农药残留方面具有更好的效果。