酯交换法合成邻苯二甲酸二异辛酯

以邻苯二甲酸二甲酯与异辛醇为原料,有机锡为催化剂,通过酯交换法在无溶剂的条件下合成了邻苯二甲酸二异辛酯,考察了反应温度、催化剂用量、反应时间及物料配比等因素对反应的影响。结果表明,最佳反应条件为：反应温度170—180℃,催化剂用量1．0g,反应时间3．5h,邻苯二甲酸二甲酯与异辛醇物质的量比1：2．10。在此条件下,收率在96．5％以上,通过折光率、红外光谱分析、核磁氢谱对产品进行了结构表征。     

Combined Toxicological Effects of Di (2-Ethylhexyl) Phthalate and UV-B Irradiation through Endoplasmic Reticulum Stress—Tight Junction Disruption in Human HaCaT Keratinocytes

Di (2-ethylhexyl) phthalate (DEHP) is widely used as a plasticizer, and human exposure to DEHP is widespread and frequent. However, information about the combined effect of DEHP and ultraviolet (UV)-B on the skin are still limited. We investigated the cytotoxic effects of DEHP and UV-B on HaCaT keratinocytes and evaluated the related underlying mechanisms involving endoplasmic reticulum (ER) stress signals and the disruption of junction complexes as an effective target for skin inflammation. Our results revealed that co-treatment with DEHP and UV-B irradiation alleviated the cell cytotoxicity and markedly decreased X-box binding protein 1 (XBP1), endoplasmic reticulum oxidoreductase 1 alpha (Ero1α), and C/EBP homologous protein (CHOP) whereas a single dose of 40 mJ/cm² UV-B generated mild ER stress to slightly less or similar levels as that seen with DEHP. DEHP was also shown to inhibit tight junctions (TJs) after UV-B irradiation, increased apoptosis by altering apoptotic gene Bax and stress kinases, JNK, and p38 MAPK. Furthermore, exposure of HaCaT cells to DEHP and UV-B irradiation resulted in the marked suppression of the nuclear factor kappa B (NF-κB)/p65 signaling pathway. Taken together, our data suggest that nontoxic DEHP and UV-B irradiation regulated ER stress and epidermal TJ disruption with the induction of apoptosis activation and the secretion of proinflammatory cytokines such as interleukin 1 beta (IL-1β) and IL-6 in human keratinocytes. Further investigation is needed to confirm the mechanisms implicated in its toxicity and determine the effects of exposure to DEHP and UV-B irradiation on markers involved in this study.     

纳米固体超强酸SO4^2-／Fe2O3催化合成邻苯二甲酸二（2-乙基己基）酯

研究了纳米固体超强酸SO4^2-／Fe2O3催化合成邻苯二甲酸二(2-乙基己基)酯(DOP)的方法。首先，合成了纳米固体超强酸，考察了该催化剂在邻苯二甲酸二(2-乙基己基)酯(DOP)合成中的催化活性，并与非纳米的SO4^2-／TiO2、SO4^2-／ZrO2、SO4^2-／Fe2O3、浓H2SO4催化剂进行了比较，同时对酯化反应的几种影响因素进行了研究，并确定了最佳工艺参数。结果表明，苯酐：2-乙基己醇=1：2．5(mol)，催化剂用量为2．8g(苯酐为0．1mol时)，反应时间为120min，反应温度为150℃，酯化率可达99．1％。该催化剂不经处理，可循环使用多次，且不污染环境，相对于一些常见催化剂具有明显的优点。     

邻苯二甲酸二-(2-乙基己基)酯对小鼠红细胞ATPase活性的影响

为了研究邻苯二甲酸二-(2-乙基己基)酯(DEHP)对小鼠红细胞ATPase活性的影响,用不同浓度的DEHP对昆明小鼠进行腹腔注射染毒.2周后,各染毒组红细胞Na -K -ATPase活力与对照组相比均明显下降(P＜0.01),并具有很好的剂量-效应关系(R=-0.942,P＜0.01).125 mg·kg-1染毒组红细胞Ca2 -ATPase活力略有下降,但无显著性差异(P＞0.05),随着染毒浓度的倍增,红细胞Ca2 -ATPase活力不断下降,与对照组相比表现出极显著性差异(P＜0.01),同时也具有很好的剂量-效应关系(R=-0.968,P＜0.01 ).结果表明,DEHP抑制了红细胞ATPase的活性,证明DEHP对红细胞造成了损伤,对机体具有明显的毒性作用.     

邻苯二甲酸二(2-乙基己基)酯对污泥好氧消化的影响

对邻苯二甲酸二(2-乙基己基)酯(DEHP)对污泥好氧消化的影响进行了研究,以期为污泥的安全资源化利用提供一定的基础资料。结果表明,对于污泥好氧消化,当进泥中DEHP投加量为20mg/L时,对VSS去除率没有明显影响;当DEHP投加量为100mg/L以上时,随DEHP投加量的增加,VSS去除率下降,同时反应器污泥中DEHP的残留浓度随之增大。     

酯交换法合成邻苯二甲酸二异辛酯

以邻苯二甲酸二甲酯与异辛醇为原料,二丁基氧化锡为催化剂,通过酯交换法在无溶剂的条件下合成了邻苯二甲酸二异辛酯。通过实验考察了反应温度、催化剂用量、反应时间及物料配比等因素对反应的影响。反应的最佳条件是：反应温度为170～180℃,催化剂用量为1．0g,反应时间为4h,邻苯二甲酸二甲酯与异辛醇物质的量的比为1：2．10。在此条件下,收率在96．5％以上,通过折光率、IR、^1HNMR对产品进行了结构表征。     

Effects of Prenatal Phthalate Exposure and Childhood Exercise on Maternal Behaviors in Female Rats at Postpartum: A Role of Oxtr Methylation in the Hypothalamus

Both the detrimental effect of prenatal exposure to di-(2-ethylhexyl)-phthalate (DEHP) and the beneficial effects of physical exercise on brain functions have been reported. The oxytocin pathway has been implicated in the onset of maternal behaviors. Epigenetic modification of the oxytocin receptor gene (OXTR) through DNA methylation has been associated with the pathogenesis of neuropsychiatric disorders. The purpose of this study was to investigate the effects of prenatal DEHP exposure on oxytocin-regulated maternal behaviors and to examine the protective effect of exercise. Pregnant rats (F0) were fed with vehicle or DEHP during gestation and the offspring females (F1) were assessed for their maternal behaviors by pup retrieval test at postpartum. The results showed that reduced pup retrieval activities without significant alteration of stress responses were observed in the prenatally DEHP-exposed females. Prenatal DEHP exposure decreased the expressions of oxytocin, Oxtr mRNA, and oxytocin receptor, and increased Oxtr methylation in the hypothalamus of postpartum female rats. There were no significant effects of exercise on behavioral, biochemical, and epigenetic measurements. These results suggest that prenatal DEHP exposure has a long-term adverse effect on maternal behaviors; Oxtr hyper-methylation may be a potential epigenetic mechanism for this alteration, which cannot be prevented by physical exercise during childhood.     

加氢法生产环己烷1,2-二甲酸二(2-乙基己)酯工艺

以邻苯二甲酸二(2-乙基己)酯（DEHP,工业级）为原料,采用固定床加氢工艺和贵金属Ru-Pd催化剂,制备环己烷1,2-二甲酸二(2-乙基己)酯。分别考察了温度、压力、空速、氢气与原料的体积比对反应活性的影响。试验结果表明：在反应温度190℃、压力15MPa、体积空速0.5h?1、氢气与原料的体积比为800∶1的条件下,原料DEHP转化率保持在99.99%以上,目标产物选择性高于99.7%。连续运行1000h,催化剂仍具有优异的加氢活性。     

邻苯二甲酸二辛酯生产工艺评述

介绍了如下工艺路线：由苯酐与２ 乙基己醇合成邻苯二甲酸二（２ 乙基）己酯,比较了几种工艺路线的优缺点。     

稳定同位素内标试剂邻苯二甲酸二(2-乙基己)酯-D4的合成

以2-乙基己醇-D2和邻苯二甲酸酐为原料,在催化剂的催化作用下简便高效的生成标题化合物。以消耗的邻苯二甲酸酐计算,标题化合物收率可达94.5%。用质谱和核磁共振波谱等表征手段对产品结构进行确定,产品的同位素丰度为99.1 atom%D,纯度为99.0%,可作为同位素内标试剂应用于食品安全检测领域塑化剂违禁物质的检测。     

Exposure to Endocrine Disruptors (Di(2-Ethylhexyl)phthalate (DEHP) and Bisphenol A (BPA)) in Women from Different Residing Areas in Italy: Data from the LIFE PERSUADED Project

Phthalates and bisphenol A (BPA) are plasticizers used in many industrial products that can act as endocrine disruptors and lead to metabolic diseases. During the LIFE PERSUADED project, we measured the urinary concentrations of BPA and Di(2-ethylhexyl)phthalate (DEHP) metabolites in 900 Italian women representative of the Italian female adult population (living in the north, centre, and south of Italy in both rural and urban areas). The whole cohort was exposed to DEHP and BPA with measurable levels above limit of detection in more than 99% and 95% of the samples, respectively. The exposure patterns differed for the two chemicals in the three macro-areas with the highest urinary levels for DEHP in south compared to central and northern Italy and for BPA in northern compared to central and southern Italy. BPA levels were higher in women living in urban areas, whereas no difference between areas was observed for DEHP. The estimated daily intake of BPA was 0.11 μg/kg per day, about 36-fold below the current temporary tolerable daily intake of 4 μg/kg per day established by the EFSA in 2015. The analysis of cumulative exposure showed a positive correlation between DEHP and BPA. Further, the reduction of exposure to DEHP and BPA, through specific legislative measures, is necessary to limit the harmfulness of these substances.     

Possible Mechanisms of Di(2-ethylhexyl) Phthalate-Induced MMP-2 and MMP-9 Expression in A7r5 Rat Vascular Smooth Muscle Cells

Proliferation and migration of vascular smooth muscle cells (VSMC) are important in the development and/or progression of many cardiovascular diseases, including atherosclerosis. Evidence shows that matrix metalloproteinase (MMP)-2 and MMP-9 are related to the pathogenesis of atherosclerosis. The expressions of MMP-2 and MMP-9 in atherosclerosis are regulated via various pathways, such as p38 mitogen activated protein kinase (MAPK), extracellular signal regulated kinase 1 and 2 (ERK1/2), Akt, and nuclear factor kappa (NF-κB). Di(2-ethylhexyl) phthalate (DEHP) has been shown to induce atherosclerosis by increasing tumor necrosis factor (TNF)-α, interleukin (IL)-6, and intercellular adhesion molecule (ICAM) productions. However, whether DEHP poses any effects on MMP-2 or MMP-9 expression in VSMC has not yet been answered. In our studies, rat aorta VSMC was treated with DEHP (between 2 and 17.5 ppm) and p38 MAPK, ERK1/2, Akt, NF-κB, and MMP-2 and MMP-9 proteins and activities were measured. Results showed that the presence of DEHP can induce higher MMP-2 and MMP-9 expression than the controls. Similar results on MMP-regulating proteins, i.e., p38 MAPK, ERK1/2, Akt, and NF-κB, were also observed. In summary, our current results have showed that DEHP can be a potent inducer of atherosclerosis by increasing MMP-2 and MMP-9 expression at least through the regulations of p38 MAPK, ERK1/2, Akt, and NF-κB.     

活性炭与光催化联用降解水中邻苯二甲酸二(2-乙基己)酯的研究

研究了臭氧活性炭与光催化联用降解饮用水中邻苯二甲酸二(2-乙基己)酯(DEHP)。当使用臭氧浓度为2.0mg/L、活性炭负载TiO_2催化剂浓度为0.02g/g、pH值10.0时,对DEHP含量为12.04mg/L的饮用水光催化降解6h,DEHP的去除率可达99.5%。研究结果表明,臭氧活性炭与光催化联用可有效去除水中邻苯二甲酸二(2-乙基己)酯。     

Equilibrium studies of the extraction of zirconium(IV) from sulfuric acid solutions with Di(2-ethylhexyl)phosphoric acid

Equilibrium studies were made at 25°C in the extraction of zirconium(IV) from sulfuric acid solutions with di(2-ethylhexyl)phosphoric acid (D2EHPA, HR) dissolved in kerosene. The reaction stoichiometry was numerically determined and the compositions of the extracted species were found to be ZrR₄ and ZrR₄(HR) at low loading ratios of D2EHPA (α < 0.09), but became ZrR₄ and ZrR₄(HR)₃ at relatively higher loading ratios (0.10 < α < 0.32). The equilibrium constants for the formation of these species were also obtained. Furthermore, numerical treatment of the experimental data excluded the existence of polynuclear complexes under the conditions studied (α < 0.32).     

环保增塑剂环己烷1,2-二甲酸二异辛酯的清洁合成

以环己烷1,2-二甲酸酐(HHPA)和异辛醇为原料,活性炭负载甲烷磺酸为催化剂,催化合成环己烷1,2-二甲酸二异辛酯。经单因素实验得到最佳工艺条件为：异辛醇和环己烷1,2-二甲酸酐的摩尔比为2.4∶1.0,催化剂的用量为醇酐总质量的2.1%,带水剂环己烷用量6 mL,反应温度160 ℃～180 ℃,反应时间2.5 h,酯化率可达99.82%。催化剂重复使用4次后酯化率仍大于90%。产品为浅黄色油状液体,经HPLC测定酯色谱纯度为99.15%。测定了其酸值、密度、加热减量、黏度、热重曲线等,结果表明,环己烷1,2-二甲酸二异辛酯符合增塑剂的性能要求。     

酸式磷酸二辛酯的合成及其在膨胀型阻燃聚丙烯中的偶联作用

以三氯氧磷、异辛醇为原料合成的酸式磷酸二辛酯是一种含磷阻燃偶联剂 ,作者研究了其对膨胀型阻燃剂 (IFR) /聚丙烯 (PP)共混材料的偶联作用。力学性能、阻燃性能测试和SEM结果表明 :酸式磷酸二辛酯是体系有效的偶联剂 ,在不损害原有阻燃性能的条件下 ,提高了共混材料的力学性能 ,明显改善共混体系的形貌结构 ,是一种可选的阻燃偶联剂。经酸式磷酸二辛酯偶联的IFR/PP拉伸强度、抗冲击强度和水平燃烧性能分别为 2 5 4MPa、4 0 2kJ·m-2 和GB 2 40 8—80II- 0 5mm ,离火 36s自熄 ,未加偶联剂的对应值为 2 2 5 7MPa、3 2 7kJ·m-2 和GB 2 40 8— 80II- 1mm ,离火 39s自熄。     

环保增塑剂环己烷1,2-二甲酸二异辛酯的合成

以环己烷1,2-二甲酸酐(HHPA)和异辛醇为原料,活性炭负载甲烷磺酸为催化剂,合成环己烷1,2-二甲酸二异辛酯。经单因素实验得到最佳工艺条件为:n(异辛醇)∶n(环己烷1,2-二甲酸酐)=2.4∶1.0,催化剂用量为醇酐总质量的2.1%,带水剂环己烷用量6 mL,反应温度160～180℃,反应时间2.5 h,酯化率可达99.82%。催化剂重复使用4次后酯化率仍大于90%。产品为浅黄色油状液体,经HPLC测定酯色谱纯度为99.15%。测定了其酸值、密度、加热减量、黏度、热重曲线等,结果表明,环己烷1,2-二甲酸二异辛酯符合增塑剂的性能要求。     

Synergic Extraction of Folic Acid with Di(2-ethylhexyl) Phosphoric Acid and Amberlite LA-2

The influences of extractants concentrations and solvent polarity on the efficiency of folic acid separation by synergic extraction with Amberlite LA-2 and di(2-ethylhexyl) phosphoric acid (D2EHPA) mixture have been analyzed. The results indicated the formation of an interfacial compound which includes one molecule of folic acid and one of D2EHPA, the hydrophobicity of this compound being increased by solvation with Amberlite LA-2 molecules. The number of aminic molecules participating in the interfacial complex formation is controlled by solvent polarity and D2EHPA concentration, decreasing from 3 to 1 with the increase of these two parameters. The results indicated that the most important synergic effect corresponds to the extractants mixture dissolved n-heptane, at low D2EHPA concentration in the organic phase (5 g/l).     

二-(2-乙基己基)磷酸合成工艺研究

研究了合成二－（2－乙基己基）磷酸的工艺优化条件，通过加入无水AlCl3，严格控制反应温度，控制三氯氧磷加入量过量3％等措施，合成的二－（2－乙基己基）磷酸萃取稀土元素性能优于标准萃取剂。     

c-Jun氨基末端激酶在邻苯二甲酸二(2-乙基)己酯诱导的尿道下裂大鼠阴茎组织中的表达

目的研究c-Jun氨基末端激酶(c-Jun N-terminal kinase,JNK)在邻苯二甲酸二(2-乙基)己酯[di(-2-ethyl-hexyl)phthalate,DEHP]诱导的尿道下裂大鼠阴茎组织中的表达变化,探讨尿道下裂发生的机制。方法将孕12 d(gestation day,GD12)的SD孕鼠随机分为2组:实验组[将DEHP溶于1.5 ml大豆油中灌胃大鼠,750 mg/(kg.d)]和对照组(以1.5 ml大豆油灌胃大鼠),每组20只,自GD12～GD19连续每天定时给药1次。各组分别取10只孕鼠正常分娩,雄性仔鼠出生后30 d,计数每窝产雄性活仔数,称量体重,并测量肛门生殖器距离(anogenital distance,AGD),逐个检查雄鼠的阴茎弯曲度和尿道开口部位,判断有无尿道下裂;其余孕鼠在怀孕第20天行剖宫产取出胎鼠,采用实时定量PCR(qPCR)和免疫组化法分别检测雄性胎鼠阴茎组织中JNK1和JNK2 mRNA和蛋白的表达水平。结果雄性仔鼠出生后30 d,实验组与对照组比较,每窝产雄性活仔数、雄性仔鼠的体重及AGD均有明显减少或缩短(P均<0.001);实验组尿道下裂发生率约为30.6%。与对照组比较,实验组胎鼠阴茎组织中JNK1和JNK2mRNA的水平明显增加(P<0.05),磷酸化JNK1和JNK2蛋白的表达水平有增加的趋势。结论 DEHP诱导的先天性尿道下裂可能与胎鼠阴茎组织中JNK通路异常表达有关。