Recent Advances of Sensitive Electrochemical Sensing Platforms for Rapid Detection of Phthalate Acid Esters

As a kind of plasticizer,phthalic acid esters(PAEs)are often added to plastics to enhance elasticity,transparency,durability and prolong service life.However,it does not chemically bind to plastics and is easy to migrate to the environment.It is difficult to degrade in the environment,and it is also enriched in the human body through the food chain and respiration,which will lead to obvious adverse reactions such as decreased learning and memory function and neurobehavioral disorders.Due to the toxicity,universality and low concentration limitations of PAEs in the environment and food,it is essential to achieve rapid and sensitive detection of PAEs in soil,atmosphere,water and food.Electrochemical(EC)sensors have the advantages of simplicity,fast,low cost,portability,easy operation,high specificity and high sensitivity,so they are applied for the detection of PAEs.Although there are a large number of studies on the detection of PAEs by EC sensors,there is no review on this aspect.In this review,we introduce the detection of PAEs from classical EC sensors,electrochemiluminescence(ECL)sensors and photo-electrochemical(PEC)sensors in the past five years.This review is beneficial to understanding the construction of EC sensors and the detection mechanism of PAEs.We also propose that the development of rapid,accurate and real-time detection methods of PAEs is key to assessing risk and preventing related diseases.

Distribution Equilibrium of o-Phthalic Acid and trans-Butenedioic in Water and Di-n-butyl Phthalate

The organic dissolvent （di-n-butyl phthalate） needs to be washed by water to recycle itself in the process of recovering maleic anhydride by organic dissolvent. The design and optimization of the extraction process require the distribution coefficients of the organic solutes, o-phthalic acid and trans-butenedioic in water and di-n-butyl phthalate, on which the extraction efficiency depends. In this study, the distribution coefficients of o-phthalic acid and trans-butenedioic in water and di-n-butyl phthalate（DBP） at 298.15 K, 318.15 K and 333.15 K were determined respectively by acid-alkali titration. The dissociation constants of o-phthalic acid and trans-butenedioic at those temperatures were obtained by fitting the measured hydrogen-ion concentrations and the known solute concentrations in the aqueous solution containing the two organic solutes. Then the distribution constants were calculated. Both the distribution coefficients and the distribution constants increase along with the temperature increasing. And the distribution coefficients at 333.15 K are large enough to ensure the efficiency of extraction process. In addition, the mutual solubility of water and di-n-butyl phthalate at 298.15 K, 318.15 K and 333.15 K was also measured respectively by High Performance Liquid Chromatography and Karl Fischer Watertitration, which was not more than 0.50/0（mass fraction）.

Anoxic biodegradation of dimethyl phthalate (DMP) by activated sludge cultures under nitrate-reducing conditions

Worldwide extensive use of plasticized plastics has resulted in phthalates pollution in different environment. Nitrates from industry and agriculture are also widely disseminated in the soils, natural waters and wastewaters. Dimethyl phthalate （DMP） biodegradation by activated sludge cultures under nitrate-reducing conditions was investigated. Under one optimized condition, DMP was biodegraded from 102.20 mg/L to undetectable level in 56 h under anoxic conditions and its reaction fitted well with the first-order kinetics. Using the high-performance liquid chromatography （HPLC） and liquid chromatography mass spectrometry （LC-MS） analysis, mono-methyl phthalate （MMP） and phthalic acid （PA） were detected as the major intermediates of DMP biodegradation. When combined with the determination of chemical oxygen demand （CODer） removal capacity and pH, DMP was found to be mineralized completely under anoxic conditions. The biodegradation pathway was proposed as DMP → MMP→ PA→…→ CO2 ＋ H2O. The molar ratio of DMP to nitrate consumed was found to be 9.0：1, which agrees well with the theoretical stoichiometric values of DMP biodegradation by nitrate-reducing bacteria. The results of the non-linear simulation showed that the optimum pH and temperature for the degradation were 7.56 and 31.4℃, respectively.

Maslinic acid supplementation prevents di(2-ethylhexyl)phthalate-induced apoptosis via PRDX6 in peritubular myoid cells of Chinese forest musk deer

Chinese forest musk deer(FMD),an endangered species,have exhibited low reproductive rates even in captivity due to stress conditions.Investigation revealed the presence of di(2-ethylhexyl)phthalate(DEHP),an environmental endocrine disruptor,in the serum and skin of captive FMDs.Feeding FMDs with maslinic acid(MA)has been observed to alleviate the stress response and improve reproductive rates,although the precise molecular mechanisms remain unclear.Therefore,this study aims to investigate the molecular mechanisms underlying the alleviation of DEHP-induced oxidative stress and cell apoptosis in primary peritubular myoid cells(PMCs)through MA intake.Primary PMCs were isolated and exposed to DEHP in vitro.The results demonstrated that DEHP significantly suppressed antioxidant levels and promoted cell apoptosis in primary PMCs.Moreover,interfering with the expression of PRDX6 was found to induce excessive reactive oxygen species(ROS)production and cell apoptosis in primary PMCs.Supplementation with MA significantly upregulated the expression of PRDX6,thereby attenuating DEHP-induced oxidative stress and cell apoptosis in primary PMCs.These findings provide a theoretical foundation for mitigating stress levels and enhancing reproductive capacity of in captive FMDs.

Phthalate Metabolites in Amniotic Fluid and Maternal Urine Samples

The objective of this study was to determine the concentrations of the metabolites of four selected phthalates, widely used industrial chemicals which possess endocrine-disrupting properties, in samples of amniotic fluid and maternal urine collected in the same day, in order to verify if the latter can be considered a measure of the fetal exposure. The quantitative determination of the metabolites was carried out by HPLC-MS/MS with isotopic dilution from 70 pregnant volunteers. Detectable concentrations of phthalates metabolites were found in amniotic fluids. As phthalate monoesters are excreted in the urine conjugated with glucuronic acid, an enzymatic hydrolysis is carried out before analysis. Amniotic fluids were tested with and without hydrolysis and only the free phthalate metabolites, not conjugated with glucuronic acid, were found. The concentration of metabolites after enzymatic hydrolysis in maternal urine is not correlated to those of amniotic fluids, but the free form concentrations are. These results suggest that only the free forms can cross the placenta. A significant number of mothers showed urine phthalate monoesters concentrations higher than non-pregnant women.

Activated sludge-mediated biodegradation of dimethyl phthalate under fermentative conditions

The biodegradation of dimethyl phthalate(DMP)was investigated under fermentative conditions in this study.The nature of the intermediate compounds and the extent of mineralization were probed using high-pressure liquid chromatography(HPLC)and liquid chromatography-mass spectrometry(LC-MS)methods.The fermentative bacteria were able to biodegrade the DMP under anaerobic conditions,with the biodegradation rate of 0.36 mg DMP/(L·h).The results demonstrated that the DMP degradation under fermentative conditions ...

邻苯二甲酸二(2-乙基己基)酯(DEHP)诱发小鼠胆汁淤积和肝损伤的作用机制

目的探讨邻苯二甲酸二(2-乙基己基)酯(DEHP)诱发小鼠胆汁淤积和肝损伤机制研究。方法体内实验:将成年雌性ICR小鼠随机分为对照组(玉米油)、DEHP组(200 mg·kg^(−1)·d^(−1)),共灌胃4周,建立胆汁淤积模型。收集所有小鼠血液与肝组织,生化仪检测血清、肝脏总胆汁酸(TBA)水平,酶标仪检测ALP、GGT;HE染色观察肝组织病理变化;实时定量PCR检测肝脏炎症因子IL-1β、IL-6和TNF-α的表达水平;液相色谱-三重四级杆质谱仪(LC-MS/MS)检测小鼠肝脏胆汁酸谱。体外实验:培养小鼠肝细胞AML-12,使用DEHP(250μmol/L)以及去氧胆酸(DCA)(125μmol/L)和鹅去氧胆酸(CDCA)(125μmol/L)处理细胞24 h,实时定量PCR检测细胞炎性因子IL-1β、IL-6和TNF-α的mRNA水平。计量资料两组间比较采用成组t检验,多组间比较采用单因素方差分析,进一步两两比较采用LSD-t检验。结果体内实验显示:与对照组相比,DEHP组小鼠肝体比,血清TBA、ALP、GGT及肝脏TBA均显著升高(t值分别为−4.396、−5.109、−8.504、−3.792和−7.974,P值均<0.05)。与对照组相比,肝脏胆汁酸谱中胆酸(CA)、CDCA、牛磺鹅去氧胆酸(TCDCA)、DCA及熊去氧胆酸(UDCA)均显著升高(t值分别为−2.802、−3.177、−2.633、−2.874和−2.311,P值均<0.05)。DEHP组小鼠肝脏HE染色显示为汇管区扩大、胆管变形、胆管周围伴有炎性细胞浸润,且肝脏炎症因子IL-1β、IL-6和TNF-αmRNA水平均显著升高(t值分别为−2.539、−2.823和−4.636,P值均<0.05)。体外实验显示:0~1000μmol/L DEHP处理后肝细胞活力实际数值相差不超过15%,分别使用125、250以及500μmol/L的DEHP刺激后,肝细胞的炎症因子IL-1β、IL-6和TNF-αmRNA水平均明显升高(P值均<0.05)。与单独使用DEHP刺激相比,CDCA联合DEHP刺激上调了细胞炎症因子IL-1βmRNA水平(P<0.01);DCA与DEHP联合刺激可显著增加细胞炎症因子IL-1β和IL-6的mRNA水平(P值均<0.01)。结论DEHP暴露导致小鼠胆汁淤积肝病的发生并诱发肝脏炎症,这可能与其促进有毒胆汁酸的产生进而加剧炎性因子分泌有关。

纳米塑料-重金属-塑化剂联合暴露对儿童肠道微生物菌群及代谢的影响

[目的]探究纳米塑料(NPs)、镉(Cd)和邻苯二甲酸二丁酯(DBP)污染对儿童肠道菌群多样性、氨基酸代谢及短链脂肪酸(SCFAs)含量的影响.[方法]利用16S rRNA高通量测序技术和高效液相色谱-质谱法LC-MS/MS分析NPs、Cd、DBP单一污染及纳米塑料聚丙烯(PP)、Cd、DBP复合污染对儿童肠道细菌群落及肠道微生物代谢产物中短链脂肪酸及氨基酸含量的变化.[结果]高通量检测结果显示,与对照相比,在门属水平上,单一污染的优势菌门属无明显变化,PP+Cd、PP+DBP+Cd复合污染优势菌门属水平丰富度与多样性显著下降;LC-MS/MS检测结果显示,在肠道微生物代谢产物中,经NPs与DBP暴露后,氨基酸含量呈现不同程度的下降,而Cd、PP+Cd、PP+Cd+DBP处理后,大多数氨基酸的含量显著增加;同时检测到丁酸、戊酸的含量也发生变化.[结论]与单一污染物处理相比NPs相关复合污染物暴露处理后其肠道微生物紊乱程度更强,且不同污染物处理均会影响肠道微生物的氨基酸代谢和SCFAs产量.肠道菌群与人体健康密切相关,探究肠道菌群及代谢功能在NPs、Cd、DBP影响下的变化,从肠道菌群层面评价NPs、Cd、DBP单一暴露和复合暴露污染下的危害和风险具有重要意义.

甲基丙烯酸水溶液萃取分离液液相平衡数据测定与关联

针对甲基丙烯酸(MAA)与水(H_(2)O)形成共沸混合物、MAA水溶液分离难的问题,开展了MAA水溶液提纯过程萃取剂筛选、MAA H_(2)O萃取剂三元液液相平衡数据测定与关联等研究。通过对甲苯、正己烷、环己烷、邻苯二甲酸二丁酯(DBP)4种萃取剂的萃取效率进行考察,确定DBP为综合性能最优的萃取剂。测定了常压条件下20、30、40℃时H_(2)O MAA DBP三元体系的液液相平衡数据,实验结果通过了Hand方程和Othmer Tobias方程对相平衡数据的一致性验证,线性相关性系数R^(2)值超0.99。使用UNIQUAC模型来拟合实验数据得到三组分二元交互作用参数,模型预测值与实验值的均方根偏差小于0.07,表明实验数据及拟合参数均有较高的准确性,为DBP应用于工业MAA水溶液提纯过程开发提供基础。

气质法对含邻苯二甲酸酯类白酒质控样的检测

为了监测实验室的检测能力,进一步提高食品中邻苯二甲酸酯类塑化剂的检验工作质量,保证检验结果的准确及可靠性,采用气质法对含邻苯二甲酸酯类塑化剂白酒质控样进行检测,采用离子监测扫描模式(SIM),以保留时间和定性离子碎片丰度比定性,同位素内标法定量。结果表明,在0~1μg/mL的质量浓度范围内,16种邻苯二甲酸酯标准曲线相关系数均大于0.997,加标回收率为90%~110%,检出值均在质控样证书中的特性值区间之内,考核结果为合格。

A Convenient and Practical Prepapation of Acetylphenyl Boronic Acids

A practical and scalable synthesis route of acetylphenylboronic acids is described. Bromoacetophenones(compounds 3a, 3b) were ketalized with ethylene glycol and triethyl orthoformate to give bromo ketals(compounds 4a_4c) in 60_80% yields. Compounds 4a_4b were treated with a Grignard reagent and then exchanged with borate to give p- and m-acetylphenyl boronic acids(compounds 5a and 5b) in 80% and 56% yields, respectively. The o-form(compound 5c) was obtained in 61% yield via the BuLi method.

住宅室内温湿度及颗粒物浓度对降尘中PAEs浓度分布的耦合影响

深入了解室内邻苯二甲酸酯(PAEs)化合物浓度分布及其影响因素对污染控制具有重要意义。本研究对266户上海住宅进行了室内降尘采集,对PAEs的种类及含量进行了测试分析,采用逻辑回归方法分析了室内温度、湿度和颗粒物浓度与3种典型PAEs浓度分布的关联性,揭示了环境参数对PAEs浓度分布的相乘交互作用和影响。结果显示:温度与邻苯二甲酸二(2-乙基)己酯(DEHP)呈显著负相关性,湿度与邻苯二甲酸二异丁酯(DiBP)呈显著负相关性;将温度、颗粒物浓度作为混淆因素调整后,湿度和DEHP呈显著正相关性;在低温和低湿度条件下,颗粒物浓度与DEHP、高分子量PAEs(HMW-PAEs)、总PAEs(TPAEs)的浓度呈显著负相关性;温度和颗粒物浓度对DEHP浓度分布存在正向相乘交互作用。因此,室内温度、湿度和颗粒物浓度均在不同程度上影响PAEs浓度分布,PAEs浓度的变化是由多个影响因素共同作用引起的。

食品中邻苯二甲酸酯类塑化剂检测技术研究进展

邻苯二甲酸酯类塑化剂在工业上被广泛使用,作为一类典型的环境激素,具有极强的生殖发育毒性,可通过多种途径进入食物链,严重威胁人体健康。本文对食品中邻苯二甲酸酯类塑化剂的污染途径,危害和限量标准进行了简要阐述,重点对现有的检测技术进行了综述,以期为食品中邻苯二甲酸酯类塑化剂污染的发现与防控提供参考。

基于响应面分析法的水质中邻苯二甲酸酯检测方法优化

建立了水质中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)的前处理及反相超高效液相色谱检测方法,通过单因素试验考察了色谱柱类型、流动相类型、流动相体积分数、流速及柱温对主峰信噪比的影响,并采用响应面分析法进行了方案优化。结果表明:氰基色谱柱优于C 18色谱柱;在最优色谱条件(流动相乙腈水溶液(体积分数64%)、流速0.22 mL/min、柱温28℃)下,DMP、DBP、DOP的主峰信噪比平均值分别为8890、6637、2991,对应的检出限分别为0.05、0.03、0.08μg/L,均低于《水质邻苯二甲酸二甲(二丁、二辛)酯的测定液相色谱法》(HJ/T 72—2001)规定的检出限,加标回收率分别为98.4%、99.8%和98.0%,相对标准偏差为0.98%、0.52%和0.83%,具有良好的灵敏度、回收率和重复性,能更好满足地下水等水体的痕量检测要求。

Perspectives on ecological risks of microplastics and phthalate acid esters in crop production systems

Microplastics(MPs)and phthalate acid esters(PAEs)co-occur as emerging contaminants of global importance.Their abundance in soil is of increasing concern as plastic-intensive practices continue.Mulching with plastic films,inclusion in fertilizers,composts,sludge application,and wastewater irrigation are all major and common sources of MPs and PAEs in soil.Here,we review studies on the concentration and effects of MPs and PAEs in soil.While there is limited research on the interactions between MPs and PAEs in agroecosystems,there is evidence to suggest they could mutually affect soil ecology and plant growth.Therefore,we propose new research into 1)establishing an efficient,accurate,and simple method to quantify different types of microplastics in soils and plants;2)exploring the behavior and understanding the mechanisms of co-transfer,transformation,and interactions with soil biota(especially in vegetable production systems);3)assessing the risk and consequences of combined and discreet impacts of MPs and PAEs on plants and soil biota,and 4)preventing or reducing the transfer of MPs and PAEs into-and within-the food chain.

冷冻法结合GC-MS/MS测定植物油中19种邻苯二甲酸酯类化合物

为了建立一种快速、高效、便捷测定植物油中19种邻苯二甲酸酯类化合物的检测方法,对冷冻法结合GC-MS/MS检测植物油中19种邻苯二甲酸酯类化合物含量的方法进行了研究。结果表明:(1)将前处理方法中–18℃冷冻保存24 h改为–36℃冷冻保存12 h,节省了样品前处理时间;(2)与LS/T 6131—2018《粮油检验植物油中邻苯二甲酸酯类化合物的测定》方法相比,除了对邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二正丁酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二异壬酯和邻苯二甲酸二异癸酯8种邻苯二甲酸酯类化合物的测定外,增加了对11种邻苯二甲酸酯类化合物的测定,包括邻苯二甲酸二烯丙酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯;(3)与LS/T 6131—2018方法中外标法定量相比,增加了同位素内标法定量,比较了同位素内标法和外标法在测定植物油中邻苯二甲酸酯类化合物的差异。结果表明,植物油中19种邻苯二甲酸酯类化合物在GC-MS/MS上线性关系良好,外标法和内标法相关系数均大于0.990,检出限和定量限均低于标准方法,且内标法精密度和准确度优于外标法。

花椒和生姜及其提取物中邻苯二甲酸酯类检测方法及迁移规律的研究

研究提出了分散固相萃取-气相色谱质谱同时测定花椒、生姜及其产品中4种邻苯二甲酸酯类的方法,并研究了超临界生产过程中邻苯二甲酸酯类污染物迁移规律。花椒和生姜及其提取物样品使用异辛烷提取,经分散固相萃取净化,采用气相色谱分离后,在电子轰击电离(EI)源和多反应监测模式下检测,邻苯二甲酸二甲酯和邻苯二甲酸二异丁酯使用外标法定量,邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基)己酯使用内标法定量。结果表明:该方法在线性范围内具有良好的线性关系,相关系数均大于0.992,线性范围在0.00~0.50μg/mL,平均回收率在94.0%~104.2%范围内。以花椒和生姜作为研究对象,研究了超临界萃取生产过程中塑化剂迁移规律,迁移率大多数在75%~120%之间。本法简便快速、准确可靠,适用于检测花椒、生姜及其产品中4种邻苯二甲酸酯类的测定,可作为日常生产过程中质量控制的方法。

Role of inflammatory lipid and fatty acid metabolic abnormalities induced by plastic additives exposure in childhood asthma

Lipid metabolism play an essential role in occurrence and development of asthma,and it can be disturbed by phthalate esters(PAEs)and organophosphate fame retardants(OPFRs).As a chronic infammatory respiratory disease,the occurrence risk of childhood asthma is increased by PAEs and OPFRs exposure,but it remains not entirely clear how PAEs and OPFRs contribute the onset and progress of the disease.We have profiled the serum levels of PAEs and OPFRs congeners by liquid chromatography coupled with mass spectrometry,and its relationships with the dysregulation of lipid metabolism in asthmatic,bronchitic(acute infammation)and healthy(non-infammation)children.Eight PAEs and nine OPFRs congeners were found in the serum of children(1–5 years old)from Shenzhen,and their total median levels were 615.16 ng/m L and 17.06 ng/m L,respectively.Moreover,the serum levels of mono-methyl phthalate(MMP),tri-propyl phosphate(TPP)and tri-n-butyl phosphate(TNBP)were significant higher in asthmatic children than in healthy and bronchitic children as control.Thirty-one characteristic lipids and fatty acids of asthma were screened by machine-learning random forest model based on serum lipidome data,and the alterations of infammatory characteristic lipids and fatty acids including palmitic acids,12,13-Di HODE,14,21-Di HDHA,prostaglandin D2 and Lyso PA(18:2)showed significant correlated with high serum levels of MMP,TPP and TNBP.These results imply PAEs and OPFRs promote the occurrence of childhood asthma via disrupting infammatory lipid and fatty acid metabolism,and provide a novel sight for better understanding the effects of plastic additives on childhood asthma.

“水晶泥”产品质量安全性分析

为测试水晶泥产品的质量安全,文中对购买的60批次水晶泥样品进行检测,主要关注水晶泥的硼酸含量、硼迁移量、可迁移元素、邻苯二甲酸酯、禁用偶氮5个风险项目,检测结果显示,水晶泥中硼酸的检出率为100%,最高值达到19767 mg/kg。96.7%的水晶泥硼迁移量不符合欧盟玩具标准对液体或粘性玩具材料≤300 mg/kg的要求,最高值达到3647 mg/kg,为欧盟标准限值的12.2倍。可迁移元素、邻苯二甲酸酯、禁用偶氮三个项目均未检出。

汽车内饰材料中邻苯二甲酸酯的风险分析

利用气质联用法对汽车内饰材料中的6种邻苯二甲酸酯类物质(DBP、BBP、DEHP、DNOP、DINP和DIDP)进行了风险分析。研究表明:建立的6种邻苯二甲酸酯类物质在0.3~10 mg/L的浓度范围内线性良好,检出限在0.1833~2.7359 mg/kg,定量限在0.6109~9.1198 mg/kg,加标回收率介于96.0%~102.8%,且相对标准偏差小于5%。同时,24种汽车内饰件中邻苯二甲酸酯类超标风险约为38%,且主要超标项集中在DEHP和DINP,这为汽车内饰材料安全标准制定提供了依据。