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.

Research Progress on Distribution,Sources and Ecological Effects of Phthalate in Soil

Phthalate esters(PAEs)are widely used as main plasticizers in plastic products,agricultural regulators,toys,and other fields.This paper reviewed the research progress on the distribution,sources,and ecological effects of PAEs.The effects of PAEs on soil microorganisms,animals,plants and soil properties were explored in sequence,providing effective theoretical basis for future research on PAEs.

N-acetylcysteine and zinc sulphate abate di-2-ethylhexyl phthalate-mediated reproductive dysfunction in rats:Focus on oxidative and sex hormone receptors mechanisms

Objective:To investigate the potential of N-acetylcysteine(NAC)and zinc sulphate(ZnSO_(4))in mitigating reproductive dysfunction caused by di-2-ethylhexyl phthalate(DEHP)in rats and to understand the underlying mechanisms,specifically oxidative stress and sex hormone receptor activity.Methods:Thirty-five male Wistar rats were randomly divided into five equal groups(n=7 per group).Group 1 was administered 0.5 mL of distilled water and served as the control group.Group 2 was given only DEHP(750 mg/kg/day),while group 3,4 and 5 were given DEHP(750 mg/kg/day)plus NAC(100 mg/kg/day),DEHP(750 mg/kg/day)plus ZnSO_(4)(0.5 mg/kg/day),and DEHP(750 mg/kg/day)plus NAC(100 mg/kg/day)as well as ZnSO_(4)(0.5 mg/kg/day),respectively.All treatments lasted for 21 days.Samples were obtained after the rats were sacrificed,and hormones levels in the serum and markers of oxidative stress in the testicles were analyzed using the enzyme-linked immunosorbent assay.The amount of androgen receptors in the testicles was determined by immunohistochemistry,and the susceptibility of testosterone and DEHP to bind to androgen receptor and 5α-reductase was determined by molecular docking studies.Results:DEHP decreased reproductive hormones,testicular antioxidant enzymes,increased malondialdehyde levels,and negatively impacted histology of the pituitary and testes.NAC or ZnSO_(4) treatment showed a marked improvement in testicular antioxidant status and hormone levels,as well as a positive effect on the histology of the pituitary and testes.The combination of both treatments appeared to be more effective.The affinity of DEHP to bind to androgen receptors may lead to disruption of androgen receptor signaling,which can further result in dysfunction of hormones related to androgen.However,NAC is more likely to form stronger binding interactions with follicle stimulating hormone and luteinizing hormone receptors,as well as gonadotropin-releasing hormone receptors,when compared to DEHP.Conclusions:The possibility that NAC and ZnSO_(4) could downregulate DEHP-induced sex hormone changes is suggested by their potential to reduce toxicity.

Research progress on classification,source,application of phytosterol esters,and their thermal oxidation stability

Phytosterol esters can effectively decrease serum cholesterol concentration in the human body and prevent cardio-cerebrovascular diseases.It was found that phytosterol esters exhibited better solubility and bioavailability than free phytosterols.In recent years,phytosterol esters have attracted increasing attention.However,during food processing,phytosterol esters are susceptible to degradation at high temperatures,resulting in certain losses and formation of potentially harmful substances for humans.This paper reviews the relevant literatures and updates on the thermal oxidation stability of phytosterol esters in recent years from the following aspects:(i)Sources,physiological activities,and applications of phytosterol esters;(ii)Oxidation mechanism of phytosterol esters;(iii)Effects of phytosterols species,the volume of addition,food matrix,heating temperature and time,and antioxidants on the thermal loss and oxidation stability of phytosterol esters.The research progress on the safety of phytosterol esters is also discussed in detail.Additionally,the prospects for future research are highlighted.

Study on the regulatory effect of liver X receptor in HEK293 cells by six main diterpene esters in Semen Euphorbiae

Background:To study the effects of the main diterpene esters in Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)on the transcriptional activity and protein expression of liver X receptor(LXR).Methods:The effect of the main diterpene ester components in Semen Euphorbiae on the viability of HEK293 cells were studied by MTT assay.The LXR-Luc plasmid vector was transfected into HEK293 cells and treated with Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)for 24 h.The effect of the main diterpene ester components of Semen Euphorbiae on LXR-Luc luciferase activity was investigated by dual luciferase reporter gene system,and the expression of LXRαprotein was detected by Western Blot.Results:Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)could significantly reduce the relative luciferase activity(RLU)of LXRα,and the expression level of LXRαprotein was significantly down-regulated.Conclusion:Euphorbia factor L_(1),L_(2),L_(3),L_(7a),L_(7b)and L_(8)can inhibit the expression of LXR protein level,which may be achieved by inhibiting the transcriptional activity of LXR.

Determination of phthalate esters in fat-containing foods by packed nanofiber solid-phase extraction column and gas chromatography

A new method for simultaneous determination of four phthalate esters （ PAEs） in commercial fat-containing foods was developed by the combination of a packed nanofibers column based on solid-phase extraction with gas chromatography-flame ionization detector （ GC-FID ）. Conditions for obtaining optimum extraction efficiency such as extraction solvents, morphologies of adsorbent, ion strength and pH were investigated and optimized in detail. Under the optimized conditions, the limits of detection （LODs） found for dibutyl phthalate （DBP） , butyl benzyl phthalate （BBP）, diethyl hexyl phthalate （DEHP） and di-n-octyl phthalate （DNOP） were 50, 25, 50 and 25 ng/g, respectively. Good linearity of four PAEs was achieved in the range of 50 to 4 000 ng/g. The proposed method was applied for analyzing different kinds of fat-containing samples. PAEs in commercial fat-containing samples can be highly extracted by a packed solid-phase extraction column of 5 mg polystyrene （ PS） nanofibers. The satisfactory average recoveries were obtained in the range of 96. 7% to 102. 3% , and the relative standard deviations （RSDs） below 5% were achieved. The proposed method reduces the organic solvent consumption, the complex and tedious procedures for sample pretreatment, and achieves high sensitivity and reproducibility for the investigated PAEs.

Cloud point extraction coupled with HPLC-UV for the determination of phthalate esters in environmental water samples

A method based on cloud point extraction was developed to determine phthalate esters including di-ethyl-phthalate （DEP）, di- （2-ethylhexyl）-phthalate （DEHP） and di-cyclohexyl-phthalate （DCP） in environmental water samples using high-performance liquid chromatography separation and ultraviolet detection （HPLC-UV）. The non-ionic surfactant Triton X-114 was chosen as extraction solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na2SO4, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, the method can achieve preconcentration factors of 35, 88, 111 and detection of limits of 2.0, 3.8, 1.0 ng/ml for DEP, DEHP and DCP in 10-ml water sample, respectively. The proposed method was successfully applied to the determination of trace amount of phathalate esters in effluent water of the wastewater treatment plant and the lixivium of plastic fragments.

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.

Analysis of Phthalate Esters in Air, Soil and Plants in Plastic Film Greenhouse

The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations of PEs in air and soil samples in plastic film greenhouse are much higher than those of contrast samples. But concentrations of PEs in plants in plastic film greenhouse are not remarkably affected by the pollution of air and soil.

Magnetic Solid-Phase Extraction of Phthalate Esters from Environmental Water Samples using Fibrous Phenyl-functionalized Fe3O4@SiO2@KCC-1

A new kind of phenyl-functionalized magnetic fibrous mesoporous silica(Fe3 O4@Si O2@KCC-1-phenyl) was prepared by copolymerization as an efficient adsorbent for the magnetic extraction of phthalate esters from environmental water samples. The obtained Fe3 O4@Si O2@KCC-1-phenyl showed monodisperse fibrous spherical morphology, fairly strong magnetic response(29 emu/g), and an abundant π-electron system, which allowed rapid isolation of the Fe3 O4@Si O2@KCC-1-phenyl from solutions upon applying an appropriate magnetic field. Several variables that affect the extraction efficiency of the analytes,including the type of the elution solvent, amount of adsorbent, extraction time and reusability, were investigated and optimized. Under optimum conditions, the Fe3 O4@Si O2@KCC-1-phenyl was used for the extraction of four phthalate esters from environmental water samples followed by high-performance liquid chromatographic analysis. Validation experiments indicated that the developed method presented good linearity(0.1-20 ng/m L), low limit of detection(7.5-29 μg/L, S/N =3). The proposed method was applied to the determination of phthalate esters in different real water samples, with relative recoveries of 93%-103.4%and relative standard deviation of 0.8%-8.3%.

Determination of phthalate esters in physiological saline solution by monolithic silica spin column extraction method

Monolithic silica spin column extraction （MonoSpin-SPE） was developed as a simple, sensitive, and eco-friendly pretreatment method which combined with ultra-fast liquid chromatography-mass spectrometry （UFLC-MS） to determine the levels of six phthalate esters, dimethyl- （DMP）, diethyl- （DEP）, dipropyl- [ DPrP], butyl-benzyl- （BBP）, dicyclohexyl- （DcHP）, and di-n-octyl-（DOP） phthalate in physiological saline samples. Under optimized experimental conditions, the method was linear in the following ranges： 0.2- 50 μg/L for DMP, DEP, DPrP, DcHP and DOP; 5- 100 μg/L for BBP. The correlation coefficients （R2 ） were in the range of 0. 9951 - 0. 9995 for all the analytes and the limits of detection （LODs） and limits of quantification （LOQs） were in the ranges of 0.02 - 0.9 μg/L and 0.08 - 2.7μg/L, respectively. The pretreatment process showed good reproducibility with inter-day and intra-day relative standard deviations （RSDs） below 8.5% and 11.2%, respectively. This method was used to determine the levels of six phthalate esters in physiological saline samples and the recoveries ranged from 71.2% to 107.3%. DMP and DEP were found in actual physical saline samples （brand A and brand B）.

Microwave Extraction Followed by Solid-phase Extraction for the Determination of Phthalate Esters in Fish Samples by Gas Chromatography

A new analytical procedure based on solid-phase extraction method coupled to GC-FID has been developed and validated for the determination of five phthalate esters （PAEs） （dimethyl-（DMP）, diethyl-（DEP）, di-n-butyl-（DBP）, di-2-ethylhexyl- （DEHP）, di-n-octyl-（DOP）） in fish samples. There was a good linear relationship in the range of 0.05-10μg with the detection limits of 0.09-0.16ng .The recoveries obtained for PAEs ranged from 88.6% to 96.4%with RSD of 4.2%-10.2%.The applicability of the developed method was demonstrated for real fish samples.

Occurrence and distribution of phthalate esters (PAEs) in wetland sediments

This study investigated the occurrence and distribution of 15 phthalate esters (PAEs) in sediments collected from Qixinghe wetlands, northeast China. Total concentration of PAEs in all sediments ranged from 128.41 to 502.79 mu g kg(-1), with the mean value of 284.61 mu g kg(-1). PAEs significantly differed among wetland types; the average PAEs concentration of surface sediments were as follows: Phragmites australis wetland (PAW, 419.87 +/- 73.61 mu g kg(-1)) > Carex lasiocarpa wetland (CLW, 304.18 +/- 56.47 mu g kg(-1)) > Deyeuxia angustifolia wetland (DAW, 129.78 +/- 18.24 mu g kg(-1)). Dimethyl phthalate (DMP), diisobutyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate (DEHP) were found in all sediments, DEHP was the most abundant PAEs congeners with concentrations varying from 37.62 to 294.9 mu g kg(-1). DMP and DEHP exhibited relatively higher concentrations in CLW and PAW wetlands than in DAW, indicating that the different deoxidization and biodegradation conditions could have important implications for the distribution patterns of PAEs in wetland sediments. The variation of PAEs concentrations in horizontal and vertical sediments with wetland types could be attributed to the migration of contaminants by surface water, groundwater and atmospheric deposition. The occurrence and distribution of PAEs in wetlands also suggests that contamination in natural ecosystems should not be overlooked.

Phthalate Esters Biodegradation by Fusarium Oxysporum in Vegetable Soil

In this research, soil samples were frst polluted with 6 PAEs （i.e. DMP, DEP, DIBP, DBP, DEHP, and BBP） at 3 different concentration gradients （0, 10, and 20 mg/kg） and then treated with a highly-efficient degradation fungus, Fusarium oxysporum （PO-Yi）, to investigate the biodegradation of PAEs in pepper and eggplant soil. The findings revealed that PO-Yi can accelerate the degradation of PAEs in vegetable soils including pepper and eggplant soil to varying degrees. The highest absolute degradation rate （up to 39.5%） was observed in DEP-treated soils at the high pollution level （20 mg/kg）, which was 14.2% higher than that at the middle pollution level （10 mg/kg）. The degradation effect in the pepper soil was superior to that in the eggplant soil. Vegetable soil, either pepper soil or eggplant soil, which was polluted by various PAEs at different pollution gradients and then treated with PO-Yi fungus presented good bioremediation results. In the pepper and eggplant soil, 76.8% and 63.1% of the PAEs with a total volume of 60 mg/kg were degraded within 30 d respectively. PO-Yi, indigenous microorganisms, and the vegetables, i.e. pepper and eggplant had good synergistic effects on the degradation of compound PAEs in PAE-polluted pot soil.

Study on Phthalate Esters Pollution in the Soil of Facility Vegetable Base in Yangling District of Xianyang City

[Objectives]To evaluate the pollution status of phthalate esters(PAEs)in the soil of facility vegetable base in Yangling District of Xianyang City.[Methods]A total of 15 kinds of PAEs in soil samples were detected and analyzed by gas chromatography-mass spectrometry.[Results]A total of 12 kinds of PAEs were detected in analyzed soil samples,with a total content of 53.4-3524.1μg/kg and an average of 602.7μg/kg.Specifically,DEHP,DBP,DIBP,DMEP,BBP and DNOP were the main PAEs pollutants in the soil,with the detection rates of 100%,100%,100%,73.3%,63.3%and 53.3%,and the average content were 286.3,167.3,123.1,157.6,121.3,and 130.5μg/kg,respectively.[Conclusions]Compared with the soil in other regions,the pollution level of PAEs in the soil of facility vegetable base in Yangling District is lower,but such compounds are widespread in the facility vegetable base,and their potential environmental risks should attract close attention.

Phthalate Esters Biodegradation by Fusarium oxysporum in Vegetable Soil

In this research, soil samples were first polluted with 6 PAEs (i.e. DMP, DEP, DIBP, DBP, DEHP, and BBP) at 3 different concentration gradients (0, 10, and 20 mg/kg) and then treated with a highly-efficient degradation fungus, Fusarium oxysporum (PO-Yi), to investigate the biodegradation of PAEs in pepper and eggplant soil. The findings revealed that PO-Yi can accelerate the degradation of PAEs in vegetable soils including pepper and eggplant soil to varying degrees. The highest absolute degradation rate (up to 39.5%) was observed in DEP-treated soils at the high pollution level (20 mg/kg), which was 14.2% higher than that at the middle pollution level (10 mg/kg). The degradation effect in the pepper soil was superior to that in the eggplant soil. Vegetable soil, either pepper soil or eggplant soil, which was polluted by various PAEs at different pollution gradients and then treated with PO-Yi fungus presented good bioremediation results. In the pepper and eggplant soil, 76.8% and 63.1% of the PAEs with a total volume of 60 mg/kg were degraded within 30 d respectively. PO-Yi, indigenous microorganisms, and the vegetables, i.e. pepper and eggplant had good synergistic effects on the degradation of compound PAEs in PAEpolluted pot soil.

Bis(2-butoxyethyl) Phthalate Delays Puberty Onset by Increasing Oxidative Stress and Apoptosis in Leydig Cells in Rats

Objective This study investigated the effects of bis(2-butoxyethyl) phthalate(BBOP) on the onset of male puberty by affecting Leydig cell development in rats.Methods Thirty 35-day-old male Sprague-Dawley rats were randomly allocated to five groups mg/kg bw per day that were gavaged for 21 days with BBOP at 0, 10, 100, 250, or 500 mg/kg bw per day. The hormone profiles;Leydig cell morphological metrics;mRNA and protein levels;oxidative stress;and AKT,mTOR, ERK1/2, and GSK3β pathways were assessed.Results BBOP at 250 and/or 500 mg/kg bw per day decreased serum testosterone, luteinizing hormone, and follicle-stimulating hormone levels mg/kg bw per day(P < 0.05). BBOP at 500 mg/kg bw per day decreased Leydig cell number mg/kg bw per day and downregulated Cyp11a1, Insl3, Hsd11b1,and Dhh in the testes, and Lhb and Fshb mRNAs in the pituitary gland(P < 0.05). The malondialdehyde content in the testis significantly increased, while Sod1 and Sod2 mRNAs were markedly downregulated, by BBOP treatment at 250–500 mg/kg bw per day(P < 0.05). Furthermore, BBOP at 500mg/kg bw per day decreased AKT1/AKT2, mTOR, and ERK1/2 phosphorylation, and GSK3β and SIRT1levels mg/kg bw per day(P < 0.05). Finally, BBOP at 100 or 500 μmol/L induced ROS and apoptosis in Leydig cells after 24 h of treatment in vitro(P < 0.05).Conclusion BBOP delays puberty onset by increasing oxidative stress and apoptosis in Leydig cells in rats.The graphical abstract is available on the website www.besjournal.com.

Pollution characteristics and risk assessment of organophosphate esters in aquaculture farms and natural water bodies adjacent to the Huanghe River delta

To date,little attention has been paid to the effects of organophosphate esters(OPEs)pollution on aquacultural environment and aquatic product safety.Huanghe(Yellow)River delta area is one of the largest aquaculture centers in China,where ecological security protection is crucial in the national strategy of China.To explore the pollution characteristics,bioaccumulation,and health risks of OPEs in aquaculture farms in the Huanghe River delta and natural water bodies in the adjacent seas,five species of organisms from different farm types nearby the Huanghe River delta,and the corresponding culture water and sediments were sampled in this study.The total concentrations of Σ_(13)OPEs in water,sediments,and organisms were 51.53-272.18 ng/L,52.63-63.17 ng/g dry weight(dw),and 46.82-108.90 ng/g dw,respectively.Among the five types of culture ponds,the water samples from the swimming crab and hairy crab culture ponds exhibited higher OPEs,the concentration of OPEs in the sediments from the few ponds was relatively balanced,and the OPEs in the organism from the holothurian ponds was higher.Tris(1,3-dichloro-2-isopropyl pho sphate)(TDCP)was the main contaminant in water samples and tripropyl phosphate(TPrP)in sediments and organisms.However,trisphenyl phosphate(TPhP)showed the strongest bioaccumulation ability,followed by 2-ethylhexyl diphenyl phosphate(EHDPP)and TPrP.The bioaccumulation capacities of the five species were as follows:prawn>holothurian>hairy crab>swimming crab>carp.These five types of organisms,as main seafood in human consumption,were at low risk of negative impacts of pollution.However,the risk from the mixture of organophosphate flame retardants(OPFRs)still requires more attention due to the increasing consumption and production in the world.

Green tea polyphenols alleviate di-(2-ethylhexyl)phthalate-induced liver injury in mice

BACKGROUND Di(2-ethylhexyl)phthalate(DEHP)is a common plasticizer known to cause liver injury.Green tea is reported to exert therapeutic effects on heavy metal exposureinduced organ damage.However,limited studies have examined the therapeutic effects of green tea polyphenols(GTPs)on DEHP-induced liver damage.AIM To evaluate the molecular mechanism underlying the therapeutic effects of GTPs on DEHP-induced liver damage.METHODS C57BL/6J mice were divided into the following five groups:Control,model[DEHP(1500 mg/kg bodyweight)],treatment[DEHP(1500 mg/kg bodyweight)+GTP(70 mg/kg bodyweight),oil,and GTP(70 mg/kg bodyweight)]groups.After 8 wk,the liver function,blood lipid profile,and liver histopathology were examined.Differentially expressed micro RNAs(miRNAs)and mRNAs in the liver tissues were examined using high-throughput sequencing.Additionally,functional enrichment analysis and immune infiltration prediction were performed.The miRNA-mRNA regulatory axis was elucidated using the starBase database.Protein expression was evaluated using immunohistochemistry.RESULTS GTPs alleviated DHEP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,liver fibrosis,and mitochondrial and endoplasmic reticulum lesions in mice.The infiltration of macrophages,mast cells,and natural killer cells varied between the model and treatment groups.mmu-miR-141-3p(a differentially expressed miRNA),Zcchc24(a differentially expressed mRNA),and Zcchc24(a differentially expressed protein)constituted the miRNA-mRNA-protein regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage in mice.CONCLUSION This study demonstrated that GTPs mitigate DEHP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,and partial liver fibrosis,and regulate immune cell infiltration.Additionally,an important miRNAmRNA-protein molecular regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage was elucidated.

Adsorption of Phthalic Acid Esters by Humic Acid and Its Research Progress

Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental pollution from PAEs.In this paper,the extraction,characterization and adsorption models of humic acid were reviewed,and the research status of adsorption of PAEs by humic acid was further summarized.Based on these,the feasibility and observable application prospect of humic acid as a cheap adsorbent were analyzed.