Synthetic phenolic antioxidants(SPAs)and parabens,particularly the high-molecularweight(HMW)SPAs and long alkyl chain(LAC)parabens with higher environmental persistence and toxicities,are widely produced and applied w...Synthetic phenolic antioxidants(SPAs)and parabens,particularly the high-molecularweight(HMW)SPAs and long alkyl chain(LAC)parabens with higher environmental persistence and toxicities,are widely produced and applied worldwide.However,their occurrence and potential risks in aquatic environments remain largely unknown.This work investigated 11 HMW SPAs and 3 LAC parabens in the river and treated industrial wastewater samples along the Yangtze River,the largest river and most important source water in China.For convenience of comparison,6 short alkyl chain(SAC)parabens were also included.In 15 industrial wastewater treatment plant effluents(effluent-IWTPs)and 34 surface water monitoring sections along the river,19 out of 20 target compounds were detected with total concentrations(TCs)from 152.5 to 1955.5 ng/L and 141.3 to 1364.9 ng/L in effluent-IWTPs and surface water,respectively.HMW SPAs 1,3,5-tris-[(3,5-di–tert–butyl–4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione(AO3114)and octadecyl 3-(3,5-di–tert–butyl–4-hydroxyphenyl)propionate(AO1076)were the dominant ones.HMWSPAs bis(3–tert–butyl–4–hydroxy-5-methylphenyl)propionate(AO245)and 4,4'-sulfanediylbis(2–tert–butyl–5-methylphenol)(AO-TBM6)and SAC parabens propylparaben(PrP)and butylparaben(BuP)posed medium to high potential ecological risks in 27 surface water monitoring sections.Additionally,AO-TBM6 also exhibited potential health risks in 2 out of 11 drinking water sources.Though the ecotoxicity data are very limited,the ubiquitous presence of the LAC parabens including hexylparaben(HeP)and octylparaben(OcP)in surface water should be of concern since these compounds usually exhibit stronger estrogen potencies than the SAC ones.Finally,kernel density analysis revealed that regulation of industrial discharges is necessary to mitigate the HMW SPA and paraben contamination.展开更多
In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detectio...In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detection and quantification of three commonly used parabens (methylparaben (MP), ethylparaben (EP) and propylparaben (PP)). We aimed to reduce the analysis time by using UPLC coupled with a short reverse phase C 18 monolithic column (25 mm×4.6 mm). Operating the monolithic column at low back-pressure resulted in high flow rates. A mobile phaseconsisting of a 25:75 (v/v) ratio of acetonitrile:0.05 Mphosphate buffer (pH 5) at a flow rate of 2.5 mL·min?1 was used to perform the separation. The amperometric detection with the BDD electrode was found to be optimal and reliably reproducible at a detection potential of 1.5 V vs. Ag/AgCl. Under these conditions, the separation of the three targetanalytes (MP, EP and PP) was achieved in 2 min and was linear within a sample concentration range of 0.1 to 50.0 mg·L?1 (r2 values of 0.9970, 0.9994 and 0.9994 for MP, EP and PP, respectively). This method was successfully applied to determine the concentrations of each parabeninsix real samples with therecoveries ranging from of 80.3% - 98.9% for all three parabensfrom samples spiked at 12, 22 and 32 mg·L?1. Therefore, the proposed method can be used as an alternative rapid and selective method for the determination of paraben levels in real samples.展开更多
Magnetic polymer Fe_(3)O_(4)@P(MMA-AA-DVB)full of carboxylate-functionalized groups was prepared via suspension polymerization method with nano Fe_(3)O_(4)as a core,methyl methacrylate(MMA)and methacrylic acid(AA)as m...Magnetic polymer Fe_(3)O_(4)@P(MMA-AA-DVB)full of carboxylate-functionalized groups was prepared via suspension polymerization method with nano Fe_(3)O_(4)as a core,methyl methacrylate(MMA)and methacrylic acid(AA)as monomers,divinylbenzene(DVB)as a crosslinker.The Fe_(3)O_(4)@P(MMA-AA-DVB)was characterized by elementary analysis(EA),powder X-ray diffraction(XRD),Fourier-transformed infrared spectrometry(FTIR),transmission electron microscopy(TEM),vibrating sample magnetometer(VSM)and thermogravimetric-differential thermal gravity(TG-DTG).The application for its adsorption and enrichment properties for parabens in aqueous solution was investigated.Furthermore,a rapid,sensitive and accurate method for the simultaneous determination of 4 kinds of parabens,i.e.,methylparaben(MPB),ethylparaben(EPB),propylparaben(PPB)and butylparaben(BPB),in water and cosmetics by magnetic solid-phase extraction(MSPE)liquid chromatography(MSPE-HPLC)was reported.The effects for MSPE,e.g.sample pH values,enrichment time,type and amount of elution solutions were investigated.The results showed that the average particle size of Fe_(3)O_(4)@P(MMA-AA-DVB)was around 20 nm,with the saturation magnetization intensity of 10.66 emu·g^(-1).The enrichment factor of the target parabens reached 250.Under the optimal condition,linearities were obtained ranging from 2-2000μg·L^(-1)with correlation coefficients(R)higher than 0.9998 for the target parabens.The average recoveries were at 93.6%-101.2%with the relative standard deviations(RSDs)in the range of 0.8%-8.5%.The limits of detection(LODs)were in the range of 0.22-1.60 ng·L^(-1)and the limits of quantification(LOQs)were between 0.8 ng·L^(-1)and 5.0 ng·L^(-1).The developed method can be applied to the routine analyses for the determination of the parabens in water and cosmetics samples.The present method has been applied in the determination of the parabens in 15 real samples.The result showed that 13 of them were found to contain MPB or PPB at concentration of1.26-347.8μg·kg^(-1)for MPB and 44.89-224.8μg·kg^(-1)for PPB,respectively.展开更多
Objective Accumulation of estrogenic compounds and other carcinogens in normal breast tissues contributes to unpredictable breast cancer incidence during adolescence and throughout life.To assess the role of parabens ...Objective Accumulation of estrogenic compounds and other carcinogens in normal breast tissues contributes to unpredictable breast cancer incidence during adolescence and throughout life.To assess the role of parabens in this phenomenon,the paraben content of adjacent normal-malignant breast tissues is measured in women with breast cancer living in Isfahan Province,Iran.Methods Adjacent normal-malignant breast tissue samples were obtained from 53 subjects.The parabens including methyl-paraben(Me PB),ethyl-paraben(Et PB),propyl-paraben(Pr PB),and butylparaben(Bu PB)were extracted from the sample supernatant and then subjected to gas chromatography analysis.Results Some risk factors for breast cancer were stimulated by parabens in adjacent malignant-normal breast tissues among young and middle-aged women with breast cancer.We observed a significant association for dose-response pattern of Me PB[OR=98.34(11.43–185.2),P=0.027]for both ER+and PR+women and Me PB[OR=164.3(CI:112.3–216.3),P<0.001]for HER2+women than women with negative receptors.The risk of 95-fold increase in Me PB dose and 164-fold increase in∑PBs dose were significant for women with hereditary breast cancer in first-degree relatives.Conclusions These results may promote future epidemiology studies and strategies to improve women's lifestyle and consume paraben-free products.展开更多
As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-conta...As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.展开更多
As a widely used food preservative,methyl paraben was experimentally evidenced with serious hormonelike adverse effects.Herein,a high performance thin-layer chromatography platformed bioluminescent bioautography and i...As a widely used food preservative,methyl paraben was experimentally evidenced with serious hormonelike adverse effects.Herein,a high performance thin-layer chromatography platformed bioluminescent bioautography and image analysis for the selective quantification and confirmation of methyl paraben was proposed and validated in vinegar and coconut juice.First,the detectability of the bioautography to the analyte on different layer materials was estimated,revealing that normal silica gel was the best choice.After that,the liquid of sample extract and working solution were separated to overcome the background noises due to co-extracted matrices.The separation result was then coupled to the optimized bioautography,enabling instant and straightforward screening of the targeted conpound.For accurate quantification,bioluninescent inhibition pattern caused by the analyte was processed by image analysis,giving useful sensitivity(LOD>16 mg/kg),precision(RSD<10.1%)and accuracy(spike-recovery rate 76.9%-112.2%).Finally,the suspected result was confirmed by determining its MS fingerprint,further strengthening the reliability of screening.展开更多
Calculations of chemical structures and photofading of parabens (PHB—4 hydroxybenzoic acid), which are p-hydroxybenzoic acid alkyl esters were performed. These compounds are used as preservatives for the substances u...Calculations of chemical structures and photofading of parabens (PHB—4 hydroxybenzoic acid), which are p-hydroxybenzoic acid alkyl esters were performed. These compounds are used as preservatives for the substances used in cosmetics. The reactivity of these derivatives with an oxidant—singlet oxygen—have been tested with a theoretical method of frontier orbitals. All-valence molecular orbital methods, AM1 and PM3, have been used to calculate frontier electron density for higher occupied HOMO and lower unoccupied LUMO orbitals, which might be sensitive to an electrophilic (with singleton oxygen atom 1O2) or nucleophilic ( superoxide anion radical) attack at a particular atom in a molecule. Using AM1 and PM3, we calculated the reactivity , superdelocalisability and electron density distributions. The obtained superdelocalisability rates allow you to explain the fastness values in different chemical molecules. The structure of parabens (PHB) was optimized by MM+, DM, AM1 or PM3, to achieve constant energy values at a convergence criterion of 0.01 kcal/mol. The performed calculations indicate that the electrophilic oxidation reaction should take place in the aromatic ring in the 2-position to the hydroxyl residue of PHB, whereas the superoxide radical reaction occurs mainly on the alkyl residues of the ester group. The reaction may take place according to superoxide mechanism or 1,2-addition, where the higher superdelocalisability values SN are located on neighboring atoms in aromatic systems.展开更多
Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine funct...Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine functions,it becomes imperative to prioritize the development of innovative bioanalytical techniques for effectively monitoring their presence in biological samples.In this study,an efficient solvent bar microextraction(SBME)was established,utilizing new hydrophobic deep eutectic solvents(DEs)to determine methylparaben and propylparaben in urine and plasma samples.The DEs comprising menthol and tris(2-ethylhexyl)phosphate(M-TEHP)at various molar ratios were synthesized for the first time to enhance the extraction capacity and promote the eco-friendliness of the DE used as an extraction solvent.Fourier-transform infrared(FT-IR)and proton nuclear magnetic resonance(1H NMR)spectroscopies were employed to confirm and investigate the properties of the successful synthesis(M-TEHP)DE at a molar ratio of 1:1.The synthesized DE exhibits low microbial toxicity and can be considered an eco-friendly solvent for extraction.Furthermore,quantum-chemical calculations were utilized to predict synthesized DE's structure and interaction energy with selected parabens.The influential operational factors of DE-SBME on the extraction efficiency(EE%)of both parabens were evaluated using response surface methodology based on central composite design,and a total of 30 extraction tests were conducted to determine the optimal conditions.The optimized DE-SBME,in combination with HPLC-DAD,exhibited low detection limits(0.54–0.91μg L^(−1)),excellent linearity(R^(2)≥0.9993),precise results(RSDs≤7.6%),satisfactory recoveries(92–97%)and negligible matrix effects.Hence,it had remarkable effectiveness and applicability in determining selected parabens in real urine and plasma samples.展开更多
基金supported by the National Key Research and Development Program of China(Nos.2021YFC3200801 and 2021YFC3200804).
文摘Synthetic phenolic antioxidants(SPAs)and parabens,particularly the high-molecularweight(HMW)SPAs and long alkyl chain(LAC)parabens with higher environmental persistence and toxicities,are widely produced and applied worldwide.However,their occurrence and potential risks in aquatic environments remain largely unknown.This work investigated 11 HMW SPAs and 3 LAC parabens in the river and treated industrial wastewater samples along the Yangtze River,the largest river and most important source water in China.For convenience of comparison,6 short alkyl chain(SAC)parabens were also included.In 15 industrial wastewater treatment plant effluents(effluent-IWTPs)and 34 surface water monitoring sections along the river,19 out of 20 target compounds were detected with total concentrations(TCs)from 152.5 to 1955.5 ng/L and 141.3 to 1364.9 ng/L in effluent-IWTPs and surface water,respectively.HMW SPAs 1,3,5-tris-[(3,5-di–tert–butyl–4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione(AO3114)and octadecyl 3-(3,5-di–tert–butyl–4-hydroxyphenyl)propionate(AO1076)were the dominant ones.HMWSPAs bis(3–tert–butyl–4–hydroxy-5-methylphenyl)propionate(AO245)and 4,4'-sulfanediylbis(2–tert–butyl–5-methylphenol)(AO-TBM6)and SAC parabens propylparaben(PrP)and butylparaben(BuP)posed medium to high potential ecological risks in 27 surface water monitoring sections.Additionally,AO-TBM6 also exhibited potential health risks in 2 out of 11 drinking water sources.Though the ecotoxicity data are very limited,the ubiquitous presence of the LAC parabens including hexylparaben(HeP)and octylparaben(OcP)in surface water should be of concern since these compounds usually exhibit stronger estrogen potencies than the SAC ones.Finally,kernel density analysis revealed that regulation of industrial discharges is necessary to mitigate the HMW SPA and paraben contamination.
文摘In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detection and quantification of three commonly used parabens (methylparaben (MP), ethylparaben (EP) and propylparaben (PP)). We aimed to reduce the analysis time by using UPLC coupled with a short reverse phase C 18 monolithic column (25 mm×4.6 mm). Operating the monolithic column at low back-pressure resulted in high flow rates. A mobile phaseconsisting of a 25:75 (v/v) ratio of acetonitrile:0.05 Mphosphate buffer (pH 5) at a flow rate of 2.5 mL·min?1 was used to perform the separation. The amperometric detection with the BDD electrode was found to be optimal and reliably reproducible at a detection potential of 1.5 V vs. Ag/AgCl. Under these conditions, the separation of the three targetanalytes (MP, EP and PP) was achieved in 2 min and was linear within a sample concentration range of 0.1 to 50.0 mg·L?1 (r2 values of 0.9970, 0.9994 and 0.9994 for MP, EP and PP, respectively). This method was successfully applied to determine the concentrations of each parabeninsix real samples with therecoveries ranging from of 80.3% - 98.9% for all three parabensfrom samples spiked at 12, 22 and 32 mg·L?1. Therefore, the proposed method can be used as an alternative rapid and selective method for the determination of paraben levels in real samples.
文摘Magnetic polymer Fe_(3)O_(4)@P(MMA-AA-DVB)full of carboxylate-functionalized groups was prepared via suspension polymerization method with nano Fe_(3)O_(4)as a core,methyl methacrylate(MMA)and methacrylic acid(AA)as monomers,divinylbenzene(DVB)as a crosslinker.The Fe_(3)O_(4)@P(MMA-AA-DVB)was characterized by elementary analysis(EA),powder X-ray diffraction(XRD),Fourier-transformed infrared spectrometry(FTIR),transmission electron microscopy(TEM),vibrating sample magnetometer(VSM)and thermogravimetric-differential thermal gravity(TG-DTG).The application for its adsorption and enrichment properties for parabens in aqueous solution was investigated.Furthermore,a rapid,sensitive and accurate method for the simultaneous determination of 4 kinds of parabens,i.e.,methylparaben(MPB),ethylparaben(EPB),propylparaben(PPB)and butylparaben(BPB),in water and cosmetics by magnetic solid-phase extraction(MSPE)liquid chromatography(MSPE-HPLC)was reported.The effects for MSPE,e.g.sample pH values,enrichment time,type and amount of elution solutions were investigated.The results showed that the average particle size of Fe_(3)O_(4)@P(MMA-AA-DVB)was around 20 nm,with the saturation magnetization intensity of 10.66 emu·g^(-1).The enrichment factor of the target parabens reached 250.Under the optimal condition,linearities were obtained ranging from 2-2000μg·L^(-1)with correlation coefficients(R)higher than 0.9998 for the target parabens.The average recoveries were at 93.6%-101.2%with the relative standard deviations(RSDs)in the range of 0.8%-8.5%.The limits of detection(LODs)were in the range of 0.22-1.60 ng·L^(-1)and the limits of quantification(LOQs)were between 0.8 ng·L^(-1)and 5.0 ng·L^(-1).The developed method can be applied to the routine analyses for the determination of the parabens in water and cosmetics samples.The present method has been applied in the determination of the parabens in 15 real samples.The result showed that 13 of them were found to contain MPB or PPB at concentration of1.26-347.8μg·kg^(-1)for MPB and 44.89-224.8μg·kg^(-1)for PPB,respectively.
基金funded by Isfahan University of Medical Sciences,Isfahan,Iran [Research Project code:397158]
文摘Objective Accumulation of estrogenic compounds and other carcinogens in normal breast tissues contributes to unpredictable breast cancer incidence during adolescence and throughout life.To assess the role of parabens in this phenomenon,the paraben content of adjacent normal-malignant breast tissues is measured in women with breast cancer living in Isfahan Province,Iran.Methods Adjacent normal-malignant breast tissue samples were obtained from 53 subjects.The parabens including methyl-paraben(Me PB),ethyl-paraben(Et PB),propyl-paraben(Pr PB),and butylparaben(Bu PB)were extracted from the sample supernatant and then subjected to gas chromatography analysis.Results Some risk factors for breast cancer were stimulated by parabens in adjacent malignant-normal breast tissues among young and middle-aged women with breast cancer.We observed a significant association for dose-response pattern of Me PB[OR=98.34(11.43–185.2),P=0.027]for both ER+and PR+women and Me PB[OR=164.3(CI:112.3–216.3),P<0.001]for HER2+women than women with negative receptors.The risk of 95-fold increase in Me PB dose and 164-fold increase in∑PBs dose were significant for women with hereditary breast cancer in first-degree relatives.Conclusions These results may promote future epidemiology studies and strategies to improve women's lifestyle and consume paraben-free products.
基金financial supports from the National Natural Science Foundation of China (Nos.41977365and 41425015)the National Key Research and Development Program of China (No.2019YFC1804503)+4 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (No.2017BT01Z032) Natural Sciences and Engineering Research Council of Canadathe Canada Research Chairs ProgramAlberta InnovatesAlberta Health for their supportsupport of Guangdong University of Technology for her visiting scholarship.
文摘As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethylparaben could be absorbed onto NS within 38 hr, whereas the maximum adsorption capacity was 0.45 mg/g under room temperature. High temperature could improve the adsorption performance of ethylparaben using NS. In particular, for the temperature of 313 K, the adsorption turned spontaneous. The well-fitted adsorption kinetics indicated that both the surface adsorption and intra-particle diffusion contribute to the overall adsorption process. The monolayer adsorption on the surface of NS was primarily responsible for the elimination of ethylparaben. The adsorption mechanism showed that hydrophobic partitioning into organic matter could largely govern the adsorption process, rather than the Zn S that was the main component of NS. Furthermore, the ethylparaben adsorbed on the surface of NS was stable, as only less than 2% was desorbed and photochemically degraded under irradiation of simulated sunlight for 5 days. This study revealed that NS might serve as a potential natural remediation agent for some hydrophobic EOCs including parabens, and emphasized the significant role of naturally abundant minerals on the remediation of EOCs-contaminated water bodies.
基金financially supported by National Natural Science Foundation of China (21804058)Shanxi Postdoc Reward (SXBYKY2022001)+1 种基金Shanxi Scholarship Council of China (2021068)Shanxi Agricultural University High-Level Talent Project (2021XG013)。
文摘As a widely used food preservative,methyl paraben was experimentally evidenced with serious hormonelike adverse effects.Herein,a high performance thin-layer chromatography platformed bioluminescent bioautography and image analysis for the selective quantification and confirmation of methyl paraben was proposed and validated in vinegar and coconut juice.First,the detectability of the bioautography to the analyte on different layer materials was estimated,revealing that normal silica gel was the best choice.After that,the liquid of sample extract and working solution were separated to overcome the background noises due to co-extracted matrices.The separation result was then coupled to the optimized bioautography,enabling instant and straightforward screening of the targeted conpound.For accurate quantification,bioluninescent inhibition pattern caused by the analyte was processed by image analysis,giving useful sensitivity(LOD>16 mg/kg),precision(RSD<10.1%)and accuracy(spike-recovery rate 76.9%-112.2%).Finally,the suspected result was confirmed by determining its MS fingerprint,further strengthening the reliability of screening.
文摘Calculations of chemical structures and photofading of parabens (PHB—4 hydroxybenzoic acid), which are p-hydroxybenzoic acid alkyl esters were performed. These compounds are used as preservatives for the substances used in cosmetics. The reactivity of these derivatives with an oxidant—singlet oxygen—have been tested with a theoretical method of frontier orbitals. All-valence molecular orbital methods, AM1 and PM3, have been used to calculate frontier electron density for higher occupied HOMO and lower unoccupied LUMO orbitals, which might be sensitive to an electrophilic (with singleton oxygen atom 1O2) or nucleophilic ( superoxide anion radical) attack at a particular atom in a molecule. Using AM1 and PM3, we calculated the reactivity , superdelocalisability and electron density distributions. The obtained superdelocalisability rates allow you to explain the fastness values in different chemical molecules. The structure of parabens (PHB) was optimized by MM+, DM, AM1 or PM3, to achieve constant energy values at a convergence criterion of 0.01 kcal/mol. The performed calculations indicate that the electrophilic oxidation reaction should take place in the aromatic ring in the 2-position to the hydroxyl residue of PHB, whereas the superoxide radical reaction occurs mainly on the alkyl residues of the ester group. The reaction may take place according to superoxide mechanism or 1,2-addition, where the higher superdelocalisability values SN are located on neighboring atoms in aromatic systems.
文摘Parabens are antimicrobial preservatives with extensive applications in cosmetics,toiletries,pharmaceuticals,and food.Considering the legitimate concerns relating to their potential to disrupt multiple endocrine functions,it becomes imperative to prioritize the development of innovative bioanalytical techniques for effectively monitoring their presence in biological samples.In this study,an efficient solvent bar microextraction(SBME)was established,utilizing new hydrophobic deep eutectic solvents(DEs)to determine methylparaben and propylparaben in urine and plasma samples.The DEs comprising menthol and tris(2-ethylhexyl)phosphate(M-TEHP)at various molar ratios were synthesized for the first time to enhance the extraction capacity and promote the eco-friendliness of the DE used as an extraction solvent.Fourier-transform infrared(FT-IR)and proton nuclear magnetic resonance(1H NMR)spectroscopies were employed to confirm and investigate the properties of the successful synthesis(M-TEHP)DE at a molar ratio of 1:1.The synthesized DE exhibits low microbial toxicity and can be considered an eco-friendly solvent for extraction.Furthermore,quantum-chemical calculations were utilized to predict synthesized DE's structure and interaction energy with selected parabens.The influential operational factors of DE-SBME on the extraction efficiency(EE%)of both parabens were evaluated using response surface methodology based on central composite design,and a total of 30 extraction tests were conducted to determine the optimal conditions.The optimized DE-SBME,in combination with HPLC-DAD,exhibited low detection limits(0.54–0.91μg L^(−1)),excellent linearity(R^(2)≥0.9993),precise results(RSDs≤7.6%),satisfactory recoveries(92–97%)and negligible matrix effects.Hence,it had remarkable effectiveness and applicability in determining selected parabens in real urine and plasma samples.
