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SEPARATION AND PURIFICATION TECHNOLOGY · 2019 · IF 5.107

Oxidative paraben removal with chlorine dioxide: Reaction kinetics and mechanism

Qianhui Mao,Qi Li,Huimin Li,Shoujun Yuan,Jibiao Zhang

This study investigated the reactivity and mechanism of paraben oxidization by chlorine dioxide. Degradation kinetics of methylparaben (MeP) and propylparaben (PrP) followed pseudo-first-order kinetics, and were studied in a pH range of 4.0–7.0 at 15 ± 1 °C. The k app values were 84.3 M −1 ·s −1 and 83.2 M −1 ·s −1 for MeP and PrP, respectively, when pH value was 5.0 and the temperature was 15 ± 1 °C. The rate constants depended on the solution pH, temperature, humic acid, and HCO 3 – concentrations. At pH values of 4–5.0, k app increased slowly, while at a pH value of 7.0, k app increased rapidly. The reaction rate constants increased with increasing temperature. Furthermore, the reaction rate was inhibited by humic acid addition, while the reaction rate increased after addition of HCO 3 – . Two main degradation products were identified by GC–MS and the reaction pathways were proposed.

研究领域: 环境科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Bisulfite-assisted surface Fenton-like degradation of dimethyl phthalate by ferrihydrite-H2O2 system

Xiru Chen,Xinyue Gu,Chao Wang,Liuqing Huang,Dingding Wu,Hao Wu,Sijia Liang,Jingyi Ling,Cheng Gu

As a common plasticizer, phthalic acid esters (PAEs) have been widely employed to improve the flexibility and workability of polymetric materials, thus leading to their widespread distribution in soils and wastewater. Moreover, PAEs raised great public concerns due to their endocrine-disrupting effects, which could damage reproductive system and body development at low exposure dose. In the present study, a ferrihydrite-H 2 O 2 -bisulfite ternary system was developed to achieve efficient degradation of dimethyl phthalate (DMP). Our results showed that 86.6 % of total DMP could be removed within 240 min by the ferrihydrite-H 2 O 2 -bisulfite ternary system, in which the respective optimum concentration of ferrihydrite, H 2 O 2 and bisulfite was set as 1.0 g/L, 5.0 mM and 2.0 mM. For comparison, negligible DMP removal was observed in the binary systems of ferrihydrite-H 2 O 2 , ferrihydrite-bisulfite and H 2 O 2 -bisulfite. Hydroxyl radical (•OH) was identified as the dominant reactive species for DMP degradation based on the results of electron paramagnetic resonance (EPR) analysis and free radicals quenching experiments. By complexing with iron species, bisulfite could accelerate the reduction of Fe(III) to Fe(II), thus increasing the generation of •OH by ∼4 times in the heterogeneous ferrihydrite-H 2 O 2 system. Furthermore, ferrihydrite exhibited excellent recyclability without any modification as indicated by the negligible decrease in the catalytic degradation efficiency of DMP. Thus, in addition to efficient degradation of PAEs in wastewater, our study would shed light on the in-situ soil remediation technology on the basis of bisulfite-assisted heterogeneous Fenton-like reactions.

CAS / MDL: 75-09-2
研究领域: 环境科学 · 化学
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TOXICOLOGY AND APPLIED PHARMACOLOGY · 2024 · IF 3.3

Long-term exposure to the mixture of phthalates induced male reproductive toxicity in rats and the alleviative effects of quercetin

Li-Lan Liu,Jun-Zhe Yue,Zhen-Yu Lu,Ru-Ya Deng,Can-Can Li,Ye-Na Yu,Wen-Jin Zhou,Min Lin,Hai-Tao Gao,Jiaming Liu,Ling-Zi Xia

Phthalates (PEs), such as di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP) and butyl benzyl phthalate (BBP) could cause reproductive and developmental toxicities , while human beings are increasingly exposed to them at low-doses. Phytochemical quercetin (Que) is a flavonoid that has estrogenic effect, anti-inflammatory and anti-oxidant effects. This study was conducted to assess the alleviative effect of Que. on male reproductive toxicity induced by the mixture of three commonly used PEs (MPEs) at low-dose in rats, and explore the underlying mechanism. Male rats were treated with MPEs (16 mg/kg/day) and/or Que. (50 mg/kg/d) for 91 days. The results showed that MPEs exposure caused male reproductive injuries, such as decreased serum sex hormones levels, abnormal testicular pathological structure, increased abnormal sperm rate and changed expressions of PIWIL1 and PIWIL2. Furthermore, MPEs also changed the expression of steroidogenic proteins in steroid hormone metabolism, including StAR, CYP11A1 , CYP17A1 , 17β-HSD, CYP19A1 . However, the alterations of these parameters were reversed by Que. MPEs caused male reproductive injuries in rats; Que. inhibited MPEs' male reproductive toxicity, which might relate to the improvement of testosterone biosynthesis.

研究领域: 毒理学 · 生殖生物学 · 药理学
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ENVIRONMENT INTERNATIONAL · 2025 · IF 9.7

Transformation metabolites of phthalate esters (PAEs) inhibited rice growth through jasmonic acid signaling pathway

Yingying Sun,Jie Chen,Wei Wang,Lizhong Zhu

Phthalate esters (PAEs) were ubiquitous in agricultural soils and could be metabolized after being absorbed by crops, posing significant implications for crop yield and quality. We hypothesize that monophthalates (mPAEs), the hydrolyzed products of PAEs, might mimic phytohormone jasmonic acid (JA) to activate the JA signaling pathway, therefore enhancing the defense towards pests and inhibiting the rice plant growth. Taking dibutyl phthalate (DBP) as a representative PAE, our study discovered that DBP exposure significantly induced JA-related outcomes including decreased larval weight (9.58–18.8%), and rice biomass (11.7–34.2%). Under the conditions where the JA content remained unchanged, monobutyl phthalate (MBP), the hydrolyzed product of DBP, triggered the JA signaling pathway, evidenced by significantly upregulated genes encoding coronatine insensitive 1 (COI1) (1.56–1.73 fold), jasmonate ZIM-domain (JAZ) (4.33–7.71 fold), MYC2 transcription factor (2.07–2.87 fold), and promoted phytoalexins production in downstream signaling. MBP conjugated with isoleucine, and the conjugate subsequently mimicked a JA bioactivator (JA-isoleucine conjugate) to occupy the binding site of COI1-JAZ co-receptor protein, thereby initiating the JA signaling pathway. These JA-related outcomes and mechanism were consistently evidenced in rice exposed to other four typical PAEs, and the aliphatic chain length of selected PAEs indicated a negative contribution to these observations. In this study, we discovered a unconventional mechanism through which the transformation metabolites of PAEs elicit pest defense while simultaneously inhibiting rice growth, providing insights into the risk assessment of PAEs on crop yields and quality.

研究领域: 环境科学 · 植物生理学 · 农业科学
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2023 ·Vol. 40 ·期 9 ·2149-2158 · IF 2.7

Hydrogenation of dimethyl 2,5-furandicarboxylate to dimethyl tetrahydrofuran-2,5-dicarboxylate over Ru/HY

Li Chengfeng,Lyu Qishen,Li Zheng,Yang Shuliang,Sun Yong,Tang Xing,Zeng Xianhai,Lin Lu

The hydrogenation of biomass-based furan compounds is an important step for the catalytic valorization of biobased chemicals. In this work, Ru-based catalysts supported on different supports, such as HY, MgO and Amberlyst-15, were prepared and estimated for the hydrogenation of dimethyl 2,5-furandicarboxylate (FDMC). Among them, Ru/HY provided a desirable yield of 99.4% for tetrahydrofuran-2,5-dicarboxylic acid dimethyl ester (THFDMC) under 90 °C and 3 MPa H 2 . Based on catalyst characterization, Ru/HY could offer more surface Ru 0 species and carbon radical intermediates than other catalysts, which could largely favor the activation of hydrogen and then promote the hydrogenation of FDMC over Ru/HY.

CAS / MDL: 39389-20-3 1309-48-4
研究领域: 催化化学 · 可再生资源化工
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MACROMOLECULAR RAPID COMMUNICATIONS · 2022 ·Vol. 44 ·期 5 ·2200765 · IF 5.006

Mechanically Strong and Tough Poly(urea-urethane) Thermosets Capable of Being Degraded under Mild Condition

Yanlong Yin,Yang Xu,Xuhao Zhang,Baorong Duan,Zhirong Xin,Chunyang Bao

The development of degradable polymeric materials such as degradable polyurethane or polyurea has been much highlighted for resource conservation and environmental protection. Herein, a facile strategy of constructing mechanically strong and tough poly(urea-urethane) (PUU) thermosets that can be degraded under mild conditions by using triple boron-urethane bonds (TBUB) as cross-linkers is demonstrated. By tailoring the molecular weight of the soft segment of the prepolymers, the mechanical performance can be finely controlled. Based on the cross-linking of TBUB units and hydrogen-binding interactions between TBUB linkages, the as-prepared PUU thermosets have excellent mechanical strength of ≈40.2 MPa and toughness of ≈304.9 MJ m −3 . Typically, the PBUU900 strip can lift a barbell with 60 000 times its own weight, showing excellent load-bearing capacity. Meanwhile, owing to the covalent cross-linking of TBUB units, all the PUU thermosets show initial decomposition temperatures over 290 °C, which are comparable to those of the traditional thermosets. Moreover, the TBUB cross-linked PUU thermosets can be easily degraded in a mild acid solution. The small pieces of the PBUU sample can be fully decomposed in 1 m HCl/THF solution for 3.5 h at room temperature.

研究领域: 材料科学 · 环境科学
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ENVIRONMENTAL POLLUTION · 2016 · IF 4.839

Carboxylesterase-involved metabolism of di-n-butyl phthalate in pumpkin (Cucurbita moschata) seedlings

Qingqi Lin,Siyuan Chen,Yuanqing Chao,Xiongfei Huang,Shizhong Wang,Rongliang Qiu

Uptake and accumulation by plants is a significant pathway in the migration and transformation of phthalate esters (PAEs) in the environment. However, limited information is available on the mechanisms of PAE metabolism in plants. Here, we investigated the metabolism of di- n -butyl phthalate (DnBP), one of the most frequently detected PAEs, in pumpkin ( Cucurbita moschata ) seedlings via a series of hydroponic experiments with an initial concentration of 10 mg L −1 . DnBP hydrolysis occurred primarily in the root, and two of its metabolites, mono- n -butyl phthalate (MnBP) and phthalic acid (PA), were detected in all plant tissues. The MnBP concentration was an order of magnitude higher than that of PA in shoots, which indicated MnBP was more readily transported to the shoot than was PA because of the former's dual hydrophilic and lipophilic characteristics. More than 80% of MnBP and PA were located in the cell water-soluble component except that 96% of MnBP was distributed into the two solid cellular fractions (i.e., cell wall and organelles) at 96 h. A 13–20% and 29–54% increase of carboxylesterase (CXE) activity shown in time-dependent and concentration-dependent experiments, respectively, indicated the involvement of CXEs in plant metabolism of DnBP. The level of CXE activity in root subcellular fractions was in the order: the cell water-soluble component (88–94%) >> cell wall (3–7%) > cell organelles (3–4%), suggesting that the cell water-soluble component is the dominant locus of CXE activity and also the domain of CXE-catalyzed hydrolysis of DnBP. The addition of triphenyl phosphate, a CXE inhibitor, led to 43–56% inhibition of CXE activity and 16–25% increase of DnBP content, which demonstrated the involvement of CXEs in plant metabolism of DnBP. This study contributes to our understanding of enzymitic mechanisms of PAE transformation in plants.

CAS / MDL: 131-70-4
研究领域: 环境科学 · 植物学 · 生化与分子生物学
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CHEMOSPHERE · 2016 · IF 3.698

Heat-activated persulfate oxidation of methyl- and ethyl-parabens: Effect, kinetics, and mechanism

Yiqun Chen,Pinya Deng,Pengchao Xie,Ran Shang,Zongping Wang,Songlin Wang

We evaluated the degradation of methylparaben (MeP) and ethylparaben (EtP), two representative parabens, using the heat-activated persulfate system in a laboratory. Both sulfate and hydroxyl radicals contributed to the removal of the two parabens. The degradations of both MeP and EtP were improved by increasing the heating temperature or persulfate dose in accordance with a pseudo-first-order reaction model. The oxidation efficiency of parabens was found to be pH-dependent; decreasing in the order pH 5.0 > 7.0 > 9.0. The presence of chloride, bicarbonate , or humic acid was found to inhibit the degradation of the two parabens to some extent because of competition for the reactive radicals, with humic acid having the most serious effect. Dealkylation of the methyl unit, decarboxylation of the carboxylic group, and subsequent hydrolysis are proposed to be involved in the degradation pathway of MeP. The results suggest that the heat-activated persulfate system might be efficiently applied in the treatment of paraben-containing water samples. This was also supported by the results of applying this system to treat a real water sample containing both MeP and EtP.

研究领域: 环境科学 · 化学工程
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CHEMOSPHERE · 2022 · IF 8.943

Enhanced water permeance and EDCs rejection using a UiO-66-NH2-predeposited polyamide membrane

Bin Zhao,Min Sun,Zhiqiang Guo,Liang Wang,Yiran Qian,Xiaojia He,Jixiang Li

Endocrine disrupting compounds (EDCs) have been increasingly detected in drinking water sources, and pose severe threat to human health. Polyamide (PA) based nanofiltration (NF) membrane has great potential for EDCs removal from water, but the removal of hydrophobic EDCs is not satisfying due to strong hydrophobic affinity. In this study, UiO-66-NH 2 /PA membranes were prepared by predepositing hydrophilic UiO-66-NH 2 onto the substrate prior to interfacial polymerization. The UiO-66-NH 2 aggregates increased the permeable area and strengthened the “gutter effect”. Therefore, the pure water flux of UiO-66-NH 2 /PA increased by 115% compared with that of the thin-film composite (TFC) membrane, and its rejection of Na 2 SO 4 was 96%. The hydrophilicity-enhanced PA film reduced its adsorption of EDCs and decreased the driving force for EDCs diffusion. Moreover, the UiO-66-NH 2 -induced hydrophilic nanochannels, including the interfacial gaps between PA film and UiO-66-NH 2 aggregates, the gaps in UiO-66-NH 2 aggregates, and the inherent pores in UiO-66-NH 2 crystals, alleviated the hydrophobic affinity and effectively restricted EDCs diffusion. The rejection rates of methylparaben, propylparaben, bisphenol A, and benzylparaben by the optimal UiO-66-NH 2 /PA were 50%, 67%, 75%, and 85%, respectively, and the water/benzylparaben selectivity was 4.4 times as high as that of TFC. The results demonstrate that incorporating hydrophilic metal-organic frameworks (MOFs) can improve the membrane hydrophilicity and create hydrophilic nanochannels, and is an effective strategy to enhance EDCs removal by nanofiltration.

研究领域: 环境科学 · 水处理 · 材料科学 · 化学工程
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POLYMER INTERNATIONAL · 2024 · IF 2.9

Preparation of biodegradable poly(lactic acid)/poly[(butylene diglycolate)-co-furandicarboxylate] blends with excellent toughness and gas barrier performance

Yong Yang,Jing Shen,Erxun Hu,Yajin Fang,Zhibo Xu,Juan Li

Poly(lactic acid) (PLA) is known as one of the most promising biodegradable polyesters, while inherent brittleness and insufficient gas barrier performance limit its potential application as a film material. Herein, poly[(butylene diglycolate)- co -furandicarboxylate] (PBDF) with excellent flexibility and good gas barrier properties was synthesized and then melt-blended with PLA. Compared with neat PLA, the elongation at break of the PLA/PBDF20 blend increased more than 40 times and reached over 176.7%. In addition, its O 2 , CO 2 and H 2 O permeability coefficients decreased by 21.3%, 50.8% and 46.3%, respectively. Moreover, the PLA/PBDF20 blend also exhibited better biodegradability, with a weight loss rate increasing from 2.7% of neat PLA to 19.0% after 5 weeks of composting. Notably, incorporation of a multifunctional epoxy compatibilizer (Joncryl ADR®-4368) into the PLA/PBDF blends further enhanced their toughness and gas barrier performance, which could be attributed to the improvement of the miscibility between PLA and PBDF. © 2024 Society of Chemical Industry.

研究领域: 材料科学 · 环境科学 · 高分子化学
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ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY · 2023 · IF 6.8

Exposure estimates of parabens from personal care products compared with biomonitoring data in human hair from Northeast China

Yunyang Li,Na Zheng,Siyu Sun,Sujing Wang,Xiaoqian Li,Jiamin Pan,Muyang Li,Le Lang,Zelin Yue,Binbin Zhou

Parabens (PBs), a class of endocrine-disrupting chemicals (EDCs), are extensively used as additives in personal care products (PCPs); however, distinguishing between endogenous and exogenous contamination from PCPs in hair remains a challenge. We conducted a comprehensive analysis of the levels, distribution patterns, impact factors, and sources of PBs in 119 human hair samples collected from Changchun, northeast China. The detection rates of methylparaben (MeP), propylparaben (PrP), and ethylparaben (EtP) in hair samples were found to be 100%. The concentration of PBs in hair followed the order of MeP (57.48 ng/g) > PrP (46.40 ng/g) > EtP (6.80 ng/g). The concentration of PrP in female hair was significantly higher (65.38 ng/g) than that observed in male hair (7.82 ng/g) ( p  < 0.05). The levels of excretion rates of MeP ( ER MeP ) and excretion rates of PrP (ER PrP ) in the hair-dying samples (ER MeP : 17.89 ng/day; ER PrP : 14.15 ng/day) were found to be 2.52 and 2.40 times higher, respectively, compared to the non-hair-dying samples (ER MeP : 7.09 ng/day; ER PrP : 6.05 ng/day). However, the system exposure dosage (SED) results revealed that although hair dyes exhibited higher PBs, human exposure was found to be lower than certain PCPs. The results of the correlation analysis revealed that toner, face cream, body lotion, and hair conditioner were identified as the primary sources of PBs in male hair. Furthermore, the human exposure resulting from the utilization of female hair dye and serum exhibited a positive correlation with hair ER MeP and ER PrP levels, indicating in the screening of samples, excluding hair samples using hair dye and haircare essential oil can effectively avoid the interference caused by exogenous contamination from PCPs.

研究领域: 环境科学 · 公共卫生 · 毒理学 · 化学分析
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2016 ·Vol. 23 ·期 22 ·23081-23091 · IF 2.76

Chlorination of parabens: reaction kinetics and transformation product identification

Mao Qianhui,Ji Feng,Wang Wei,Wang Qiquan,Hu Zhenhu,Yuan Shoujun

The reactivity and fate of parabens during chlorination were investigated in this work. Chlorination kinetics of methylparaben (MeP), ethylparaben (EtP), propylparaben (PrP), and butylparaben (BuP) were studied in the pH range of 4.0 to 11.0 at 25 ± 1 °C. Apparent rate constants ( k app ) of 9.65 × 10 −3  M -0.614 ·s −1 , 1.77 × 10 −2  M -1.019 ·s −1 , 2.98 × 10 −2  M -0.851 ·s −1 , and 1.76 × 10 −2  M -0.860 ·s −1 for MeP, EtP, PrP, and BuP, respectively, were obtained at pH 7.0. The rate constants depended on the solution pH, temperature, and NH 4 + concentration. The maximum k app was obtained at pH 8.0, and the minimum value was obtained at pH 11.0. The reaction rate constants increased with increasing temperature. When NH 4 + was added to the solution, the reaction of parabens was inhibited due to the rapid formation of chloramines. Two main transformation products, 3-chloro-parabens and 3,5-dichloro-parabens, were identified by GC-MS and LCMS-IT-TOF, and a reaction pathway was proposed. Dichlorinated parabens accumulated in solution, which is a threat to human health and the aqueous environment.

研究领域: 环境科学 · 化学
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