Alkylphenols Research Articles

53 Pre-implantation exposure to bisphenol A and 4-tert-octylphenol result in disruption of calcium channels

Miscarriage due to blastocyst implantation failure occurs in up to two-thirds of all miscarriage cases in humans. Calcium (Ca2+) has been shown to involve many cellular signal transduction pathways as well as regulation of cell adhesion, which is necessary for the physiology process of endometrial epithelial cell transformation and stromal cell decidualization during embryo implantation. Exposure to endocrine-disrupting chemicals (ED) can regulate the expression of genes associated with calcium transport in during pregnancy such as TRPV5, TRPV6, PMCA, and NCX1. Additionally, exposure to ED during early gestation results in disrupted intrauterine implantation, uterine receptive, leading to implantation failure. In this study, oestrogen (E2), bisphenol A (BPA), octylphenol (OP), and/or ICI 182,780 (oestrogen receptor antagonist, ICI) were injected subcutaneously from gestation Day 1 to gestation Day 3 post coitus. The number of implantation sites was significantly lower in the OP group, and no implantation site was observed in the E2 and ED+ICI groups. There were differences in the expression of calcium transient transport channel between maternal uterine and implantation. The level of TRPV6 and TRPV5 mRNA and protein was significantly increased by ED and/or ICI treatment in the uterus. The levels of TRPV5 and TRPV6 gene expression were significantly increased by ED with/without ICI treatment in the uterus. However, TRPV5 and TRPV6 gene expression was significantly lower in implantation site samples. The NCX1 and PMCA1 mRNA levels were significantly decreased by OP and BPA in the implantation site samples. Both mRNA and protein levels of MUC1 were markedly higher in all groups, except the BPA group when compared with the vehicle group in the uterus. The LIF and HOXA-10 mRNA were significantly low in E2; BPA+ICI; OP; and/or ICI in both the uterus and implantation site. Expression of the oestrogen receptor (ERa) and progesterone receptor (PR) was significantly lower in all groups except the BPA group when compared with the vehicle group. Taken together, E2, BPA, and OP disrupt the success of implantation through altered expression of calcium transport genes.

Octylphenol influence growth and development of Rana chensinensis tadpoles via disrupting thyroid function

Octylphenol (OP), a class of endocrine disrupting chemicals (EDCs), could produce adverse effects on developmental process of animals. Thyroid hormone is one of the important hormones involved in animal development. To determine whether OP affect the growth and development of amphibian larvae via interfering the thyroid function, Rana chensinensis larvae at Gosner stage 29 were exposed to 10−8, 10−7 and 10−6 mol/L OP in the present study. Results demonstrated that OP could decrease the body length and mass and retard the development of tadpoles. The histologic evaluation showed microscopic structures of thyroid gland were changed in 10−7 and 10−6 mol/L OP treated groups on day 40. The expression levels of Dio2, Dio3, TRα and TRβ mRNA in the liver, brain, skin and tail of tadpoles were detected by qRT-PCR, when treated with OP for 20, 30, 40 and 50 day, respectively. The results of qRT-PCR showed OP could affect the expressions of Dio2, Dio3, TRα and TRβ mRNA in the four tissues, and then influence the activity and function of THs, further affecting the growth and development of the tadpoles.

Decomposition of 15 aromatic compounds in supercritical water oxidation

Supercritical water oxidation (SCWO) of 15 aromatic compounds, including bisphenol A (BPA), nonylphenol (NP) and octylphenol (OP), was investigated under temperature and reaction time ranged of 350–550 °C and 0.5–6 min, respectively, with 300% excess oxygen, resulted in the degradation rate constants of total organic carbon (kTOC) were 0.130–0.392 min−1. To further explore the relationship between TOC removal and molecular characteristics, density functional theory (DFT) method had been used to calculate the quantum descriptors of the 15 aromatic compounds. The result of correlation analysis showed that the most positive partial charge on the H atom, namely q(H)x, played a significant role in TOC removal, which implied the more q(H)x value was, the easier H atom could lose, resulted in higher kTOC constant. Different substituent groups in the phenyl ring could lead to different TOC removal efficiencies. It presented that the more F(0) value was, the more easily to be attacked by radicals, as a result, the kTOC followed the order that benzenesulfonic acid (BSA) > phenol > methylbenzene (MB) > 3-phenylpropionic acid (3-PPA), as well as BPA < OP < NP.

Oxidative stress and hepatotoxicity of Rana chensinensis exposed to low doses of octylphenol

This study investigated the effects of low doses of octylphenol (OP) on the oxidative stress and hepatotoxicity in amphibian liver. The frog, Rana chensinensis, were exposed to 10−8, 10−7, 10−6 mol/L OP for 10, 20 and 30 days. The activities of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) in liver were reduced at first, then recovered slightly, and the content of malondialdehyde (MDA) and hydrogen peroxide (H2O2) were increased significantly. Histopathology showed that in some liver tissues of OP treated frogs, the hematococoel expansion, the fat accumulation, the cytoplasmic vacuolization and even hepatocyte necrosis were present. Ultrastructure revealed that there were lipid droplet accumulation, mitochondria deformation and nuclear condensation in some hepatocytes. These results confirm that low doses OP exposure can give rise to oxidative stress in the liver of frogs, reduce antioxidant enzymes activities, lead to partial organelles damage in hepatocyte and the fat accumulate in hepatic tissue.

Adsorption driven preferential degradation of alkyl phenols on hydrophobic perfluoroalkyl modified {0 0 1}-TiO2

Preferential degradation of low concentrated contaminants with high toxicity is of great environmental significant. Perfluoroalkyl group was adopted as functional group to construct hydrophobic surface on highly exposed {0 0 1}-TiO2 for preferential degradation of nonyl phenol. The modified electrode showed superior hydrophobicity with contact angle of more than 160° after optimization of preparation condition. Besides, the modified electrode improved light absorbance ability of visible light, leading to better photocatalytic property. The degradation of NP, OP and HP on the modified {0 0 1}-TiO2 was obviously more efficient over that unmodified, which was about 1.5 times in the kinetic constant, showing preferential degradation of alkyl phenols on perfluoroalkyl decorated {0 0 1}-TiO2. Preferential degradation on the modified {0 0 1}-TiO2 was due to the superior adsorption ability to alkyl phenols. The adsorption capacity to alkyl phenols on the modified electrode was more than 2 times over the that unmodified. The adsorption of alkyl phenols on the hydrophobic electrode was further studied by in-situ infrared. It was found that there was specific hydrophobic interaction between the alkyl group of alkyl phenols and the perfluoroalkyl group modified on photocatalyst surface, which was the reason of alkyl phenols preferential degradation on the hydrophobic photocatalytic interface. The results showed great potential applications in selective wastewater treatment.

Differential Toxicity of Alkylphenols in JEG-3 Human Placental Cells: Alteration of P450 Aromatase and Cell Lipid Composition.

Alkylphenols (APs) are a diverse class of chemicals that can cross the placental barrier and interfere with embryonic and fetal development. This work investigates the comparative toxicity, ability to inhibit aromatase activity, and to alter the lipid composition of 10 alkylphenols in the human placenta choriocarcinoma cell line JEG-3. Among the selected APs, 4-dodecylphenol (DP), 4-heptylphenol (HP), and 4-cumylphenol (CP) showed the highest cytotoxicity (EC50: 18-65 µM). Aromatase inhibition was closely related to the hydrophobicity of APs. HP significantly induced the generation of reactive oxygen species (ROS) (43-fold), inhibited placental aromatase activity (IC50: 41 µM), and induced a general dose-dependent depletion of polyunsaturated lipids (10-20 µM), which were attributed to high levels of oxidative stress. In contrast, 2,4,6-tri-tert-butylphenol (TTBP) significantly induced the intracellular accumulation of triacylglycerides (TGs), whereas DP increased the synthesis of phosphatidylcholines (PCs) and TGs at the expense of diacylglycerides (DGs). Overall, this study evidences the different modes of action of alkylphenols in human placental JEG-3 cells, describes differential lipidomic fingerprints, and highlights DP, HP, CP, and TTBP as the ones that caused the most harmful effects.

Balancing Tricks and Mini-pigs: Steps along the Road to Propofol

Balancing Tricks and Mini-pigs: Steps along the Road to Propofol

Chemical transformations in technical cashew nut shell liquid and isolated mixture of cardanols, evaluation of the antioxidant activity and thermal stability of the products for use in pure biodiesel

Biodiesel demand is increasing all over the world. The maintenance of oxidative stability is extremely important to biodiesel market, from the point of view of the quality of the fuel as the economic amount involved. In the present work, we synthesized new antioxidant candidates for biodiesel from chemical transformations in alkyl phenols present in technical cashew nut shell liquid (t-CNSL) and, more specifically, in cardanols isolated from t-CNSL. This raw material is viable, easy accessed and low cost. Five chemical transformations were performed in both t-CNSL and cardanols with yields from 50% to 92%. The starting materials and their respective derivatives were characterized by 1H NMR, 13C NMR and IR. Antioxidant activity and thermal stability of the products were evaluated. The induction period for pure biodiesel was 6.35 h and the addition of 0.5% (w/w) of cardanols increased to 7.37 h. Two products presented excellent antioxidant activity, epoxidized cardanols (4) and hydrolyzed cardanols (6). They increased the induction period to 15.05 h and 18.62 h, respectively. The oxygenated derivatives also showed better thermal stability than the starting materials.

Controlled Synthesis of Carbon Nanospheres via the Modulation of the Hydrophilic Length of the Assembled Surfactant Micelles.

A co-polymerization-carbonization method was employed to synthesize porous carbon nanospheres (PCNSs) using pyrrole-aniline polymers as a carbon source and alkyl phenol non-ionic surfactants as templates. The effect of the hydrophilic length on the carbon nanosphere size was systematically investigated. The so-prepared PCNSs were characterized via high-magnification scanning electron microscopy, dynamic light scattering (DLS) analysis, and N2 adsorption and desorption analysis. The results indicate that the obtained nanosphere diameter can be tuned by changing the length of the hydrophilic groups. The length of the hydrophilic groups mainly affects the size of the vesicles or micelles formed by the assembly of the surfactant in solution, as was verified by the DLS results. After activation by KOH, the typical sample EO(30)-PCNS has a high specific surface area of 2137 m2/g and a large pore volume of 1.76 cm3/g. Electrochemical tests in 6 M KOH demonstrated that the assembled EO(30)-PCNS supercapacitor electrode displays good capacitive properties, such as a high specific capacitance of 221 F/g at 1.0 A/g and a good rate capacity of 68% retention at 10.0 A/g. This finding suggests that the uniform particle shape and high specific surface area are beneficial for the ion transportation, leading to good electrochemical performances. Our work provides a novel synthetic strategy for the fabrication of carbon nanospheres or other nanosphere materials for the construction of high-performance supercapacitors by optimizing few parameters, such as the length of the hydrophilic or hydrophobic groups of the surfactants.

Revealing the pathways of catalyst deactivation by coke during the hydrodeoxygenation of raw bio-oil

Virtually all processes aiming for fuels and chemicals from biomass entail no less than one step for removing oxygen by hydrodeoxygenation (HDO). The bottleneck of HDO is the formation of deactivating carbonaceous species on the catalyst surface. In this work, we have studied the deactivation pathways of catalysts based on noble metal nanoparticles (Pt-Pd) supported on mildly acid supports during the HDO of raw bio-oil. At conditions of accelerated deactivation, monitoring the evolution with time on stream of hydrocarbon and oxygenated compounds in the reaction medium, the intermediates on the catalyst surface and the nature-location of deactivating species, two parallel deactivation routes have been revealed: the deposition of (i) thermal or pyrolytic lignin from alkylmethoxy phenols, on the catalyst mesopores and favored at low temperature, and; of (ii) aromatic coke from polycyclic aromatic hydrocarbons, starting on the catalyst micropores through condensation reactions and promoted by acidic sites and high temperature. Nevertheless, catalyst deactivation can be controlled within limits at harsh temperature conditions (450 °C) due to the preferential HDO of alkyl(methoxy) phenols into aromatics and the formation-hydrocracking steady state of the aromatic precursors of coke.

Catalytic Fast Pyrolysis of Kraft Lignin With Conventional, Mesoporous and Nanosized ZSM-5 Zeolite for the Production of Alkyl-Phenols and Aromatics.

The valorization of lignin that derives as by product in various biomass conversion processes has become a major research and technological objective. The potential of the production of valuable mono-aromatics (BTX and others) and (alkyl)phenols by catalytic fast pyrolysis of lignin is investigated in this work by the use of ZSM-5 zeolites with different acidic and porosity characteristics. More specifically, conventional microporous ZSM-5 (Si/Al = 11.5, 25, 40), nano-sized (≤20 nm, by direct synthesis) and mesoporous (9 nm, by mild alkaline treatment) ZSM-5 zeolites were tested in the fast pyrolysis of a softwood kraft lignin at 400–600°C on a Py/GC-MS system and a fixed-bed reactor unit. The composition of lignin (FT-IR, 2D HSQC NMR) was correlated with the composition of the thermal (non-catalytic) pyrolysis oil, while the effect of pyrolysis temperature and catalyst-to-lignin (C/L) ratio, as well as of the Si/Al ratio, acidity, micro/mesoporosity and nano-size of ZSM-5, on bio-oil composition was thoroughly investigated. It was shown that the conventional microporous ZSM-5 zeolites are more selective toward mono-aromatics while the nano-sized and mesoporous ZSM-5 exhibited also high selectivity for (alkyl)phenols. However, the nano-sized ZSM-5 zeolite exhibited the lowest yield of organic bio-oil and highest production of water, coke and non-condensable gases compared to the conventional microporous and mesoporous ZSM-5 zeolites.

Synthesis, Properties and Applications of Anionic Phosphate Ester Surfactants: A Review

Abstract This paper reviews the various technologies involved in the synthesis of anionic phosphate ester surfactants. Use of base material such as alcohol ethoxylates, alkyl phenol ethoxylates, fatty acid ethoxylates and phosphating reagents plays a key role on the applications and properties of phosphate ester surfactants. Also roles are played by the reaction conditions maintained and charging conditions on the mono-diester ratio. In this paper attempt has been made to review the base materials used for the synthesis of phosphate esters, synthesis processes and their effect on the properties of phosphate esters, applications and global scenario of phosphate ester surfactants.

Bisphenols and Alkylphenols in Food: From Farm to Table

Bisphenols and Alkylphenols in Food: From Farm to Table

Use of ESI FT–ICR MS to investigate molecular transformation in simulated aerobic biodegradation of a sulfur-rich crude oil

Achieving an understanding of the biodegradation of organic sulfur compound(s) (OSC) in crude oils has been hampered by limitations in separation methods and analytical techniques. In this study, a simulated aerobic biodegradation experiment was performed on a sulfur-rich crude oil, from which a series of biodegraded oils from slight to moderate degrees of biodegradation were obtained. Molecular transformations in these biodegraded oils were investigated by gas chromatography–mass spectrometry (GC–MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS) under both positive- and negative-ion electrospray ionization (ESI) modes. The variations in the distributions of saturated hydrocarbons, OSCs, and acidic components during aerobic biodegradation were studied. A gradual decrease of OSCs with alkyl chains during biodegradation, especially in those with few sulfur-containing or naphthenic/aromatic rings, was observed. In addition, sulfur-containing phenols with alkyl chains also exhibited a trend of gradual decrease similar to alkyl phenols, with fewer ring numbers being more susceptible to biodegradation. The biodegradation pathways for OSCs and sulfur-containing acids, as well as certain other heteroatomic compounds, are discussed. Terminal oxidation, rather than sulfur-specific degradation, is the more likely biodegradation pathway of these OSCs, as in the case of n-alkanes in this study. Sulfur-containing carboxylic acids may be the biodegradation products of these OSCs.

Analysis of Bisphenol A, Alkylphenols, and Alkylphenol Ethoxylates in NIST SRM 2585 and Indoor House Dust by Gas Chromatography-Tandem Mass Spectrometry (GC/MS/MS).

Background: Ingestion of house dust has been demonstrated to be an important exposure pathway to several contaminants in young children. These compounds include bisphenol A (BPA), alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analysis of these compounds in house dust is challenging because of the complex composition of the sample matrix. Objective: The objective was to develop a simple and sensitive method to measure BPA, APs, and APEOs in indoor house dust. Methods: An integrated method that involved solvent extraction using sonication, sample cleanup by solid-phase extraction, derivatization by 2,2,2-trifluoro-N-methyl-N-(trimethylsilyl)acetamide, and analysis by GC coupled with tandem MS was developed for the simultaneous determination of BPA, APs, and APEOs in NIST Standard Reference Material (SRM) 2585 (Organic contaminants in house dust) and in settled house dust samples. Results: Target analytes included BPA, 4-tert-octylphenol (OP), OP monoethoxylate, OP diethoxylate, 4-n-nonylphenol (4nNP), 4nNP monoethoxylate (4nNP1EO), branched nonylphenol (NP), NP monoethoxylate, NP diethoxylate, NP triethoxylate, and NP tetraethoxylate. The method was sensitive, with method detection limits ranging from 0.05 to 5.1 μg/g, and average recoveries between 82 and 115%. All target analytes were detected in SRM 2585 and house dust except 4nNP and 4nNP1EO. Conclusions: The method is simple and fast, with high sensitivity and good reproducibility. It is applicable to the analysis of target analytes in similar matrixes, such as sediments, soil, and biosolids. Highlights: Values measured in SRM 2585 will be useful for future research in method development and method comparison.

Bisphenol A and octylphenol exacerbate type 1 diabetes mellitus by disrupting calcium homeostasis in mouse pancreas

In pancreatic β cells, which produce and secrete insulin, Ca2+ signals contribute to insulin production and secretion. Bisphenol A (BPA) and octylphenol (OP) are reported to increase plasma insulin levels and insulin transcription factors, but regulation of plasma glucose levels did not decrease proportionally to the insulin increase. We hypothesized that BPA and OP disrupt calcium homeostasis resulting in insulin resistance through induction of endoplasmic reticulum (ER) stress. BPA and OP treatment leads to survival of pancreatic β cells against streptozotocin, but despite an increased insulin level, serum glucose regulation is not properly regulated. The expression of genes involved in transporting calcium ions to the cytosol and ER decreased while the expression of those affecting the removal of calcium from the cytosol and ER increased. Depletion of calcium from the ER leads to ER stress and can induce insulin resistance. Insulin resistance is also confirmed by insulin-responsive gene, such as glucose transporter 4 (GLUT4) and IRS2, expression. Taken together, these results imply that disruption of calcium homeostasis by BPA and OP induces ER stress and leads to insulin resistance, especially in a streptozotocin (STZ) -induced type 1 diabetes mellitus model.

The effect of TGF-β signaling on regulating proliferation of uterine leiomyoma cell via ERα signaling activated by bisphenol A, octylphenol and nonylphenol in vitro.

To study the transforming growth factor beta (TGF-β) signaling pathway in interactions with estrogen receptor alpha (ERα) signaling pathway mediating the growth of human uterine leiomyoma (UL) activated by phenolic environmental estrogens (EEs). The subcultured UL cells were used to determine the validation of TGF-β3 for the viability of human UL cells using CCK-8 assay, mRNA expressions of ERα, and c-fos by quantitative reverse transcription polymerase chain reaction method, and expressions of p-Smad3, SnoN, and c-fos proteins by Western blot assay in each treatment group. Compared with each of EEs or TGF-β3 treatment, slightly decrease in the proliferation rate of UL was detected in the coexistence of each EE with TGF-β3. Interestingly, mRNA expressions of ERα and c-fos reduced in the setting of coexistence of TGF-β3 and EEs. Somehow, the expression of p-Smad3 and c-fos proteins significantly decreased in each of E2, bisphenol A (BPA), nonylphenol (NP), and octylphenol (OP) group, as well as the expression of SnoN protein significantly reduced only in BPA and NP groups, followed by TGF-β3 treatment. With the overlaid action of ICI 182,780, the expression of p-Smad3 protein significantly increased in OP group, but slightly increased in E2, BPA, NP, and OP groups. However, compared with the control group, the expression of SnoN and c-fos proteins significantly decreased in the same setting. Both ERα signaling pathway and TGF-β signaling pathway have different roles in governing UL cell proliferation. The phenolic EEs can be a promoter to the proliferation of UL cells, which is mediated by ERα signaling pathway and cross-talked with TGF-β signaling pathway.

Alkylphenol and bisphenol A contamination of urban runoff: an evaluation of the emission potentials of various construction materials and automotive supplies.

Alkylphenol (AP) and bisphenol A (BPA) contamination of urban runoff has already been established. Potential sources of these contaminants in runoff are endogenous to the urban watershed and are mainly related to traffic and leaching from construction materials. This article summarizes the results of experimental work carried out on a selection of building materials, automotive materials, and consumables, which can be in contact with rain, to assess their potential emission of alkylphenols, alkylphenol ethoxylates, and bisphenol A into runoff. 36 samples of materials, new and used, across 7 major families of building materials (PVC, concrete, polycarbonate, SBS-modified bitumen, drainage materials) and automotive materials (body, tires) were subjected to leaching tests with methanol and then, for a selection of them, with water. Automotive fluids were also directly analyzed. The results demonstrate the ubiquitous presence of APs and BPA in urban materials and their extractable character with water. The compounds with the strongest emission rates were bisphenol A and nonylphenol. The most important BPA emissions into water (10 to 300ng/g) were measured for polycarbonate, tires, some car bodies, and PVC. Nonylphenol was leached in large quantities (1 to 10ng/g) from PVC, some concretes, SBS-modified bitumen, and body samples. The tires were the only materials having a strong emission in octylphenol (1 to 10ng/g). The analysis of automotive fluids confirmed the presence of BPA (0.3 to 5.5g/L) and nonylphenol (2.3 to 2.9mg/L) in brake fluids, while APs and BPA were found at trace levels in coolants and windscreen washer. Graphical abstract ᅟ.

Fast pyrolysis of corn stovers with ceramic ball heat carriers in a novel dual concentric rotary cylinder reactor

Fast pyrolysis of corn stovers with ceramic ball heat carriers in a dual concentric rotary cylinder reactor was studied to explore the product yields and characteristics in response to temperature. The reactor was confirmed to successfully scale up to a 25 kg/h pilot plant, with its performance being excellent. The highest bio-oil yield of 48.3 wt% at 500 °C was attained with the char and gas yields being 26.8 and 24.9 wt%. Phenols content was reduced from 22.3% to 18.9% when elevating temperature from 450 until 600 °C, with guaiacols and alkyl phenols being the predominant compounds, while ketones accounted for 15.8–23.0% and their content showed a continuous increase, with hydroxyacetone being the paramount ketonic one. Acetic acid was the dominant acidic compound with its peak content of 9.4% at 500 °C. The char characteristics in response to temperatures were determined for subsequent processing and high value-added utilization.

Biodegradation in seawater of PAH and alkylphenols from produced water of a North Sea platform

Operational planned discharges of produced water (PW) to the marine environment from offshore oil production installations, contain low concentrations of dispersed oil compounds, like polycyclic aromatic hydrocarbons (PAHs) and alkylated phenols (APs). Biotransformation in natural seawater (SW) of naphthalenes/PAHs and phenol/APs in field-collected PW from a North Sea platform was investigated in this biodegradation study. The PW was diluted in SW from a Norwegian fjord, and the biodegradation study was performed in slowly rotating carousels at 13 °C over a period of 62 days. Naphthalenes/PAHs and phenol/APs biotransformation was determined by first-order rate kinetics, after normalization against the recalcitrant biomarker 17α(H),21β(H)-Hopane. The results from this study showed total biotransformation half-lives ranging from 10 to 19 days for groups of naphthalenes and PAHs, while half-lives for APs (C0- to C9-alkylated) were 10–14 days. Biotransformation half-lives of single compounds ranged from 8 to >100 days for naphthalenes and PAHs (median 16 days), and from 5 to 70 days (median 15 days) for phenols and APs. Four of the tested PAHs (chrysene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(g,h,i)perylene) and one AP (4-tert-butylphenol) showed biotransformation half-lives >50 days. This is one of a few studies that has investigated the potential for biodegradation of PW in natural SW. Methods and data from this study may be used as a part of Risk Based Approaches (RBA) for assessments of environmental fate of PW released to the marine environment and as part of the persistence related to risk.