Graphene oxide/ layered double hydroxides@ sulfonated polyaniline: A sorbent for ultrasonic assisted dispersive solid phase extraction of phthalates in distilled herbal beverages.

In this study, the ultrasonic-assisted dispersive solid phase extraction (UA-d-SPE) method coupled to gas chromatography-mass spectrometry (GC-MS) was applied for the analysis of phthalate esters in drinking water and distilled herbal beverages (Rosa, Mentha, Cichorium). A new nanocomposite based on layered double hydroxide supported on graphene oxide was synthesized and modified by sulfonated polyaniline via a simple one-pot in-situ polymerization method. The structure and morphology of the nanocomposite was confirmed by means of complementary techniques: Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy. The effects of key parameters including adsorbent mass, type and amount of back extraction solvent, extraction and desorption time, pH of the solution and ionic strength were optimized and good precision and sensitivity were achieved. Under the optimum conditions, the limits of detection were between 0.06-0.3 ng mL-1 in aqueous solutions. The hybrid nanomaterial exhibited good adsorption ability toward phthalates in drinking water and distilled herbal beverages. The relative standard deviations (RSD%) for beverage samples varied from 0.1% to 9.9% (n = 3). The relative recoveries varied from 54.5% to 112.6%.

Removal of phthalic acid esters from sea buckthorn (Hippophae rhamnoides L.) pulp oil by steam distillation and molecular distillation.

Sea buckthorn (Hippophae rhamnoides L.) pulp oils (SPOs) are rich in a variety of beneficial bioactive ingredients. Nevertheless, SPOs would be exposed to plastic equipment during processing, resulted in increasing phthalates contents and edible risk, as well as affecting oil quality. For these reasons, the effects of two stages steam distillation (SD2) and two stages molecular distillation (MD2) on phthalic acid esters (PAEs) content were investigated and compared in the present work. Compared with SD2, MD2 showed higher removal rates of seven selected PAEs from the SPO. Even if the initial concentration of DBP and DEHP in R-SPO were 1.626 and 10.933 mg/kg respectively, the concentration of DBP and DINP could be reduced below the limit set by China government after treated with MD2. Besides that, there was no trans-fatty acids generated in SPO during the distillation process.

Phthalate and alternative plasticizers in indwelling medical devices in pediatric intensive care units.

The present study aimed to identify plasticizers present in indwelling plastic medical devices commonly used in the pediatric intensive care unit (PICU). We have analyzed a wide range of medical devices (n = 97) daily used in the PICUs of two academic hospitals in Belgium and the Netherlands. Identified compounds varied between the samples. Most of the indwelling medical devices and essential accessories were found to actively leach phthalates and alternative plasticizers. Results indicated that DEHP was predominantly present as plasticizer (60 of 97 samples), followed by bis(2-ethylhexyl) adipate (DEHA, 32 of 97), bis(2-ethylhexyl) terephthalate (DEHT, 24 of 97), tris(2-ethylhexyl) trimellitate (TOTM, 20 of 97), and tributyl-O-acetyl citrate (ATBC, 10 of 97). Other plasticizers, such as di-isononyl-cyclohexane-1,2-dicarboxylate (DINCH, 2 of 97), di-isononyl phthalate (DiNP, 4 of 97), di(2-propylheptyl) phthalate (DPHP, 4 of 97) and di-isodecyl phthalate (DiDP, 2 of 97) were detected in < 5% of the investigated samples. Several devices contained multiple plasticizers, e.g. devices containing TOTM contained also DEHP and DEHT. Our data indicate that PICU patients are exposed to a wide range of plasticizers, including the controversial DEHP. Future studies should investigate the exposure to APs in children staying in the PICU and the possible health effects thereof.

Solid phase microextraction of phthalic acid esters from vegetable oils using iron (III)-based metal-organic framework/graphene oxide coating.

A hybrid composite featuring an iron-based metal-organic framework Material of Institute Lavoisier-88(Fe) and graphene oxide (MIL-88(Fe)/GO) was synthesized and used as the solid-phase microextraction (SPME) coating. The SPME fiber was prepared by covalent bonding of the MIL-88(Fe)/GO composite onto the stainless steel substrate. The fiber had a good durability and allowed >100 replicate extractions. The developed method, which combined the MIL-88(Fe)/GO coated fiber based SPME with gas chromatography-flame ionization detection (GC-FID), achieved low limits of detection (0.5-2.0 ng g-1, S/N = 3) and good linearity (r2 > 0.994) for the phthalic acid esters (PAEs) from various vegetable oil samples. The repeatability and fiber-to-fiber reproducibility were in the range of 4.0-9.1% and 5.7-11.4%, respectively. The method was successfully applied to the analysis of PAEs from vegetable oil samples with good recoveries (83.1-104.1%) and satisfactory precisions (RSDs < 10.5%), indicating that the MIL-88(Fe)/GO hybrid composite is a good coating material for the SPME of PAEs.

[One-step extraction method of phthalate esters in vegetable oils].

In order to develop a fast investigation method for phthalate esters (PAEs) from vegetable oils, a gas-liquid micro-extraction (GLME) technique that combined with GC-MS was established. A vegetable oil sample (0.1 g) was directly added into the GLME device. The integrated process of extraction, clean-up, and concentration of PAEs was completed within 5 min. Internal standard method was applied to ensure the accuracy of the results. Soybean oil, blend oil, olive oil, and sesame oil were spiked with 200 µg/kg of a mixed 15 PAEs standard, and the ranges of the recoveries and RSDs were between 60.0% to 112.3% and 0.9% to 28.4%, respectively. Compared with some traditional sample pretreatment methods such as liquid-liquid extraction, liquid-liquid micro-extraction, gel permeation chromatography, this method is simple and fast, with high accuracy, good repeatability and low matrix effect. This study verified the suitability of the GLME method for field detection of food products in food safety sector and exhibits great significance for the completion of food safety system in China.

A porous carbon derived from amino-functionalized material of Institut Lavoisier as a solid-phase microextraction fiber coating for the extraction of phthalate esters from tea.

In this work, a porous carbon derived from amino-functionalized material of Institut Lavoisier (C-NH2 -MIL-125) was prepared and coated onto a stainless-steel wire through sol-gel technique. The coated fiber was used for the solid-phase microextraction of trace levels of phthalate esters (diallyl phthalate, di-iso-butyl ortho-phthalate, di-n-butyl ortho-phthalate, benzyl-n-butyl ortho-phthalate, and bis(2-ethylhexy) ortho-phthalate) from tea beverage samples before gas chromatography with mass spectrometric analysis. Several experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimal conditions, the linearity existed in the range of 0.05-30.00 µg/L for green jasmine tea beverage samples, and 0.10-30.00 µg/L for honey jasmine tea beverage samples, with the correlation coefficients (r) ranging from 0.9939 to 0.9981. The limits of detection of the analytes for the method were 2.0-3.0 ng/L for green jasmine tea beverage sample, and 4.0-5.0 ng/L for honey jasmine tea beverage sample, depending on the compounds. The recoveries of the analytes for the spiked samples were in the range of 82.0-106.0%, and the precision, expressed as the relative standard deviations, was less than 11.1%.

Ortho-phthalic acid esters in lipophilic extract from the cell culture of Aconitum baicalense Turcz ex Rapaics 1907.

Optically active bis-2R(-)ethylhexyl o-phthalate was obtained with 0.18% yield from dry cultured cells of Aconitum baicalense Turcz ex Rapaics 1907 by extraction with petroleum ether followed by silica gel column chromatography. Its structure was confirmed by the analysis of 13C and 1H NMR spectra. Seasonal fluctuations of quantitative phthalate content in A. baicalense cells were identified. The tests were performed under conditions excluding the presence of phthalates in reagents, materials, and laboratory dishes. The same substance was shown to be produced by cultivated cells of other plants. Biosynthesis of esters of ortho-phthalic acid by cultivated plant cells was discovered for the first time.

Determination of total phthalates in edible oils by high-performance liquid chromatography coupled with photodiode array detection.

The previously reported procedure for the determination of the total phthalate in fatty food involved the extraction of phthalates using chloroform/methanol followed by the removal of the solvents before alkaline hydrolysis requiring 20 h and derivatization of phthalic acid. In this study, a phase-transfer catalyst (tetrabutylammonium chloride) was used in the liquid-liquid heterogeneous hydrolysis of phthalates in oil matrix shortening the reaction time to within 25 min. The resulting phthalic acid in the hydrolysate was extracted by a novel molecular complex based dispersive liquid-liquid microextraction method coupled with back-extraction before high-performance liquid chromatography coupled with photodiode array detection. Under the optimal experimental conditions, the linearity of the method was in the range of 0.5-12 nmol/g with the correlation coefficients (r) >0.997. The detection limit (S/N = 3) was 0.11 nmol/g. Intraday and interday repeatability values expressed as relative standard deviation were 3.9 and 7.1%, respectively. The recovery rates ranged from 82.4 to 99.0%. The developed method was successfully applied for the analysis of total phthalate in seven edible oils.

Optimisation and establishment of separation conditions of organic acids from Usnea longissima Ach. by pH-zone-refining counter-current chromatography: Discussion of the eluotropic sequence.

The major bioactive constituents of Usnea longissima Ach. are organic acids. However, few recent literatures involve the preparative separation of these organic acids. In the present study, pH zone-refining counter-current chromatography is used to separate organic acids from crude sample of U. longissima Ach. The crude extract was separated with the two-phase solvent system Pet-EtAc-MeOH-H2O (5:5:3:7, v/v) with 10mM TFA in organic stationary phase and different concentration of the eluter in aqueous mobile phase for the screening of the most suitable separation conditions. From the crude extract (1.2g), 74.0mg of orsellinic acid at 92.7% purity, 55.5mg of 4-O-methylorsellinic acid at 97.7% purity, 353.5mg of evernic acid at 93.8% purity, 102.0mg of barbatic acid at 94.8% purity, 19.4 mg of diffractaic acid at 92.2% purity, and 44.9 mg of usnic acid at 95.7% purity were obtained using the selected conditions in which the concentration of TFA in stationary phase was 10mM and the concentration of NaOH in mobile phase was 10-20mM. The purities of the separated organic acids were measured by HPLC. And the data of electrospray ionization-liquid chromatography/mass spectrometry (ESI-LC/MS), (1)H NMR, and (13)C NMR were used for confirming chemical structures.

[Operational Characteristics of the Simultaneous Nitrogen and Phosphorus Removal and Removal of Phthalate Esters by Three-dimensional Biofilm-electrode Coupled with Iron/Sulfur Reactor].

In order to explore the technological characteristics of the simultaneous removal of phthalate esters (PAEs) as well as nitrogen and phosphorus by the novel technology of three-dimensional biofilm-electrode coupled with iron/sulfur reactor (3DBER-S-Fe), the changes of the total nitrogen (TN),total phosphorus (TP),DBP,DEHP,NO3--N, SO42- and pH value were analyzed under the hydraulic retention time (HRT) of 8 h, 6 h and 4 h respectively. The results showed that 3DBER-S-Fe could remove nitrogen, phosphorus and PAEs effectively. Under the HRT of 8 h, 6 h and 4 h, the removal rates of TN were 80.99%, 78.85% and 64.76%; TP were 65.18%, 67.17% and 43.44%; DBP were 96.72%, 97.32% and 96.53%; DEHP were 91.89%, 81.57% and 74.30%, respectively. There were heterotrophic denitrification, hydrogen autotrophic denitrification and sulfur autotrophic denitrification processes in the 3DBER-S-Fe, the elemental sulfur could compensate for the relative shortage of denitrification electron donor caused by the increase of NO3--N load in the influent as a result of maintaining a high efficiency of the denitrification system when the HRT was shortened from 8h to 4h; the iron ions produced by the corrosion of the sponge iron filler in the system had a sustainable and efficient function of removing phosphorus by precipitation; the 3DBER-S-Fe process combined the interactions of physical adsorption, biological degradation and electrochemical processes which supported its high removal rates of DBP and DEHP under the different HRT conditions.

Rapid screening of edible oils for phthalates using phase-transfer catalyst-assisted hydrolysis and liquid phase microextraction coupled to high performance liquid chromatography-tandem mass spectrometry.

Edible oil is easily contaminated with phthalic acid esters (PAEs). Conventional procedures to analyze individual PAEs require very rigorous experimental conditions that are extremely labor-intensive due to significant procedural contaminations generated by the ubiquitous presence of PAEs in the laboratory environment. In this study, a rapid screening method for PAEs in edible oil was successfully developed. Using a phase-transfer catalyst (terabutylammonium bromide) during oil/water biphasic base hydrolysis of PAEs, the hydrolysis time was decreased from a previously reported time of 20 h to 10 min (80 °C). The resulting phthalic acid in the acidified hydrolysate was extracted with 600 µL of tributyl phosphate and then analyzed by high performance liquid chromatography-tandem mass spectrometry in 6 min. Parameters affecting the hydrolysis of PAEs and the extraction of phthalic acid were optimized, and the analytical method was validated. No obvious matrix effect existed in the edible oils whether an external or internal standard method was used. The detection limit was 1.0 µmol kg(-1), and the quantification limit was 1.3 µmol kg(-1). The recovery rates varied from 86 to 107% with relative standard deviations equal to or lower than 9.9% in all of the tested conditions. Twenty-six samples were analyzed, and the background corrected total PAE content was found to be in the range of

Preparation of C18-functionalized Fe3O4@SiO2 core-shell magnetic nanoparticles for extraction and determination of phthalic acid esters in Chinese herb preparations.

The extraction and determination of phthalic acid esters (PAEs) residue in Chinese herbal preparations (CHP) by C18-functionalized magnetic nanoparticles (C18-FS-MNP) has been firstly performed. It was synthesized through coating Fe3O4 nanoparticles with sodium silicate, followed by freeze-drying technique and then modified with C18 groups. C18-FS-MNPs prepared via freeze-drying technique were superior to those particles prepared via common vacuum drying method in terms of dispersion and extraction recovery. C18-FS-MNPs demonstrated obvious enrichment effect for four model PAEs and 478-627-fold enrichment factors were obtained. The limit of detection was <1.89ng/mL and relative standard deviation was ranging from 3.7 to 5.8%. It was successfully applied for determination of trace PAEs residue in CHP with good recoveries.

Simultaneous determination of 17 phthalate esters in edible vegetable oils by GC-MS with silica/PSA-mixed solid-phase extraction.

A quantified method for the determination of 17 phthalate esters (PAEs) in edible vegetable oil by GC-MS with the pretreatment of acetonitrile extraction and silica/N-(n-Propyl)ethylenediamine-mixed SPE column was established. By the quantification of internal standard of D(4)-di(2-ethylhexyl) phthalate, a good linearity range of related 17 PAEs was observed. The correlation coefficient was ranged at 0.994~1.000, and the standard lowest quantified level was 0.05~0.15 mg/L. The spiking recoveries of 17 PAEs were 78.3~108.9% with the relative standard deviations of 4.3~12.1% (n = 6). The method detection limits were 0.1~0.2 mg/kg. Meanwhile, PAEs were determined in 30 plastic buckets of edible vegetable oil from supermarkets in Hangzhou city of China. The survey of 30 oil samples showed di(2-ethylhexyl) phthalate (DEHP) had the 100% (30/30) detection rate. The levels of diisobutyl phthalate with 86.7% (26:30), di-n-butyl phthalate (DBP) with 70% (21:30) and diethyl phthalate with 10% (3:30) were detected. It was worth note that DBP with 16.7% (5:30) samples and DEHP with 10% (3:30) samples were beyond the regular migrating limit, which indicated that more attention should be paid to the PAEs in oil with plastic package.

Development of multiresidue analysis for twenty phthalate esters in edible vegetable oils by microwave-assisted extraction-gel permeation chromatography-solid phase extraction-gas chromatography-tandem mass spectrometry.

A novel multiresidue analysis method is developed for the determination of twenty phthalate esters at the µg/kg level in edible vegetable oils by microwave-assisted extraction-gel permeation chromatography-solid phase extraction-high resolution gas chromatography-tandem mass spectrometry (MAE-GPC-SPE-HRGC-MS/MS). The samples were extracted with methanol under microwave incubation. Cleanup was carried out with GPC followed by a further C18 SPE column and then separated by the HP-5MS capillary column under a temperature program. The eluents were qualitatively and quantitatively determined by tandem mass analyzer with selected reaction monitoring (SRM) type and positive ion mode. The calibration curves showed good linearity in the range 5 µg/kg to 2.50 mg/kg with correlation coefficients larger than 0.999. Low detection limits (LODs) of 0.218-1.367 µg/kg and quantification limits (LOQ) of 0.72-4.51 µg/kg were achieved. The mean recoveries were in the range from 93.04% to 104.6% at 5, 15, and 40 µg/kg spiked levels, and the relative standard deviations (RSDs) were in the range of 1.01% and 5.26% (n = 7). This method could potentially overcome the interference from large amounts of lipids and pigment. The real sample test showed this method can be used for sensitive and accurate determination and confirmation of phthalate ester residues in high-fat and complex samples.

[Study on the chemical constituents from the ethyl acetate extracts of Cremastra appendiculata].

OBJECTIVE: To study the chemical constituents from the ethyl acetate extracts of Cremastra appendiculata. METHODS: The compounds from the ethyl acetate extracts were isolated by the silica gel column and Sephadex LH-20 column chromatography, their structures were elucidated by the spectral analysis and chemical evidence. RESULTS: Seven componds were separated and identified as fumaric acid (1), dimethylhexyl phthalate (2), L-pyroglutamic acid (3), 2-furoic acid (4), vanillic acid (5), p-coumaric acid (6), protocatechuic acid (7). CONCLUSIONS: Compounds 1 to 6 are obtained from this plant for the first time.

[Ru/AC catalyzed ozonation of recalcitrant organic compounds].

Ozonation and Ru/AC catalyzed ozonation of dimethyl phthalate (DMP), phenols and disinfection by-products precursors were studied. It shows that Ru/AC catalyst can obviously enhance the mineralization of organic compounds. In the degradation of DMP, TOC removal was 28.84% by ozonation alone while it was 66.13% by catalytic ozonation. In the oxidation of 23 kinds of phenols, TOC removals were 9.57%-56.08% by ozonation alone while they were 41.81%-82.32% by catalytic ozonation. Compared to ozonation alone, Ru/AC catalyzed ozonation was more effective for the reduction of disinfection by-products formation potentials in source water. The reduction of haloacetic acids formation potentials was more obvious than thichlomethane formation potentials. After the treatment by catalytic ozonation, the haloacetic acids formation potentials decreased from 144.02 microg/L to 58.50 microg/L, which was below the standard value of EPA. However ozonation alone could not make it reach the standard. The treatments of source water by BAC, O3 + BAC, O3/AC + BAC and Ru/AC + O3 + BAC were also studied. In the four processes, TOC removal was 3.80%, 20.14%, 27.45% and 48.30% respectively, COD removal was 4.37%, 27.22%, 39.91% and 50.00% respectively, UV254 removal was 8.16%, 62.24%, 67.03% and 84.95% respectively. Ru/AC + O3 + BAC process is more effective than the other processes for the removal of TOC, COD and UV254 and no ruthenium leaching observed in the solution. It is a promising process for the treatment of micro polluted source water.

[Emergent treatment of source water contaminated by representative chemicals].

Emergent treatment of source water polluted by representative chemical bisphenol-A (BPA) and Di-ethyl phthalate (DEP) was researched. The results indicate that activated carbon adsorption could achieve high efficiencies to remove the two chemicals. The pseudo second-order adsorption kinetic model and Elovich kinetic model can be used to describe the powdered activated carbon (PAC) adsorption process of BPA and DEP in raw water. In pilot test, 50 mg/L PAC dosage can get the pollution concentration of 500 microg/L BPA or 3.3 mg/L DEP comply with the requirement of water quality standard. The dynamic adsorption of carbon-sand filter was also studied, and removal efficiencies of BPA and DEP were hardly influenced by their original concentrations and the filtering velocity among 5.1-15.3 m/h of carbon-sand filter. When PAC adsorption was combined with carbon-sand filter, PAC adsorption contributes most to removing pollution, and carbon-sand filter as the supplement of PAC can strengthen safety. DEP can't be oxidized by KMnO4 or Cl2, but 850 microg/L BPA can be almost completely oxidized by 3 mg/L KMnO4 and 1.5 mg/L Cl2. The oxidation products of BPA as well as their toxicity need further study. PAC adsorption combined with 1.5 mg/L KMnO4 preoxidation can't improve the removal efficiency of DEP, but can improve BPA removal efficiency.

New phthalates from Phyllanthus muellerianus (Euphorbiaceae).

Species of the genus Phyllanthus are known for their medicinal values and many are explored phytochemically. Some of them produce phthalates which usually have antimicrobial properties. This paper deals with the phytochemical investigation on Phyllanthus muellerianus. As a result, five compounds, bis(2-ethyloctyl)phthalate (1), bis(2-ethylicosyl)phthalate (2), 3-friedelanone (3), beta-sitosterol (4), and methyl gallate (5), have been isolated and characterized. Metabolites 1 and 2 are new compounds, while 3-5 have been isolated for the first time from this source. Structures of all the isolates were established on the basis of MS, 1D and 2D NMR spectral data and in comparison with the reported data.

Antiviral activity of bis(2-methylheptyl)phthalate isolated from Pongamia pinnata leaves against White Spot Syndrome Virus of Penaeus monodon Fabricius.

White Spot Syndrome Virus (WSSV) is an extremely virulent, contagious, causative agent of the White spot syndrome of shrimp and causes high mortality and affects most of the commercially important cultured marine crustacean species globally. Oral administration of ethanolic extract and purified compound from the leaves of Pongamia pinnata, an indigenious Indian "medicinal plant" "has increased the survival of WSSV infected Penaeus monodon". Pelletized feed impregnated with ethanolic extract of the leaves of P. pinnata was fed to shrimp prior and after WSSV infection at 200 and 300 microg/g of body weight of shrimp/day. The survival rate for the WSSV-infected shrimp that were fed with 200 and 300 microg extract/g were 40% and 80%, respectively. The active WSSV antiviral compound 1 that was isolated from the leaves of P. pinnata was identified as bis(2-methylheptyl)phthalate. Thus, the present work revealed that oral administration of the crude and purified compound from the leaves of P. pinnata effectively inhibited WSSV pathogenesis and reduced the mortality of infected shrimp.

Headspace solid-phase microextraction of phthalic acid esters from vegetable oil employing solvent based matrix modification.

A new solvent-free analytical procedure based on headspace solid-phase microextraction (SPME) coupled to gas chromatography employing an electron capture detector (GC/ECD) or alternatively a mass spectrometric detector (GC/MSD) has been developed for the determination of phthalic acid esters (dimethyl-[DMP], diethyl-[DEP], di-n-butyl-[DnBP], butylbenzyl-[BBP], di-2-ethylhexyl-[DEHP] and di-n-octyl [DnOP] phthalate) in vegetable oils. Four different fiber coatings were evaluated, among them polydimethylsiloxane with a thickness of 100 microm appeared to be the best choice for allowing extraction of the whole group of analytes. Various solvents were tested as sample matrix modification agents with the aim to facilitate the transfer of esters with low vapour pressure (DEHP and DnOP) from oil matrix into the headspace. The addition of methanol resulted in optimal set-up applicable for all phthalate esters. Temperature control and the way of sample stirring were recognized as critical points of the whole procedure. Primarily, because shaking rather than stirring of the sample is carried out using a CombiPal multipurpose sampler, the automation of the SPME method employing this instrument was found to be not fully suitable for efficient stripping of phthalates from the oil matrix into the sample headspace. Nevertheless, the optimized manual SPME method, encompassing GC/ECD or GC/MSD for the separation and detection of target analytes, offers a unique solution and showed acceptable performance characteristics: linear response in the range of 0.5-2 mg kg(-1) and repeatability expressed as R.S.D. between 14 and 23% at the spiking level of 2 mg kg(-1).