Membrane-protected covalent organic framework fiber for direct immersion solid-phase microextraction of 17beta-estradiol in milk.

17beta-estradiol (E2) could accumulate in human body through milk and cause various diseases by interfering with the endocrine system. Herein, we coated stainless steel wire with covalent organic framework LZU1 (COF-LZU1) and Nafion protected by dialysis membrane for direct immersion solid phase microextraction (DI-SPME) and coupled with gas chromatography-flame ionization detection (GC-FID) for the detection of trace E2 in milk samples. With dialysis membrane protection, the stability of SPME fiber was improved and the extraction efficiency was only reduced by 7% after repeated use of 160 times. The extraction efficiency of E2 with the home-made fiber COF-LZU1 was 22.1, 8.4, 3.6 times higher than that of bare stainless steel wire, PDMS/DVB and PDMS, respectively. The method had been successfully applied to milk samples, and the relative recoveries were between 77.27% and 108.26%. It can provide an effective and general method for the pretreatment of complex matrix samples.

Facile covalent preparation of carbon nanotubes / amine-functionalized Fe3O4 nanocomposites for selective extraction of estradiol in pharmaceutical industry wastewater.

As a typical steroid hormone drug, estradiol (E2) is also one of the most frequently detected endocrine disrupting chemicals (EDCs) in the aquatic environment. Herein, in response to the potential risk of E2 in steroid hormone pharmaceutical industry wastewater to human and wildlife, a novel carbon nanotubes / amine-functionalized Fe3O4 (CNTs/MNPs@NH2) nanocomposites with magnetic responsive have been developed for the enrichment and extraction of E2 in pharmaceutical industry wastewater, where amino-functionalized Fe3O4 magnetic nanoparticles (MNPs@NH2) were used as a magnetic source. The resultant CNTs/MNPs@NH2 possessed both the features of CNTs and desired magnetic property, enabling to rapidly recognize and separate E2 from pharmaceutical industry wastewater. Meanwhile, the CNTs/MNPs@NH2 had good binding behavior toward E2 with fast binding kinetics and high adsorption capacity, as well as exhibited satisfactory selectivity to steroidal estrogen compounds. Furthermore, the change of pH value of aqueous phase in adsorption solvent hardly affected the adsorption of E2 by CNTs/MNPs@NH2, and the adsorption capacity of E2 ranged from 19.9 to 17.2 mg g-1 in the pH range of 3.0 to 11.0, which is a latent advantage of the follow-up development method to detect E2 in pharmaceutical industry wastewater. As a result, the CNTs/MNPs@NH2 serving as a solid phase extraction medium were successfully applied to efficiently extract E2 from pharmaceutical industry wastewater. Therefore, the CNTs/MNPs@NH2 nanocomposites could be used as a potential adsorbent for removing steroidal estrogens from water. More importantly, the developed method would provide a promising solution for the monitoring and analysis of EDCs in pharmaceutical industry wastewater.

Highly sensitive determination of endocrine disrupting chemicals in foodstuffs through magnetic solid-phase extraction followed by high-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Endocrine disrupting chemicals (EDCs), proved to be potential carcinogenic threats to human health, have received great concerns in food field. It was essential to develop effective methods to detect EDCs in food samples. The present study proposed an efficient method to determine trace EDCs including estrone (E1), 17ß-estradiol (E2), estriol (E3) and bisphenol A (BPA) based on magnetic solid-phase extraction (MSPE) coupled high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in meat samples. RESULTS: Fe3 O4 @COF(TpBD)/TiO2 nanocomposites were synthesized via functionalization of magnetic covalent organic frameworks (COFs) with titanium dioxide (TiO2 ) nanoparticles, and used as absorbents of MSPE to enrich EDCs. The efficient EDCs enrichment relies on π-π stacking interaction, hydrogen bonding, and the interaction between titanium ions (IV, Ti4+ ) and hydroxyl groups in EDCs, which improves the selectivity and sensitivity. Under the optimized conditions, target EDCs were rapidly extracted through MSPE with 5 min. Combining Fe3 O4 @COF(TpBD)/TiO2 based MSPE and HPLC-MS/MS to determine EDCs, good linearities were observed with correlation coefficient (R2 ) ≥ 0.9989. The limits of detection (LODs) and limits of quantification (LOQs) were 0.13-0.41 µg kg-1 and 0.66-1.49 µg kg-1 , respectively. Moreover, the proposed method was successfully applied to real samples analysis. CONCLUSIONS: The established MSPE-HPLC-MS/MS method was successfully applied to determine EDCs in meat samples with rapidness, improved selectivity and sensitivity. It shows great prospects for EDCs detection in other complicated matrices. © 2020 Society of Chemical Industry.

Efficient Low-Cost Procedure for Microextraction of Estrogen from Environmental Water Using Magnetic Ionic Liquids.

In this study, three magnetic ionic liquids (MILs) were investigated for extraction of four estrogens, i.e., estrone (E1), estradiol (E2), estriol (E3), and ethinylestradiol (EE2), from environmental water. The cation trihexyl(tetradecyl)phosphonium ([P66614]+), selected to confer hydrophobicity to the resulting MIL, was combined with tetrachloroferrate(III), ferricyanide, and dysprosium thiocyanate to yield ([P66614][FeCl4]), ([P66614]3[Fe(CN)6]), and ([P66614]5[Dy(SCN)8]), respectively. After evaluation of various strategies to develop a liquid-liquid microextraction technique based on synthesized MILs, we placed the MILs onto a magnetic stir bar and used them as extracting solvents. After extraction, the MIL-enriched phase was dissolved in methanol and injected into an HPLC-UV for qualitative and quantitative analysis. An experimental design was used to simultaneously evaluate the effect of select variables and optimization of extraction conditions to maximize the recovery of the analytes. Under optimum conditions, limits of detection were in the range of 0.2 (for E3 and E2) and 0.5 µg L-1 (for E1), and calibration curves exhibited linearity in the range of 1-1000 µg L-1 with correlation coefficients higher than 0.998. The percent relative standard deviation (RSD) was below 5.0%. Finally, this method was used to determine concentration of estrogens in real lake and sewage water samples.

Efficient Removal 17-Estradiol by Graphene-Like Magnetic Sawdust Biochar: Preparation Condition and Adsorption Mechanism.

The occurrence of environmental endocrine disrupting chemicals (EDCs) in aquatic environments has caused extensive concern. Graphene-like magnetic sawdust biochar was synthesized using potassium ferrate (K2FeO4) to make activated sawdust biochar and applied for the removal of 17-estradiol (E2). The characterization showed that the surface morphology of five graphene-like magnetic sawdust biochars prepared with different preparation conditions were quite different. The specific surface area and pore structure increased with the increment of K2FeO4 addition. The results have shown that graphene-like magnetic sawdust biochar (1:1/900 °C) had the best removal on E2. The experimental results indicated that pseudo-first-order kinetic model and the Langmuir model could describe the adsorption process well, in which the equilibrium adsorption capacity (qe,1) of 1:1/900 °C were 59.18 mg·g-1 obtained from pseudo-first-order kinetic model and the maximum adsorption capacity (qmax) of 1:1/900 °C were 133.45 mg·g-1 obtained from Langmuir model at 298K. At the same time, lower temperatures, the presence of humic acid (HA), and the presence of NaCl could be regulated to change the adsorption reaction in order to remove E2. Adsorption capacity was decreased with the increase of solution pH because pH value not only changed the surface charge of graphene-like magnetic sawdust biochar, but also affected the E2 in the water. The possible adsorption mechanism for E2 adsorption on graphene-like magnetic sawdust biochar was multifaceted, involving chemical adsorption and physical absorption, such as H-bonding, π-π interactions, micropore filling effects, and electrostatic interaction. To sum up, graphene-like magnetic sawdust biochar was found to be a promising absorbent for E2 removal from water.

A self-powered photoelectrochemical cathodic aptasensor for the detection of 17ß-estradiol based on FeOOH/In2S3 photoanode.

In this work, a novel self-powered photoelectrochemical (PEC) aptasensor integrated photoanode and photocathode for the accurate and selective detection of 17ß-estradiol (E2) was proposed for the first time. FeOOH/In2S3 heterojunction was built initially and used as a substitute for platinum (Pt) counter electrode. The matched band gap edge of FeOOH and In2S3 facilitated the transfer of photo-generate electrons to photoanode, while the holes left in the valence band of photocathode (CuInS2) can be attracted by the electrons flowed from the photoanode, which reduced the recombination of electron-hole pairs and promote the cathodic photocurrent. Under optimal conditions, the constructed cathodic aptasensor of E2 presented linear scope in 10 fg/mL-1 µg/mL with detection limit of 3.65 fg/mL. Besides, the cathodic aptasensor exhibited admiring selectivity, stability and reproducibility. This work verified that the cathodic photocurrent response can be regulated by the corresponding photoanode which provided a new design thought for PEC aptasensor on the basis of p-type semiconductor.

Chitosan/Al2O3-HA nanocomposite beads for efficient removal of estradiol and chrysoidin from aqueous solution.

Alumina, as a support material, was loaded together with chitosan and hydroxyapatite to form chitosan/Al2O3-HA composite beads and was used for estradiol and chrysoidin removal from aqueous solution in the present work. The physicochemical properties of the beads were studied with Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectrometry (FTIR), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) surface area analysis. FTIR spectra confirmed that the chitosan was loaded successfully on Al2O3-HA, and functional groups were immobilized onto the surface of the beads after the synthesis. The adsorption condition including pH, the amount of adsorbent, initial concentration and time were evaluated during the batch experiments. Isotherm data best matched the Langmuir model and the pseudo-second-order model best described the adsorption kinetics. The maximum adsorption capacity was found to be 39.78 mg/g and 23.26 mg/g for estradiol and chrysoidine, respectively. The adsorbed estradiol and chrysoidin were completely eluted from the composite beads with the eluent of 0.1 M H2SO4/MeOH and the regenerated material was used in several cycles without deterioration in its initial performances. This study suggests that the developed composite beads have high potential for the efficient removal estradiol and chrysoidin from aqueous solution.

Introduction of electropolymerization of pyrrole as a coating method for stir bar sorptive extraction of estradiol followed by gas chromatography.

In this study, fabrication of a stir bar sorbent is presented by electropolymerization of pyrrole via cyclic voltametry for the first time. The fabricated stir bar was applied as an efficient sorbent for extraction and pre-concentration of trace amounts of estradiol in urine samples through stir bar sorptive extraction (SBSE) method followed by gas chromatography-flame ionization detector. For this purpose, first the surface of stainless steel rod was modified by hyroxide functional group. Then electropolymerization of pyrrole monomers took place on the surface of functionalized steel rod under the optimized conditions including pyrrole concentration of 0.03 mol L-1, equal concentration ratio of pyrrole to sodium dodecyl sulfate, 10 cycles of cyclic voltammetry and potential scan rate of 10 mV s-1. Characterization of the produced sorbent was confirmed by scanning electron microscope imaging and energy-dispersive X-ray and infrared spectroscopy. Evantually, under the optimized conditions, the stir bar sorbent was used for extraction of estradiol from human urine samples. The presented SBSE method showed a good linearity range of 50-700 ng mL-1 with coefficient of determination 0.9910, limit of detection 10 ng mL-1 and theoretical limit of quantification 33 ng mL-1. Moreover, better enrichment factor (87) and extraction recovery (43%) were obtained using the fabricated stir bar compared with two commercial stir bars for estradiol. The intra- and inter-bar relative recoveries were obtained 92.0% and their coefficient of variations were less than 5.4%.

Enhanced adsorption of steroid estrogens by one-pot synthesized phenyl-modified mesoporous silica: Dependence on phenyl-organosilane precursors and pH condition.

In this study, the phenyl-modified mesoporous materials were successfully synthesized using phenyl-organosilanes (trimethoxyphenylsilane and triethoxyphenylsilanea) by one-pot co-condensation method for the removal of estrone (E1), 17ß-estradiol (E2), and 17α-ethinyl estradiol (EE2). Both the triethoxyphenylsilane-modified material (20%EtPh-MCM-41) and trimethoxyphenylsilane-modified material (20%MePh-MCM-41) could rapidly achieve equilibrium in 30 min at low adsorbent dosage of 0.025 g L-1. But the different hydrolysable groups of trimethoxyphenylsilane and triethoxyphenylsilane led to the discrepancies in physicochemical properties of the 20%EtPh-MCM-41 and 20%MePh-MCM-41, and thus affected adsorption performance. The 20%EtPh-MCM-41 exhibited the faster estrogen adsorption rates expressed in pseudo-second-order kinetic constant than the 20%MePh-MCM-41 due to the more hydrophobicity. Conversely, the 20%MePh-MCM-41 had much more estrogen adsorption capacities than the 20%EtPh-MCM-41 because of the more available adsorption sites. The addition of the phenyl-organosilane improved estrogen adsorption by π-π and hydrophobic interactions, and the Langmuir-model-based maximum adsorption amounts could reach 99.02, 83.47, and 53.60 mg g-1 for EE2, E2, and E1, respectively. But excessive concentration of phenyl-organosilane decreased adsorption capacities due to poor pore structure. Alkaline solution, which induced estrogen deprotonation and negative surface charge of absorbents, inhibited estrogen adsorption by electrostatic repulsion and the decreased hydrophobic interaction, but acidic and neutral solutions, ionic strength, and humic acid did not significantly affect estrogen removal. This work not only showed the high potential of trimethoxyphenylsilane-modified MCM-41 used in water purification for steroid estrogens, but also demonstrated the suitable selection of organosilane precursors was key in producing favorable materials with designed functionality.

Study of the adsorption of endocrine disruptor compounds on typical filter materials using a quartz crystal microbalance.

Drinking water containing environmental endocrine disruptor compounds (EDCs) endangers human health, and researching the purification process of drinking water for the effective removal of EDCs is vitally important. Filtering plays a crucial role in the bio-adsorption of EDCs, but the adsorption mechanism that occurs between the EDCs and filters remains unclear. In this study, a quartz crystal microbalance (QCM) was employed to elucidate the adsorption mechanism because QCM is a label-free method that possesses high selectivity, high stability, and high sensitivity. The results indicated that a pseudo-first-order kinetic model best fits the adsorption process of four different EDCs, which included bisphenol A (BPA), estrone (E1), estradiol (E2), and sulfamethoxazole (SMZ), on silica (quartz sand), a typical filter material surface. The order of the amount of individual EDCs absorbed on the silica surface was qE2 > qE1 > qSMZ > qBPA and related to their molecular structure, polarity, and chargeability. As the initial EDC concentration increased, the adsorbed amount of the four EDCs on the silica surface increased; however, the initial concentration had little effect on removal efficiency. The calculated Freundlich exponent (1/n) demonstrated SMZ and BPA showed a greater tendency for adsorption than E1 and E2. The mass response time on the surface of the silica gradually increased as the pH increased (from 5.5 to 8.5), indicating the adsorption rate was inhibited by the increase in pH. The addition of electrolytes shortened the mass response time of EDCs on the QCM chip. The pH and ionic strength produced no significant effects on adsorption because hydrophobicity was the primary contributor to adsorption. This study facilitated a better understanding of the interaction between EDCs and filters in water treatment.

Recent advances in the detection of 17ß-estradiol in food matrices: A review.

Pollution of endocrine disrupting chemicals has become a global issue. As one of the hormonally active compounds, 17ß-estradiol produces the strongest estrogenic effect when it enters the organism exogenously including food intakes, bringing potential harmfulness such as malfunction of the endocrine system. Therefore, in order to assure food safety and avoid potential risks of 17ß-estradiol to humans, it is of great significance to develop rapid, sensitive and selective approaches for the detection of 17ß-estradiol in food matrices. In this review, the harmfulness and main sources of 17ß-estradiol are firstly introduced, followed by the description of the principles and applications of different approaches for 17ß-estradiol detection including high performance liquid chromatography, electrochemistry, Raman spectroscopy, fluorescence and colorimetry. Particularly, applications in detecting 17ß-estradiol in food matrices over the years of 2010-2018 are discussed. Finally, advantages and limitations of these detection methods are highlighted and perspectives on future developments in the detection methods for 17ß-estradiol are also proposed. Although many detection approaches can achieve trace or ultratrace detection of 17ß-estradiol, further studies should be focused on the development of in-situ and real-time methods to monitor and evaluate 17ß-estradiol for food safety.

In situ decomposition of deep eutectic solvent as a novel approach in liquid-liquid microextraction.

In this study, a novel approach for effective liquid-liquid microextraction based on deep eutectic solvent (DES) decomposition was suggested for the first time. It was established that DESs synthesized from tetrabutylammonium bromide and long-chain alcohols decomposed in aqueous phase resulting in in situ dispersion of organic phase and extraction of hydrophobic analyte(s). It this process long-chain alcohol acted as an extraction solvent and tetrabutylammonium bromide acted as a dispersive agent and promoted mass transfer between aqueous and organic phases as a salting out agent. Phenomenon of DES decomposition was studied in detail and applied for separation and preconcentration in chemical analysis for the first time. The developed approach was applied for 17ß-estradiol microextraction from transdermal gel samples as a proof-of-concept example. The results showed that the in situ dispersed organic phase obtained can provide efficient extraction of 17ß-estradiol with good extraction recovery (95 ±â€¯5%) and excellent reproducibility (6%). The reported approach proves to be fast, simple, and inexpensive.

N-propyl functionalized spherical mesoporous silica as a rapid and efficient adsorbent for steroid estrogen removal: Adsorption behaviour and effects of water chemistry.

To achieve an enhanced and selective adsorption of steroid estrogens, the n-propyl functionalization was applied to the mesoporous silica material (MCM-41) according to the physico-chemical property analysis of steroid estrogens. Adsorption behaviour and water chemistry effects were evaluated with the most concerned steroid estrogens: estrone (E1), 17ß-estradiol (E2) and 17α-ethinyl estradiol (EE2) based on the materials characterization. The results showed the uptakes of E1, E2, and EE2 onto the modified MCM-41 were enhanced and accelerated by the n-propyl functionalization, which was positively correlated with the hydrophobicity of the synthesized materials. Kinetic data fitted the pseudo-second-order model well. Based on the Langmuir model, the maximum adsorption capacities of the n-propyl modified MCM-41 were up to 119.87, 88.38, and 86.91 mg g-1 for EE2, E1, and E2, respectively. Importantly, both acid and neutral solutions were beneficial to estrogen removal, but ionic strength and humic acid did not affect the estrogen adsorption. The above results suggested that the n-propyl functionalized MCM-41 would be a promising adsorbent for the rapid and efficient removal of estrogens with the selectivity from natural organic matter like humic acid. Mechanism analysis showed the key role of hydrophobic interaction, and it also confirmed the contribution of the carbonylic lone pair electrons of E1, which helped the formation of stronger hydrogen bonds with silicon hydroxyls and enhanced the dipole-dipole interaction between E1 and the synthesized materials.

Efficient extraction of estrogen receptor-active compounds from environmental surface water via a receptor-mimic adsorbent, a hydrophilic PEG-based molecularly imprinted polymer.

We report an efficient screening procedure for the selective detection of compounds that are actively bound to estrogen receptor (ER) from environmental water samples using a receptor-mimic adsorbent prepared by a molecularly imprinted polymer (MIP). To mimic the recognition ability of ER, we improved the typical MIP preparation procedure using a hydrophilic matrix with a polyethylene glycol (PEG)-based crosslinker and a hydrophobic monomer to imitate the hydrophobic pocket of ER. An optimized MIP prepared with methacrylic acid as an additional functional monomer and estriol (E3), an analogue of 17ß-estradiol (E2), exhibited highly selective adsorption for ER-active compounds such as E2 and E3, with significant suppression of non-specific hydrophobic adsorption. The prepared MIP was then applied to the screening of ER-active compounds in sewage samples. The fraction concentrated by the MIP was evaluated by in vitro bioassay using the yeast two-hybrid (Y2H) method and liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOFMS). Compared to an authentic adsorbent, styrene-divinylbenzene (SDB)-based resin, the fraction concentrated by the MIP had 120% ER activity in the Y2H assay, and only 25% peak volume was detected in LC-Q-TOFMS. Furthermore, a few ER-active compounds were identified only from the fraction concentrated by the MIP, although they could not be determined in the fraction concentrated by the SDB-based resin due to ion suppression along with high levels of hydrophobic compounds. These results indicated that the newly developed MIP effectively captured ER-active compounds and while allowing most non-ER-active compounds to pass through.

Automated SPE-based synthesis of 16α-[18F]fluoroestradiol without HPLC purification step.

[18F]fluoroestradiol ([18F]FES) is well-established PET radiotracer for diagnosing and monitoring treatment of estrogen-positive breast cancer. The radiotracer is produced via one-pot two steps synthesis using cyclic sulfate precursor and is usually purified by semi-preparative HPLC. Here we suggested simple SPE purification procedure using OASIS WAX 3cc and Sep-Pak QMA light cartridges that afforded [18F]FES in typically 15% RCY (corrected for decay) within 45 min formulated in 5% EtOH/saline. All purity parameters were well within specifications recommended in the Investigator's Brochure for [18F]Fluoroestradiol.

Selective separation and purification of ß-estradiol from marine sediment using an optimized core-shell molecularly imprinted polymer.

The core-shell molecularly imprinted polymers were optimized to provide reliable connections that allow molecularly imprinted polymers to be fixed on SiO2 surface for the efficient separation and purification of ß-estradiol from marine sediment for the first time. To achieve the goal, different preparation methods were used and finally the polymer using 3-methacryloxypropyltrimethoxysilane as coupling agent exhibited the best result, which further confirmed that 3-methacryloxypropyltrimethoxysilane played an indispensable role on improving the inter-particle connections. An offline molecularly imprinted solid-phase extraction with high-performance liquid chromatography method was successfully applied to the isolation and enrichment of ß-estradiol from marine sediment samples with high adsorption capacity, excellent clean-up efficiency, and great enrichment effect as well as high recovery (>90%) and accuracy (RSD < 8.5%, n = 3). It proved the successful grafting of molecularly imprinted polymers on SiO2 surface and the applicability of the offline molecularly imprinted solid-phase extraction method in the selective extraction and enrichment of ß-estradiol from marine sediment.

Zipper-like magnetic molecularly imprinted microspheres for on/off-switchable recognition and extraction of 17ß-estradiol from food samples.

Zipper-like on/off-switchable and magnetic molecularly imprinted microspheres (SM-MIMs) were constructed using acrylamide (AAm) and 2-acrylamide-2-methyl propanesulfonic acid (AMPS) as functional monomers for 17ß-estradiol (17ß-E2) recognition and extraction. The imprinted polymer interactions between poly(AAm) (PAAm) and poly(AMPS) (PAMPS) with on/off-switchable property to temperature, exhibited dissociation at relatively higher temperatures (such as 30 °C) and helped 17ß-E2 enter into imprinted sites, leading to higher binding capability. Conversely, the interpolymer complexes between PAAm and PAMPS formed and blocked 17ß-E2 access to imprinted sites at lower temperature (such as 20 °C). SM-MIMs were used as dispersive solid phase extraction (SPE) adsorbent with HPLC for 17ß-E2 pretreatment and detection in food samples, and low limit detection (2.52 µg L-1) and quantification (10.76 µg L-1) with higher recovery were obtained. Therefore, SM-MIMs may be a promising adsorbent for 17ß-E2 pretreatment in food samples owing to its advantages of on/off-switchable recognition, eco-friendly elution, and efficient separation.

Effect of cultivation conditions on ß-estradiol removal in laboratory and pilot-plant photobioreactors by an algal-bacterial consortium treating urban wastewater.

The use of microalgal consortia for urban wastewater treatment is an increasing trend, as it allows simultaneous nutrient removal and biomass production. Emerging contaminants proposed for the list of priority substances such as the hormone 17ß-estradiol are commonly found in urban wastewater, and their removal using algal monocultures has been accomplished. Due to the inherent potential of algae-based systems, this study aimed to assess the capability of native photobioreactor biomass to remove 17ß-estradiol under indoor and outdoor conditions. At the same time, the microbial community changes in regular and bioaugmented operations with Scenedesmus were assessed. The results show that almost complete removal (>93.75%) of the hormone 17ß-estradiol can be attained in the system under favourable seasonal conditions, although these conditions greatly influence biomass concentrations and microbial diversity. Even under the harsh conditions of low temperatures and solar irradiation, the established consortium removed more than 50% of the pollutant in 24 h. While species from genus Chlorella were stable during the entire operation, the microbial diversity analysis revealed that assorted and evenly distributed populations stimulate the removal rates. Bioaugmentation assays proved that the input of additional biomass results in higher overall removal and decreases the yield per mg of biomass.

Removal and Biodegradation of 17ß-Estradiol and Diethylstilbestrol by the Freshwater Microalgae Raphidocelis subcapitata.

Natural steroidal and synthetic non-steroidal estrogens such as 17ß-estradiol (E2) and diethylstilbestrol (DES) have been found in natural water, which can potentially endanger public health and aquatic ecosystems. The removal and biodegradation of E2 and DES by Raphidocelis subcapitata were studied in bacteria-free cultures exposed to single and mixture treatments at different concentrations for 96 h. The results showed that R. subcapitata exhibited a rapid and strong ability to remove E2 and DES in both single and mixture treatments by biodegradation. At the end of 96 h, the removal percentage of single E2 and DES achieved 82.0%, 80.4%, 74.6% and 89.9%, 73.4%, 54.1% in 0.1, 0.5, and 1.5 mg·L-1, respectively. With the exception of the 0.1 mg·L-1 treatment at 96 h, the removal capacity of E2 was more efficient than that of DES by R. subcapitata. Furthermore, the removal percentage of mixture E2 and DES achieved 88.5%, 82.9%, 84.3% and 87.2%, 71.8%, 51.1% in 0.1, 0.5, and 1.5 mg·L-1, respectively. The removal percentage of mixed E2 was significantly higher than that of the single E2. The presence of DES could accelerate the removal of E2 from the mixture treatments in equal concentrations. In addition, the removal was mainly attributed to the biodegradation or biotransformation process by the microalgae cells rather than simple sorption and accumulation in the cells. The microalgae R. subcapitata demonstrated a high capability for the removal of the E2 and DES indicating future prospects for its application.

Poly(3,6-diamino-9-ethylcarbazole) based molecularly imprinted polymer sensor for ultra-sensitive and selective detection of 17-ß-estradiol in biological fluids.

In this work, we reported the synthesis of 3, 6-diamino-9-ethylcarbazole and its application as a new monomer for preparation of molecularly imprinted polymer (MIP) electrochemical sensor. The as prepared MIP sensor exhibited ultrahigh sensitivity and selectivity for the detection of 17-ß-estradiol in attomolar levels (1 × 10-18molL-1). The sensor works by detecting the change of the interfacial impedance that is derived from recognition of 17-ß-estradiol on the MIP layer. The MIP sensor based on 3, 6-diamino-9-ethylcarbazole monomer revealed better performance than that of unmodified carbazole monomer. The monomer/template ratio, electropolymerization scanning cycles, and the incubation pH values were optimised in order to obtain the best detection efficiency. Under the optimised condition, the MIP sensor exhibits a wide linear range from 1aM to 10µM (1 × 10-18 ̶ 1 × 10-5molL-1). A low detection limit of 0.36aM (3.6 × 10-19molL-1) and a good selectivity towards structurally similar compounds were obtained. The proposed MIP sensor also exhibits long-term stability and applicability in human serum samples. These advantages enabled this MIP sensor to be a promising alternative of electrochemical sensor and may be extended to detection of other endogenous compounds.