Adsorption Of E2 Research Articles

Molecular imprinting based sensor system developed using polymeric nanoparticles for detecting 17β‐estradiol in agricultural wastewater

AbstractMicro pollutants pose a significant issue in water ecosystems. Particularly high concentrations of 17β‐estradiol (E2) have been identified in agricultural wastewater, which poses harmful effects on aquatic organisms and disrupts ecosystem balance. Therefore, effective determination of E2 from water sources is crucial. This study developed a biosensor capable of detecting E2 in wastewater using specific polymer nanoparticle synthesis through molecular imprinting. Est‐imp‐poly(multi‐walled carbon nanotubes‐glycidyl methacrylate [MWCNT‐GMA]) polymer nanoparticles were synthesized using a surfactant‐free emulsion polymerization method, and their characterization was conducted using FTIR and scanning electron microscopy (SEM) technologies. The Qmax value for Est‐imp‐poly(MWCNT‐GMA) nanoparticles in a 1 mg/mL E2 solution was determined to be 140 ppm. Comparing adsorption capacities, the molecularly imprinted nanoparticles (MIP) showed nearly five times higher E2 adsorption compared to non‐imprinted polymers (NIP). The Est‐imp‐poly(MWCNT‐GMA)‐Nafion/screen‐printed electrode (SPE) system was employed for analyzing wastewater samples. The current measurements taken at various concentrations in the wastewater consistently matched the E2 concentration calibration curve. The limit of detection (LoD) and limit of quantification (LoQ) were determined to be 0.042 and 0.12 μM, respectively. The biosensor demonstrated a linear working range from 0.12 to 50 μM, with a high correlation coefficient (R2 = 0.9927). These results highlight the potential of the developed biosensor for detecting E2 in real samples.

First-Principles Structure Search Study of 17-β-Estradiol Adsorption on Graphene.

17-Beta-estradiol (E2), a steroid hormone synthesized from cholesterol, has various impacts on health and the environment. Currently, the gold standard for its measurement in the body is a conventional blood test (mass spectrometry), but carbon-based electrochemical sensors have been proposed as an alternative due to their advantages, such as rapid analysis time and sensitivity. To improve the atomic-level understanding of the interactions at the substrate surface, we performed density functional theory (DFT) simulations to study the nature of the adsorption of E2 on pristine graphene. Bayesian Optimization Structure Search (BOSS) was employed to reduce human bias in the determination of the most favorable adsorption configurations. Two stable adsorption minimum configurations were found. Analysis of their electronic properties indicates that E2 physisorbs on graphene. Embarking upon complex carbonaceous materials, the importance of finding all possible minimum candidates with automated structure search tools is highlighted. Computational investigations facilitate tailoring substrate materials with outstanding performance and applications in neuroscientific research, fertility monitoring, and clinical trials. Combining them with experimental research carries significant potential to advance sensor design beyond the current state-of-the-art.

17β-estradiol (E2) removal in anode-electrodialysis (anode-ED) during nutrient recovery from pig manure digestate

Nutrient recovery from anaerobic digestate through electrodialysis technology (ED) has been investigated and shown high promise, but the removal of 17β-estradiol (E2), which is a natural estrogen and widely found in manure digestate, is not clear. This study examined the mechanism of membrane adsorption and anodic oxidation of E2 during recovering nutrient from manure digestate, and further investigated the performance of Anode-ED in E2 removal. The results showed that the removal of E2 in conventional ED was primarily attributed to membrane adsorption, resulting in no detectable E2 in the product solution. The adsorption capacity of the anion exchange membrane for E2 was significantly higher compared to that of the cation exchange membrane. During Anode-ED operation, E2 was efficiently removed by electrochemical oxidation, in which the chlorination played a primary role. Moreover, the oxidation intermediates of E2 were further removed after 40 min. Even though the carbonate, volatile fatty acid (VFA), and humic acid in the real wastewater have a negative impact on E2 oxidation, the E2 was completely removed from digestate during nutrient recovery in the anode-ED. This study indicates that anode-ED is a promising technology for the removal of E2 during nutrient recovery from digestate.

Preparation of Immobilised 17β-Estradiol-Imprinted Nanoparticles onto Bacterial Cellulose Nanofibres to Use for the Removal of 17β-Estradiol from Wastewater.

Estradiol, a phenolic steroid oestrogen, is one of the endocrine-disrupting chemicals (EDCs) found in natural and tap waters. The detection and removal of EDCs is attracting attention daily as they negatively affect animals' and humans' endocrine functions and physiological conditions. Therefore, developing a fast and practical method for the selective removal of EDCs from waters is essential. In this study, we prepared 17β-estradiol (E2)-imprinted HEMA-based nanoparticles onto bacterial cellulose nanofibres (E2-NP/BC-NFs) to use for the removal of E2 from wastewater. FT-IR and NMR confirmed the structure of the functional monomer. The composite system was characterised by BET, SEM, µCT, contact angle, and swelling tests. Additionally, the non-imprinted bacterial cellulose nanofibres (NIP/BC-NFs) were prepared to compare the results of E2-NP/BC-NFs. Adsorption of E2 from aqueous solutions was performed in batch mode and investigated via several parameters for optimisation conditions. The effect of pH studies was examined in the 4.0-8.0 range using acetate and phosphate buffers and a concentration of E2 of 0.5 mg/mL. The maximum E2 adsorption amount was 254 µg/g phosphate buffer at 45 °C. The experimental data show that the Langmuir is a relevant isotherm model for E2 adsorption. Additionally, the relevant kinetic model was the pseudo-second-order kinetic model. It was observed that the adsorption process reached equilibrium in less than 20 min. The E2 adsorption decreased with the increase in salt at varying salt concentrations. The selectivity studies were performed using cholesterol and stigmasterol as competing steroids. The results show that E2 is 46.0 times more selective than cholesterol and 21.0 times more selective than stigmasterol. According to the results, the relative selectivity coefficients for E2/cholesterol and E2/stigmasterol were 8.38 and 86.6 times greater for E2-NP/BC-NFs than for E2-NP/BC-NFs, respectively. The synthesised composite systems were repeated ten times to assess the reusability of E2-NP/BC-NFs.

Sorption kinetics, isotherms and molecular dynamics simulation of 17β-estradiol onto microplastics

Microplastic is a new type of pollutant, which can act as a carrier for organic contaminants. It affects the migration and bioavailability of chemicals and potentially threatens the ecology. This work investigated the adsorption kinetics, isotherm and influencing factors of 17β-estradiol (E2) on three dominate microplastics. Then, used molecular dynamics (MD) simulation to analyze the adsorption mechanism. The results showed that E2 adsorption onto microplastics conformed well to the Pseudo-second-order kinetics and Redlich-Petersen isotherm model. The adsorption capacity of E2 on microplastics was polyethylene (PE) > polypropylene (PP) > polystyrene (PS). The small particle size of microplastics was conducive to the adsorption due to its large specific surface area. The thermodynamic parameters demonstrated the adsorption of E2 was a spontaneous and exothermic process, so low temperature was benefit for the adsorption. The MD simulation results indicated the adsorption of E2 on MPs belonged to surface adsorption. The order of E2 adsorption energy by three microplastics obtained by molecular dynamics simulation is consistent with the experimental results. This work may help to understand the molecular adsorption process and provide a theoretical basis for the combined ecotoxicity of microplastics.

Comparison of 17β-Estradiol Adsorption on Corn Straw- and Dewatered Sludge-Biochar in Aqueous Solutions.

Removal of steroid hormones from aqueous environment is of prevailing concern because of their adverse impact on organisms. Using biochar derived from biomass as adsorbent to remove pollutants has become more popular due to its low cost, effectiveness, and sustainability. This study evaluated the feasibility of applying corn straw biochar (CSB) and dewatered sludge biochar (DSB) to reduce 17β-estradiol (E2) from aquatic solutions by adsorption. The experimental results showed that the adsorption kinetics and isotherm behavior of E2 on the two biochars were well described by the pseudo-second-order (R2 > 0.93) and Langmuir models (R2 > 0.97). CSB has higher E2 adsorption capacity than DSB, and the maximum adsorption capacity was 99.8 mg/g obtained from Langmuir model at 298 K, which can be attributed to the higher surface area, porosity, and hydrophobicity of this adsorbent. Higher pH levels (>10.2) decreased the adsorption capacities of biochar for E2, while the ionic strength did not significantly affect the adsorption process. The regeneration ability of CSB was slightly better than that of DSB. The possible adsorption mechanism for E2 on biochar is suggested as π–π interactions, H–bonding, and micropores filling. These results indicated that CSB has more potential and application value than DSB on reducing E2 from aqueous solutions when considering economy and removal performance.

Removal behaviors of aerobic granular sludge on estrogens: Adsorption kinetics and removal mechanism

Aerobic granular sludge (AGS) has the advantages of high biomass and compact structure for withstanding the shocks and toxins. In this study, the removal behaviors of two typical endocrine disrupting chemicals (EDCs), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2), by AGS were investigated. 93.5% of E2 and 84.8% of EE2 were removed at a concentration of 10 μg/L during 120 d operation, with the removal efficiencies of COD, NH4+-N and TP reaching the same level as those in the control group. Batch experimental results showed that the biodegradation was the dominant mechanism of E2 removal, while EE2 was more bio-refractory and mainly removed via adsorption. The adsorption of E2 and EE2 followed heterogeneous multilayer and chemical processes, owing to the active adsorption sites provided by amides, carboxylic groups, hydroxyl groups and polysaccharides on AGS. At the same time, Zoogloea, Sphingomonas, Pseudomonas and Brevundinomas were highly enriched under the pressure of estrogens, which assisted in the stability of AGS reactors by EPS secretion and estrogens degradation.

Facile fabrication and characterization of kenaf core as natural biochar for the highly efficient removal of selected endocrine-disrupting compounds.

This study aims to formulate and fabricate the optimum condition of modified kenaf core (MKC) for the removal of targeted endocrine-disrupting compounds in a batch adsorption system. Kenaf core was chemically modified using phosphoric acid as an activating agent, which involved the pyrolysis step. Results indicated a significant difference (p < 0.05) for unmodified and novel modified biochar, observed in characteristic performance analysis via ultimate analysis, Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy (FTIR) spectrum, and Brunauer-Emmett-teller (BET) surface area. The removal percentage of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in individual and binary mixture systems was examined in order to ascertain the highest removal percentage for MKC application in an aqueous solution. The main and interaction effects of three prepared variables such as incorporate of impregnation concentration of an acid catalyst (0.1-1.0M), particle size (45-1,000µm), and dosage (1.0-20.0g/L) were examined and statistically analyzed via design of experiment (DoE) through developed quadratic models. The removal efficiency of E2 and EE2 in an individual system leads to T2KC > T1KC > T3KC, whereas that in the binary mixture system leads to T2KC > T1KC > T3KC and T1KC > T2KC > T3KC for E2 and EE2 adsorption, respectively, through hydrogen bonding and the π-π interaction mechanism. Thus, the findings revealed T2KC at a moderate level of acid concentration (0.5M H3PO4) to be a potential biochar, with an environmentally safe and sound profile for opposing emerging pollutant issues as well as for the attainment of sustainable development goals.

Organic matter interference with steroid hormone removal by single-walled carbon nanotubes − ultrafiltration composite membrane

Composite adsorbent−ultrafiltration membranes for micropollutant removal are an interesting concept, although water matrix compounds, such as organic matter (OM), may interfere with micropollutant adsorption. To prevent this interference, the adsorbents such as single-walled carbon nanotubes (SWCNTs) can be deposited on the permeate side of an ultrafiltration membrane (UF) that can retain OM. In this study, the ‘shielding’ effect by different UF MWCOs of such an SWCNT−UF composite was evaluated for nine different types of OM. All nine OM types competed with 17β-estradiol (E2) for adsorption to varying extents, and tannic acid (TA, 1.7 kDa) reduced E2 adsorption by SWCNT−UF most drastically. TA interference mechanisms included direct competition with hormones for adsorption sites, and indirect competition via TA−hormone interactions. TA was not fully retained by the composite membrane with an MWCO range of 3−100 kDa, resulting in ineffective shielding. In contrast, humic acid was mostly retained by the composite with low MWCO of 3−10 kDa and allowed high E2 adsorption. This study demonstrates that tailoring composite membranes by carefully choosing UF MWCO can prevent interference of OM types in micropollutant adsorption by permeate-side adsorbents.

Estradiol Removal by Adsorptive Coating of a Microfiltration Membrane.

This work demonstrates the enhancement of the adsorption properties of polyethersulfone (PES) microfiltration membranes for 17β-estradiol (E2) from water. This compound represents a highly potent endocrine-disrupting chemical (EDC). The PES membranes were modified with a hydrophilic coating functionalized by amide groups. The modification was performed by the interfacial reaction between hexamethylenediamine (HMD) or piperazine (PIP) as the amine monomer and trimesoyl chloride (TMC) or adipoyl chloride (ADC) as the acid monomer on the surface of the membrane using electron beam irradiation. The modified membranes and the untreated PES membrane were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), water permeance measurements, water contact angle measurements, and adsorption experiments. Furthermore, the effects of simultaneous changes in four modification parameters: amine monomer types (HMD or PIP), acid monomer types (TMC or ADC), irradiation dosage (150 or 200 kGy), and the addition of toluene as a swelling agent, on the E2 adsorption capacity were investigated. The results showed that the adsorption capacities of modified PES membranes toward E2 are >60%, while the unmodified PES membrane had an adsorption capacity up to 30% for E2 under similar experimental conditions, i.e., an enhancement of a factor of 2. Next to the superior adsorption properties, the modified PES membranes maintain high water permeability and no pore blockage was observed. The highlighted results pave the way to develop efficient low-cost, stable, and high-performance adsorber membranes.

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.

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.

Removal of 17β-Estradiol by Activated Charcoal Supported Titanate Nanotubes (TNTs@AC) through Initial Adsorption and Subsequent Photo-Degradation: Intermediates, DFT calculation, and Mechanisms

A low-cost composite of activated charcoal supported titanate nanotubes (TNTs@AC) was developed via the facile hydrothermal method to remove the 17β-estradiol (E2, a model of pharmaceutical and personal care products) in water matrix by initial adsorption and subsequent photo-degradation. Characterizations indicated that the modification occurred, i.e., the titanate nanotubes would be grafted onto the activated charcoal (AC) surface, and the micro-carbon could modify the tubular structure of TNTs. E2 was rapidly adsorbed onto TNTs@AC, and the uptake reached 1.87 mg/g from the dual-mode model fitting. Subsequently, the adsorbed E2 could be degraded 99.8% within 2 h under ultraviolet (UV) light irradiation. TNTs@AC was attributed with a unique hybrid structure, providing the hydrophobic effect, π−π interaction, and capillary condensation for E2 adsorption, and facilitating the electron transfer and then enhancing photocatalytic ability for E2-degradation. In addition, the removal mechanism of E2 was elucidated through the density functional theory calculation. Our study is expected to provide a promising material for environmental application.

Influence of microplastics occurrence on the adsorption of 17β-estradiol in soil

High levels of steroid estrogens are continuously detected in the soil environment, and even the concentration in vegetables and fruits has reached levels that have an impact on children's health, which has attracted growing attention. Moreover, microplastics (MPs) in the soil system are also of increasing concern worldwide. The effects of MPs on the adsorption of organic pollutants in soil systems, however, remain largely unexplored. In this study, MPs common in greenhouse vegetable soil (polyethylene, polyvinyl chloride and polystyrene) were selected to investigate the effect of MPs occurrence on the adsorption of 17β‑estradiol (E2) in soil under various conditions. The experimental results showed that the adsorption capacity of MPs to E2 is stronger than that of soil. Moreover, the occurrence of MPs in soil increased the adsorption capacity for E2, and the addition amount and aging of MPs enhanced the promotion effect. This enhancement indicated that the input of MPs into soil might reduce the mobility of E2 by improving the adsorption capacity of the soil. These results deepen the understanding of the adsorption behavior of E2 in the coexisting system of MPs and soil and provide a theoretical basis for E2 pollution control.

17β-Estradiol removal routes by moving bed biofilm reactors (MBBRs) under various C/N ratios

This study evaluated the contribution of biotic and abiotic routes to the 17β-estradiol (E2) removal in moving bed biofilm reactors (MBBRs), and uncovered the interrelation between the E2 removal routes and biofilm characteristics, which was not researched in previous literature. Three MBBRs with different C/N ratios (0 for C/N0; 2 for C/N2; and 5 for C/N5) were operated in continuous mode. A 65-day degradation demonstrated that the MBBRs had high potential to remove E2 regardless of the C/N (E2 removal greater than 99% for all MBBRs; P > 0.05). Further batch tests showed that the E2 removal mainly resulted from heterotrophic activities for all MBBRs, accounting for approximately 85% for all MBBRs (P > 0.05), followed by nitrification (10–11%) and adsorption (4–5%). Importantly, lower adhesive force likely led to higher E2 adsorption onto biofilms. Besides, enhanced ammonia oxidizing rate (AOR) was consistent with the high contribution of nitrification to the E2 attenuation. Importantly, heterotrophic activity was positively correlated with its contribution to E2 removal (r = 0.99, P < 0.05). To sum, the results obtained in this study helped to understand the E2 removal routes in nitrifying biofilm systems.

Comparing the effects of different types of inorganic nanoparticles on 17β-estradiol adsorption by graphene oxide

This study compared the effects of five types of inorganic nanoparticles (INPs) on the 17β-estradiol (E2) adsorption to graphene oxide (GO). The results showed that INPs increased the equilibrium time for the adsorption of E2 to GO. Higher Brunauer-Emmett-Teller (BET) surface area of INPs resulted in lower diffusion rate of E2, and thus the adsorption rate constant (k2) calculated from pseudo-second-order kinetic model negatively correlated with the BET surface area of INPs (p = 0.037). In addition, INPs decreased the adsorption amount of E2 to GO, and the inhibition effects declined in the order of Al2O3 > ZnO > TiO2 > SiO2 > Fe2O3. This is determined by the interactions between GO and INPs. The positively charged ZnO and Al2O3 strongly heteroaggregate with GO via electrostatic attraction, and then significantly inhibited E2 adsorption to GO. In contrast, the homoaggregation of GO was superior to its heteroaggregation with negatively charged SiO2 and TiO2, and then lower inhibition of E2 adsorption to GO was induced. Fe2O3 with less negative charge (−8.48 mV) led to the lowest inhibition effect on E2 adsorption to GO because of its preferable homoaggregation. The results were further confirmed by Derjaguin-Landau-Verwey-Overbeek calculation, transmission electron microscopy, and sedimentation experiments. This study revealed how the properties of INPs influence their effects on the adsorption of E2 by GO, and the findings are critical to understand the behavior and fate of GO and pollutants in natural aquatic environment.

Combined effects of 17β-estradiol and copper on growth, biochemical characteristics and pollutant removals of freshwater microalgae Scenedesmus dimorphus

Contamination by estrogens and heavy metals can cause great environment concern and necessitate efficient approaches for their removals. In this study, the combined effects of 17β-estradiol (E2) and Cu(II) on microalgae growth and biochemical characteristics were investigated. Results showed that 1 mg/L Cu(II) promoted the growth of Scenedesmus dimorphus, while 2 mg/L Cu(II) exhibited growth inhibition, compared with the same concentration of E2. Biochemical characteristics including enzyme activities as well as the contents of chlorophyll, protein and carbohydrate were significantly affected by the coexistence of E2 and Cu(II) after 12 d of cultivation. S. dimorphus exhibited high E2 and Cu(II) removal efficiencies (89.9% of E2 and 76.6% Cu(II) under the coexistence of 0.5 mg/L E2 and 1 mg/L Cu(II), respectively). Lower concentration of Cu(II) might serve as a bridge during E2 removal by S. dimorphus while competitive adsorption of Cu(II) and E2 occurred under the condition of excessive Cu(II). Results could confirm that S. dimorphus was a potential bioresource for the effective removal of E2 and Cu(II).

Comparison of 17β-estradiol adsorption on soil organic components and soil remediation agent-biochar

Steroid estrogen residues (SEs) in the soil have attracted growing attention because of their potential for endocrine disruption. Soil organic matter (SOM) and soil remediation agent-biochar, both have important influences on the fate of SEs in the soil environment. This study compared the adsorption of 17β-estradiol (E2) on wheat straw biochar (W-BC) and cow manure biochar (C-BC) with main SOM components including biomacromolecules (cellulose, collagen and lignin) and humic acids (HA). The impact of pyrolysis temperature (350 °C, 550 °C, and 700 °C) on the adsorption capacity of biochar and different concentrations NaClO oxidation on the adsorption capacity of HA were also investigated. The experimental results showed that the adsorption of E2 by biomolecules conformed to the linear isotherm (R2 > 0.88), and the adsorption of E2 on biochars and HA were well described by the Langmuir and Freundlich isotherm (R2 > 0.94). Meanwhile, the order of the E2 adsorption capacity of sorbents was W-BC > C-BC > HA > lignin > collagen > cellulose. The adsorption capacity of biochar and SOM for E2 increased with the enhancement of aromaticity and hydrophobicity and the reduction of polarity. In addition, the increase of pyrolysis temperature of biochars also promoted the adsorption capacity of E2, while oxidation treatment with NaClO reduced the adsorption capacity of HA to E2. These results deepened the understanding of the adsorption behaviour of E2 on SOM and biochar, and expanded the understanding of the behaviour of SEs in the soil environment.

Synthesis a graphene-like magnetic biochar by potassium ferrate for 17β-estradiol removal: Effects of Al2O3 nanoparticles and microplastics.

A graphene-like magnetic biochar (GLMB) was synthesized using lotus seedpod and potassium ferrate with simple step and applied for E2 adsorption. GLMB was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), Raman, X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and BET surface area. Several common (solution pH, ionic strength, humic acid and foreign ions) and new (Al2O3 nanoparticles and microplastics (MPs)) water experiment conditions were investigated. Characterization results demonstrated that the sample was fabricated successfully and it possessed some graphene-like properties and a large surface area (828.37m2/g). Adsorption results revealed that the pseudo-second-order kinetics and Langmuir isotherm models could provide a better description for E2 uptake behavior. The E2 adsorption capacity could be influenced by solution pH, ionic strength and SO42- ions, and the effect of humic acid and background electrolyte (Na+, K+, Ca2+, Mg2+, Cl-, NO3-, PO43-) could be neglected. The presences of Al2O3/MPs significantly decreased the time to reach adsorption equilibrium for E2 adsorption on GLMB, but had no obvious improvement or inhibiting effects on E2 removal when the adsorption reached equilibrium. The adsorption mechanism for E2 adsorption on GLMB was multiple, which involving π-π interactions, micropore filling effects, electrostatic interaction. The regeneration experiments showed that GLMB possessed a good regeneration performance. Based on the experimental results and comparative analysis with other adsorbents, GLMB was an economical, high-efficiency, green and recyclable adsorbent for E2 removal from aqueous solution.

Supramolecular Protein Assembly Retains Its Structural Integrity at Liquid–Liquid Interface

AbstractAdsorption of globular proteins at liquid–liquid interface results in compromised structures and functionalities to maintain a thermodynamically favorable state. However, the structural behavior of highly symmetrical supramolecular protein assemblies, adsorbed at the liquid–liquid interface, is not well understood. In this study, a model supramolecular protein assembly, E2 protein nanocage, a dodecahedral cage‐structured protein, is studied upon adsorption at the oil–water interface by both theoretical and experimental analyses. Molecular dynamics simulations and force estimation reveal that noncovalent interactions between E2 subunits dominate over the tangential force experienced by E2 at the interface allowing it to retain its structural integrity. Experimental analyses confirm the adsorption of E2 on the liquid–liquid interface with negligible penetration depth. Molecular structural analyses further suggest the structural integrity of the caged structure of E2 at the oil–water interface with minimal change in the tertiary and secondary structures. In conclusion, this study brings new insights into the behavior of highly symmetrical supramolecular protein assemblies at liquid–liquid interface which is important in preserving their functionalities.