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At present, an in-depth knowledge of polycyclic aromatic hydrocarbons (PAHs) in the multimedia system of the urban environment remains limited. Taking the Naples metropolitan area (NMA) for instance, we simulated the cross-media transfer of PAHs using a multimedia urban model, involving air, water, soil, sediment, vegetation, and impervious film. The results indicated that the predicted PAH values in 2015 match well with their corresponding in-situ monitoring data. The PAH emission inventory and the simulated mass in various media all showed a downward trend from 2015 to 2020 due to national energy conservation policies and Corona Virus Disease 2019. The simulated mass of PAHs in the soil and sediment phases was 896.8 and 232.7 kg in 2020, respectively, contributing together to 96.7% of PAHs in the NMA. And they were identified as the greatest sinks for PAHs, and exhibited the longest retention duration, with values of PAH persistence reaching approximately 548.8 - 2,0642.3 hours. The results of transfer fluxes indicated that local emissions and atmospheric advection were the primary routes affecting the distribution of PAHs. The sensitivity analysis indicated that atmospheric advection rate was the most critical parameter for air, soil, vegetation, and film, whereas water concentration and sediment degradation rate were vital for water and sediment, respectively. This study offered valuable insights into how human activity contributes to the status and fate of PAHs in the urban environment.

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The methods that can accurately measure the concentrations of nonextractable residues (NERs) of hydrophobic organic contaminants (HOCs) in soil are still lacked in current studies. In this study, three methods, namely methanolic saponification treatment (MST), silylation treatment (ST), and acid deashing treatment (ADT), were investigated and then combined to extract the NERs of six types of polycyclic aromatic hydrocarbons (PAHs) from nine soil samples. The NER concentrations of PAHs obtained by ST (2.43-521.73 ng g-1) were comparable to or significantly higher than those obtained by MST (1.94-291.54 ng g-1), owing to the properties of soil and target compounds. Additionally, ADT could further release a considerable amount of PAH NERs (0.39-276.99 ng g-1) from the soils that had been treated with ST. The mechanism was that acid solution dissolved mineral components, significantly increasing the pore size of the soil matrices from 9.37-15.57 nm to 17.11-27.51 nm. The average percentage of each PAH obtained by ADT (the ratio of the amount obtained by ADT to the total NER content) exhibited a negative correlation with their ring numbers (R2 = 0.62, p < 0.05), whereas the percentage of targets recovered through ST increased linearly with their log KOW values (R2 = 0.75, p < 0.05). Moreover, there is a positive correlation (R2 = 0.73, p < 0.05) between the NER percentages of phenanthrene (obtained by ST-ADT) and the specific surface areas of soils, and the NER percentages of benzo(g,h,i)perylene is positively correlated to the content of total organic carbon (R2 = 0.62, p < 0.05). These results suggested that the amounts and locations of NERs were influenced by both the physicochemical characteristics of PAHs and soils. These findings provide some basic understandings of the entrapped mechanisms of PAH NERs, helping to establish strategies for improving their detection accuracy.

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Conventional chemical extraction methods may lead to overestimate or underestimate bioaccessibility due to their inability to provide realistic kinetic information regarding PAHs in soils. In this study, we propose the use of magnetic solid phase extraction (MSPE) technique for assessing the bioaccessibility of PAHs in the soil-earthworm system. Firstly, a novel polydopamine-coated magnetic core-shell microspheres (Fe3O4-C16@PDA) was developed by a one-pot sol-gel and self-polymerization method. The PDA coatings not only enhance the hydrophilicity of material surfaces but also exhibit excellent biocompatibility. The maximum adsorption capacity of Fe3O4-C16@PDA for 16 PAHs was 52.72 mg g-1, indicating that the proposed material fulfills the assessment requirements for highly contaminated soil. To compare the measurement of PAHs and their uptake by earthworms (Eisenia fetida), experiments were conducted using four different soils with varying properties. The desorption kinetics data obtained from these experiments demonstrated that the capability of the MSPE in accurately predicting the bioavailable portions of PAHs. After a 28-day exposure, the best predictor of bioavailable PAHs in earthworms was MSPE method exhibited the highest correlation coefficient (R2 > 0.90), and its slopes in the four soils were 0.972, 0.961, 1.012, and 0.962, respectively, all close to 1. These results demonstrate that the MSPE method successfully mimics the conditions encountered in soil-earthworm systems and effectively assess bioaccessibility of PAHs in soils.

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Plastic pollution control, involving the whole life cycle management of plastic production, consumption, sorting, recycling, and disposal, has become necessary for global sustainable development. Research on public attitudes is vital to understanding whether plastic pollution control policies are being successfully implemented and the degree to which the public is involved. However, few studies have assessed public attitudes toward plastic pollution control from the whole life cycle perspective, especially using big data. Based on China's whole life cycle management policy of plastics, this study collected more than 200,000 relevant comments and user information from Sina Weibo to analyze and evaluate public attitudes and opinions toward plastic pollution control. Spatial-temporal analysis was conducted to discover the regional and temporal differences in public attention. Using a sentiment classification method based on semantic analysis, the emotional tendencies of the public attitudes toward ten subdivided plastic pollution control links were studied. It was found that more people held a positive attitude and paid more attention to reusing and sorting links, while the negative emotions were concentrated on the collection and sorting links. Using a topic modeling method, the negative opinions in various links were revealed, such as lack of supervision and industry standards; over packaging or insufficient packaging; food safety problems caused by the reuse; high costs, poor use and possibly greater waste of substitutes; unclear sorting rules and insufficient supporting measures. Graph theory was applied to display these opinions. Finally, some policy implications derived from the discussions are given.

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The rapid determination of the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils is challenging due to their slow desorption rates and the insufficient extraction efficiency of the available methods. Herein, magnetic poly(ß-cyclodextrin) microparticles (Fe3O4@PCD) were combined with hydroxypropyl-ß-cyclodextrin (HPCD) or methanol (MeOH) as solubilizing agents to develop a rapid and effective method for the bioaccessibility measurement of PAHs. Fe3O4@PCD was first validated for the rapid and quantitative adsorption of PAHs from MeOH and HPCD solutions. The solubilizing agents were then coupled with Fe3O4@PCD to extract PAHs from soil-water slurries, affording higher extractable fractions than the corresponding solution extraction and comparable to or higher than single Fe3O4@PCD or Tenax extraction. The desorption rates of labile PAHs could be markedly accelerated in this process, which were 1.3-12.0 times faster than those of single Fe3O4@PCD extraction. Moreover, a low HPCD concentration was sufficient to achieve a strong acceleration of the desorption rate without excessive extraction of the slow desorption fraction. Finally, a comparison with a bioaccumulation assay revealed that the combination of Fe3O4@PCD with HPCD could accurately predict the PAH concentration accumulated in earthworms in three field soil samples, indicating that the method is a time-saving and efficient procedure to measure the bioaccessibility of PAHs.

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ß-Cyclodextrin (ß-CD) is an inexpensive and reproducible material derived from corn starch. It is possible that tetrafluoroterephthalonitrile-crosslinked ß-cyclodextrin polymer (TFN-CD), a cheap but efficient adsorbent, could be a suitable binding agent for use in the passive sampling technique, diffusive gradients in thin-films (DGT). Herein, the TFN-CD binding gel was prepared and then evaluated as the binding phase of DGT to sample six endocrine disrupting chemicals (EDCs) in water. The TFN-CD dispersed uniformly in the binding gel due to its hydrophilicity. The quantitative recoveries (99.3%-106%) of EDCs from the TFN-CD binding gel could be conveniently achieved by ultrasonic extraction using 5 mL methanol for 10 min. Compared with the excellent HLB (hydrophilic-lipophilic-balanced resin) binding gel, the TFN-CD binding gel had comparable or even faster adsorption kinetics, although the equilibrium adsorption capacity was slightly lower. The effective adsorption capacities of TFN-CD-based DGT (TFN-CD-DGT) were roughly estimated to enable a 7-days deployment in EDC solution of 25.7-30.0 µg L-1. Studies of influencing factors showed that the ionic strength (0-0.5 M), pH (3.73-9.13), dissolved organic matter (0-20 mg L-1) and long-term storage (204 days) had negligible influence on the performance of TFN-CD-DGT. Finally, the TFN-CD-DGT was successfully used to record sudden increases in bulk concentrations during simulated discharge events in pond water. These results demonstrate that TFN-CD is a suitable binding agent for sampling of EDCs, and the low cost of TFN-CD could be conducive to the application of DGT in large-scale sampling.

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Exploring commercial and inexpensive sorbents for extraction of organic pollutants is still an active area of research. Ultrahigh molecular weight polyethylene sieve plate (UMPESP) is a commercially available, low-cost, and porous frit, which has been widely used in solid-phase extraction cartridges to fix the filling materials. In this work, UMPESP was investigated for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water samples. The desorption and sorption efficiencies of UMPESP were first evaluated and compared with two previously reported sorbents, low-density polyethylene plastic pellet (LDPEP) and silicone rod (SR). The comparative results showed that quantitative desorption of analytes from UMPESP, which could be easily achieved with 2 × 1.5 mL n-hexane, was more effective than that of LDPEP (>6 × 1.5 mL n-hexane) and comparable to that of SR. Additionally, shorter equilibrium time was rendered by UMPESP (shaking for 120 min) compared with SR (>480 min), due to the porous structure and larger surface area of the former. Different parameters that affect the extraction efficiency, including organic modifier, ionic strength, and pH value, were then studied. The optimized method coupled with gas chromatography-mass spectrometry afforded good linearity in a concentration range of 10-5000 ng L-1 (except acenaphthene in the range of 25-5000 ng L-1) with coefficients of determination ranging from 0.9957 to 0.9995 and relative standard deviations below 13.8%. The limits of detection and quantification were 0.04-3.35 ng L-1 and 0.13-11.16 ng L-1, respectively. Finally, the method was successfully applied to determine PAHs in real water samples, and the results showed no statistically significant difference with the concentrations derived from liquid-liquid extraction.

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Chemical methods used to predict the bioaccessibility of hydrophobic organic compounds (HOCs) still need further development and improvement. In this work, magnetic solid-phase extraction (MSPE) based on poly(ß-cyclodextrin)-coated magnetic polydopamine (Fe3O4@PDA@PCD) was first introduced to assess the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils. Due to its good hydrophilicity and submicrometer scale, Fe3O4@PDA@PCD displayed a higher extraction rate for PAHs in an aqueous solution (equilibrium time < 5 min) than Tenax resin, which had an equilibrium time longer than 30 min. The merits of Fe3O4@PDA@PCD are beneficial to accelerate the desorption of PAHs from soil, especially for high molecular weight PAHs, in which the amounts extracted by Fe3O4@PDA@PCD were 1.2-2.8 times higher than those extracted by Tenax resin. The desorption kinetics data were well fitted with a two- or three-fraction model. The fitting results indicated that the MSPE method can be used to predict the bioaccessible fractions of PAHs. By comparing the prediction results obtained from the MSPE method with bioassays using earthworms, a significant linear correlation (R2 = 0.98) with a slope statistically close to 1 was obtained. These results suggested that the MSPE method can act as a simple and efficient method to measure the bioaccessibility of PAHs in soil.

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Due to the trace levels of polycyclic aromatic hydrocarbons (PAHs) in soil and the complexity of soil matrices, effective sample pretreatment methods are of great significance to obtain accurate analytical results. In this paper, polydopamine (PDA) encapsulated Fe3O4 particles were used as seeds for in situ polymerization of divinylbenzene (DVB) to derive magnetic hybrid material Fe3O4@PDA@PDVB. Coupled with pressurized liquid extraction, Fe3O4@PDA@PDVB was investigated as a selective adsorbent for the extraction and cleanup of PAHs in soil. The prepared magnetic material was characterized and demonstrated to possess strong hydrophobicity and superparamagnetism. Under optimal conditions, Fe3O4@PDA@PDVB can effectively extract 15 PAHs from a 30% methanol solution within 2 min, and it is more selective for PAHs than for n-alkane in soil extracts. The matrix effect significantly decreased after extraction by the prepared material, which showed superiority to a silica gel column method (EPA 3630C Method). The developed method was linear (5-1000 ng g-1) with coefficient of determination (R2) ranging from 0.9986-0.9998, and the limits of detection were 0.13-0.54 ng g-1. Additionally, repetitive experiments indicated that the prepared material was reproducible and reusable with relative standard deviations below 8.4% and 8.6%, respectively. Finally, the new method was successfully employed to determine the concentrations of PAHs in genuine soil and standard reference material, and the results were comparable to those of widely utilized EPA methodology.

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Bioaccessibility measurements of polycyclic aromatic hydrocarbons (PAHs) in soils are significant for exposure risk assessment. The current physicochemical methods require tedious operation processes, underestimate the actual risks, or are unsuitable for high organic content soils. In this work, an efficient and convenient method based on polydopamine-coated polyethylene sieve plate (PDA@PESP) and hydroxypropyl-ß-cyclodextrin (HPCD) was developed to predict the bioaccessibility of PAHs in multi-type soils. The PDA@PESP can be prepared via in situ self-polymerization, allowing to extract PAHs from HPCD solution quantitatively and rapidly. When applied to evaluate the bioaccessibility with PDA@PESP as an adsorption sink and HPCD as a diffusive carrier, the proposed method can significantly improve the extractable fraction of PAHs compared to single HPCD extraction in particular for high organic carbon content soil and high-ring PAHs. The desorption kinetics data indicated that the method can predict the bioaccessible fraction of PAHs. In addition, the method predicted a satisfactory accumulation into earthworms (Eisenia fetida) with a slope statistically approximated to 1. A highly significant linear regression (R2 = 0.95) was also found between the proposed method and Tenax desorption in historically contaminated soils, demonstrating that the method is an efficient and convenient approach for the bioaccessibility prediction of PAHs in soils.

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A new application of MOFs as adsorbents in the cleanup procedure of polycyclic aromatic hydrocarbons (PAHs) in soils was explored. Four MOFs, specifically MIL-101(Cr), MIL-125(Ti), MIL-100(Fe) and UiO-66(Zr), were synthesized and characterized. A screening study was carried out to select the best adsorbent for the purification of sixteen PAHs in complex soil extract. It is found that the nature of metal ion, pore size, surface area and surface charge affect the purification efficiencies of the various MOFs. MIL-101(Cr) was then selected because of its best purification efficiency. The effects of amount of adsorbent, cleanup solvent and cleanup time on cleanup efficiency were investigated. Under the optimum conditions, the matrix effect of the target analytes was reduced by more than 65%. The method was then combined with ultrasonic extraction and quantitation by gas chromatography with triple quadrupole mass spectrometric detection. The method allows for the determination of PAHs in soils with linear in the range of 5-5000 ng g-1 and with LODs between 50 and 420 pg g-1. The method was applied to the analysis of (spiked) soil samples, and results compared well with the established EPA method. Graphical abstract Schematic presentation of metal organic frameworks (MOF) as cleanup adsorbents for purifying polycyclic aromatic hydrocarbons in soil organic matter (SOM) and further determined by gas chromatography with triple quadrupole mass spectrometry detection (GC-MS/MS).

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Accurate analysis of polycyclic aromatic hydrocarbons (PAHs) in soils remains a challenge due to the complexity of sample matrices. In this paper, phenyl-modified magnetic mesoporous silica (Fe3O4@mSiO2-Ph-PTSA) was synthesized with p-toluenesulfonic acid (PTSA) as the catalyst and used as a selective adsorbent for the clean-up of PAHs extracted from soils. The material prepared without PTSA as the catalyst (Fe3O4@mSiO2-Ph) was synthesized for comparison. The synthesized materials were first systematically characterized and evaluated. It was found that the grafting amount of the phenyl group onto Fe3O4@mSiO2-Ph-PTSA was higher than that onto Fe3O4@mSiO2-Ph. The extraction efficiency obtained by extracting PAHs from the extracted soil matrix solution demonstrated that Fe3O4@mSiO2-Ph-PTSA possessed a much higher extraction efficiency than that of Fe3O4@mSiO2-Ph, which can be attributed to the greater amount of phenyl groups grafted on Fe3O4@mSiO2 in the presence of the PTSA catalyst. Moreover, contrast experiments showed that Fe3O4@mSiO2-Ph-PTSA displayed higher selectivity towards PAHs than towards n-alkanes and that the π-π interaction played a key role in the adsorption process. In the presence of the soil extract matrix, the parameters affecting the extraction efficiency of Fe3O4@mSiO2-Ph-PTSA for PAHs were optimized. Under the optimal conditions, coupled with pressurized liquid extraction and gas chromatograph-mass spectrometer, the proposed method for the determination of PAHs in soils was linear in the range of 5-500 ng g-1, and the correlation coefficients (R) ranged between 0.9994 and 0.9999. The limits of detection (LODs) and limits of quantification (LOQs), which were based on signal-to-noise ratios of 3 and 10, respectively, were in the range of 0.07-0.41 ng g-1 and 0.24-1.37 ng g-1. The developed method displayed a better clean-up effect than that for silica gel column method, and the matrix effect markedly decreased compared to that of the uncleaned condition. Finally, the developed method was successfully applied for the detection of PAHs in environmental soils, and the data were consistent with the results obtained by the silica gel column method. The analytical results were also consistent with those for the real environment.

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A time-saving method was applied to synthesize methyltrimethoxy-modified magnetic mesoporous silica with or without p-toluenesulfonic acid as the catalyst for magnetic solid-phase extraction. The synthesized materials were systematically characterized. Results demonstrated that methyltrimethoxy modified magnetic mesoporous silica with p-toluenesulfonic acid as the catalyst has a relatively smaller aperture and extreme hydrophobicity (water contact angle of 135°). To evaluate the feasibility of these prepared materials as effective adsorbents, it was combined with gas chromatography and electron capture detection to determine 26 polychlorinated biphenyls in environmental water. The result revealed that methyltrimethoxy modified magnetic mesoporous silica with p-toluenesulfonic acid as the catalyst had the best extraction efficiency and recovery. Under the optimized extracted conditions, the proposed method showed good linearity within the concentration range of 5 to 200 ng/L with correlation coefficients of 0.9969 to 0.9999. The limits of detection and quantification based on signal-to-noise ratios of 3 and 10 were in the range of 0.16 to 0.91 and 0.52 to 3.0 ng/L, respectively. The polychlorinated biphenyl concentrations in environmental water samples were successfully determined using the developed method. PCB008 and PCB110 were 4.05 and 8.52 ng/L in Red-Star lake water (Hubei Province, China), respectively.

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A novel amino-functionalized magnetic silica (Fe3O4@SiO2-NH2) was easily prepared via a one-step method integrating the immobilization of 3-aminopropyltriethoxysilane with a sol-gel process of tetraethyl orthosilicate into a single process. This showed significant improvement in the adsorption capacity of anionic dyes. The product (Fe3O4@SiO2-NH2) was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray spectrometry, zeta potential and vibrating sample magnetometry. The adsorption performance of Fe3O4@SiO2-NH2 was then tested by removing acid orange 10 (AO10) and reactive black 5 (RB5) from the aqueous solutions under various experimental conditions including initial solution pH, initial dye concentrations, reaction time and temperature. The results indicated that the maximum adsorption capacity of AO10 and RB5 on Fe3O4@SiO2-NH2 was 621.9 and 919.1 mg g-1 at pH 2, respectively. The sorption isotherms fit the Langmuir model nicely. Similarly, the sorption kinetic data were better fitted into the pseudo-second order kinetic model than the pseudo-first order model. In addition, the thermodynamic data demonstrated that the adsorption process was endothermic, spontaneous and physical. Furthermore, Fe3O4@SiO2-NH2 could be easily separated from aqueous solutions by an external magnetic field, and the preparation was reproducible.

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Alkyl moieties which can retain target analytes due to their lipophilicity are important in sample preparation. In this work, hexadecyl-functionalized magnetic core-shell microspheres (Fe3O4@SiO2-C16) was successfully prepared by one-pot sol-gel method and used for magnetic solid-phase extraction of polychlorinated biphenyls (PCBs) in environmental water samples. Optimized preparation method was achieved by altering the adding moment of hexadecyl-silane. The resultant materials were systematically characterized by scanning electron microscope, transmission electron microscope, Fourier transform infrared spectroscopy, energy dispersive X-ray spectrometry, tensionmeter, and vibrating sample magnetometer. The results demonstrated that the optimized adsorbent exhibited core-shell structure, superparamagnetic (66 emu/g), and extremely hydrophobic (water contact angle of 122°) properties. To evaluate the extraction performance, the prepared material coupled with gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) was applied to determinate PCBs. The extraction conditions were optimized. Under the optimal conditions, the proposed method showed a good linearity range of 1-100 ng L-1 with correlation coefficients (R) of 0.9989-0.9993. Based on a signal-to-noise ratio of 3 and 10, the limits of detection (LODs) and limits of quantification (LOQs) were in the range 0.14-0.27 and 0.39-0.91 ng L-1, respectively. The intra- and inter-day relative standard deviations (RSDs) were less than 9.06%. The absolute recoveries of PCBs in spiked real water samples were in the range of 75.17 to 101.20%. Additionally, reusability and batch-to-batch reproducibility of the resultant material were acceptable with RSDs less than 5.64 and 3.25%, respectively. Graphical Abstract The synthesis procedure of Fe3O4@SiO2-C16 and determination of PCBs in water sample 129 × 50 mm (300 × 300 DPI).

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N-nitrosamines are trace organic contaminants of environmental concern when present in groundwater and river water due to their potent carcinogenicity. Therefore, N-nitrosamine analysis is increasingly in demand. Gas chromatography-mass spectrometry (GC-MS) and GC-tandem mass spectrometry (GC-MS/MS), both with electron ionization (EI), were compared for analysis of nine N-nitrosamines extracted from environmental water matrices. A total of 20 fishpond water, river water, and groundwater samples from Sihui and Shunde, China were collected for a survey of N-nitrosamine concentrations in real water samples. Various solid-phase extraction (SPE) conditions and GC conditions were first examined for the pre-concentration and separation steps. The analysis of N-nitrosamines in environmental waters demonstrated that their quantification with GC-MS poses a challenge due to the occurrence of co-eluting interferences. Conversely, the use of GC-MS/MS increased selectivity because of the fragmentation generated from precursor ions in the 'multiple reaction monitoring' (MRM) mode, which is expected to extract target analytes from the environmental water matrix. Thus, the high performance of GC-MS/MS with EI was used to quantify nine N-nitrosamines in environmental waters with detection limits of 1.1-3.1 ng L-1. N-nitrosodimethylamine (NDMA) concentrations were in the range of N.D. to 258 ng L-1. Furthermore, other N-nitrosamines, except N-nitrosomethylethylamine (NMEA), N-nitroso-di-n-propylamine (NDPA) and N-nitrosopiperidine (NPIP), were also detected. Our findings suggest that GC-MS/MS with EI would be widely applicable in identifying N-nitrosamines in environmental waters and can be used for routine monitoring of these chemicals.

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Selective and effective enrichment of phosphopeptides from complex samples is essential in phosphoproteome study by mass spectrometry (MS). In this work, we compared perovskites (MgTiO3, CaTiO3, SrTiO3, BaTiO3 and CaZrO3) with metal oxides (ZrO2 and TiO2) in their capability for the selective enrichment of phosphopeptides. It was found here that perovskites exhibited higher selectivity towards phosphopeptides than commonly used ZrO2 and TiO2, even though they all have high affinity to phosphopeptides. As for perovskites, CaTiO3 exhibited better selectivity for enrichment of phosphopeptides than SrTiO3, MgTiO3, BaTiO3 and CaZrO3, which might be ascribed to their crystal structures and electrophilic abilities. Moreover, to further confirm the performance of CaTiO3, CaTiO3 and TiO2 were applied to the enrichment of phosphopeptides from tryptic digest of proteins of human Jurkat-T cell lysate, respectively. The results showed CaTiO3 has much higher selectivity than TiO2 in the enrichment of phosphopeptides from the complex biological sample. Taken together, here we show that CaTiO3 is an excellent material for the highly selective enrichment of phosphopeptides and it could be potentially used in the large-scale phosphoproteome study.

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As one of the most important types of post-translational modifications, reversible phosphorylation of proteins plays crucial roles in a large number of biological processes. However, owing to the relatively low abundance and dynamic nature of phosphorylation and the presence of the unphosphorylated peptides in large excess, phosphopeptide enrichment is indispensable in large-scale phosphoproteomic analysis. Metal oxides including titanium dioxide have become prominent affinity materials to enrich phosphopeptides prior to their analysis using liquid chromatography-mass spectrometry (LC-MS). In the current study, we established a novel strategy, which encompassed strong cation exchange chromatography, sequential enrichment of phosphopeptides using titania-coated magnetic mesoporous hollow silica microspheres (TiO2/MHMSS) and zirconium arsenate-modified magnetic nanoparticles (ZrAs-Fe3O4@SiO2), and LC-MS/MS analysis, for the proteome-wide identification of phosphosites of proteins in HL60 cells. In total, we were able to identify 11,579 unique phosphorylation sites in 3432 unique proteins. Additionally, our results suggested that TiO2/MHMSS and ZrAs-Fe3O4@SiO2 are complementary in phosphopeptide enrichment, where the two types of materials displayed preferential binding of peptides carrying multiple and single phosphorylation sites, respectively.

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A novel strategy for the effective enrichment of phosphopeptides based on magnetic hydro-xyapatite (HAp) clusters was developed in the current study. The structure of HAp ensures its probable separation capability, including cation exchange with P-sites (negatively charged pairs of crystal phosphates), calcium coordination, anion exchange with C-sites (positively charged pairs of crystal calcium ions). The prepared magnetic HAp clusters showed good performance on the efficient enrichment of phosphopeptides from the digestion mixture of ß-casein and BSA. Compared to commercial HAp particles, the magnetic HAp clusters exhibited better selectivity toward phosphopeptides. In addition, the use of magnetic material greatly simplified the enrichment procedure, which avoided the tedious centrifugation steps in a typical phosphopeptides enrichment protocol. Finally, the material was successfully applied in the enrichment of phosphopeptides from human serum. Taken together, the efficient enrichment of the phosphopeptides by the easily prepared magnetic HAp clusters demonstrated a rapid and convenient strategy for the purification of phosphopeptides from complex samples, which may facilitate protein phosphorylation studies.

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Mesoporous silica embedded pipette tips (mSiO2-Tips) were successfully prepared by a simple method and applied to rapid enrichment of endogenous peptides for the first time. The prepared mSiO2-Tips showed low back pressure when solvent was pipetted up and down. As a result, mSiO2-Tip could selectively trap peptides and exclude high-MW proteins simultaneously based on size-exclusion mechanism due to the uniform mesopore structure of the sorbent bed. The in-pipette-tip SPE approach was proved to be easy-operation, sensitive and fast (less than 2 min) for the analysis of peptides, which was further successfully applied in the efficient enrichment of peptides from human plasma.

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