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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Ultrasensitive and Green Bubbling Extraction Strategies: An Extensible Solvent-Free Re-Enrichment Approach for Ultratrace Pollutants in Aqueous Samples

Yuanji Gao,Hongru Feng,Bing Xia,Lei He,Congling Yang,Lijuan Zhao,Yuanjiang Pan

Ultratrace organic pollutants in the environment pose severe threats to human health; hence, their accurate detection is essential. In this study, we develop a secondary solvent-free enrichment strategy based on bubbling extraction (BE). Especially, we used BE solid-phase microextraction and BE carbon nanotube paper absorption to capture aerosols from a liquid water surface, desorb analytes, and analyze the analytes using mass spectrometry. The application of a solvent-free enrichment strategy helps overcome technical challenges in implementing BE technology, including reproducibility, quantification, and sensitivity. This approach objectively demonstrates the enrichment efficiency of BE, resulting in improved mass spectrometry response and quantification. It effectively tackles the difficulties in detecting and quantifying ultratrace environmental pollutants in mass spectrometric analysis. The present study successfully conducted a quantitative analysis of 16 polycyclic aromatic hydrocarbons and 7 antibiotics in 48 environmental water samples. This strategy proved effective in detecting the presence and distribution of polar and nonpolar environmental pollutants in rivers and lakes. Moreover, this strategy has several advantages, such as ultrahigh sensitivity at the femtograms per liter level, good greenness, multiplexed quantitation, low sample consumption, and ease of operation. Overall, the utilization of the ultrasensitive and environmentally friendly BE approach presents a reliable and adaptable method for the identification of ultratrace environmental pollutants in water specimens, thereby enabling early monitoring of pollutant levels.

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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Biochar nanosphere- and covalent organic framework nanosphere-functionalized titanium dioxide nanorod arrays on carbon fibers for solid-phase microextraction of organic pollutants

Mingxia Sun,Juanjuan Feng,Jiaqing Feng,Haili Sun,Yang Feng,Xiangping Ji,Chunying Li,Sen Han,Min Sun

To improve the extraction efficiency of carbon fibers (CFs) toward organic pollutants, TiO 2 nanorod arrays (NARs) were grown in situ on CFs. Subsequently, biochar nanospheres and covalent organic framework nanospheres were separately introduced to functionalize the NARs. A sequence of materials was produced by regulating the reactant concentrations and characterized using a scanning electron microscope, an X-ray photoelectron spectrometer, an X-ray diffractometer, a Raman spectrometer, and a specific surface area analyzer. The materials were then deposited into separate poly(etheretherketone) tubes for in-tube solid-phase microextraction (IT-SPME). These tubes were evaluated with different types of organic pollutants (polycyclic aromatic hydrocarbons (PAHs), estrogens, bisphenols, and phthalate esters) using a combination of high-performance liquid chromatography and IT-SPME, and they exhibited diverse extraction performance. The extraction mechanism of each material is carefully discussed, and the structure–performance relationship is also summarized based on the chemical structures and extraction properties of the materials. The most efficient extraction materials for different analytes were discovered and used to develop analytical methods. Three online methods were used to sensitively detect PAHs, estrogens, and bisphenols in real water samples, respectively. Satisfactory results were obtained, including enrichment factors up to 6784, detection limits as low as 0.001 μg L −1 , linear ranges of 0.003–15.0 μg L −1 , and relative standard deviations ranging from 0.2% to 15.2%. The results indicate that these methods have some advantages over previous material-based methods.

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Arabian Journal of Chemistry · 2021 · IF 5.165

Carbon fibers modified with carbon nanoparticles by a facile and fast flame preparation for in-tube solid-phase microextraction

Qiong Jiang,Juanjuan Feng,Min Sun

Carbon fibers (CFs) were modified with carbon nanoparticles (CNPs) by a facile and fast flame preparation method. CNPs-CFs were observed by scanning electron microscope, and the nano-scaled granular structure on the surface was found. This material was also characterized by Raman microscope and X-ray photoelectron spectroscope. It was placed into a polyetheretherketone tube to get an extraction tube, which was connected with high performance liquid chromatography for online analysis. The tube displayed the effective extraction to several polycyclic aromatic hydrocarbons (PAHs), based on the possible hydrophobic and π stacking mechanism. Under the optimized conditions (60 mL of sample volume, 2.00 mL min −1 of sample rate, 0.5% of methanol in sample, 2.0 min of desorption time), an analytical method towards these PAH targets was established. The low limits of detection (0.001–0.005 μg L −1 ), satisfactory linear ranges (0.003–5.0 μg L −1 , 0.003–10.0 μg L −1 ) and efficient enrichment factors (1012–3164) were presented. The method was applied to detect trace targets in several water samples and satisfactory results were obtained. The method provided some superiorities over other analytical methods, like online test, shorter time and better sensitivity.

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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Rapid and sensitive screening of multiple polycyclic aromatic hydrocarbons by a reusable fluorescent sensor array

Linfeng Chen,Xike Tian,Yong Li,Chao Yang,Yunjie Huang,Yulun Nie

Simple and rapid sensing of polycyclic aromatic hydrocarbons (PAHs) remains a great technical challenge due to their chemical stability and structural similarity. Here, a simple, sensitive and cost-effective sensing strategy is proposed to detect multiple PAHs by utilizing the inner filter effect (IFE) and a reusable fluorescent sensor array consisting of four polyvinyl alcohol (PVA) composite carbon quantum dots (CDs) film sensors. The CDs/PVA films have a wide and tunable excitation range, which provide sufficient spectral overlap with PAHs and ensure the efficient occurrence of IFE. Under different excitations, the diverse UV absorption capacities of PAHs resulted in diverse spectral responses , enabling a unique chemical fingerprint for each PAH. Upon multivariate pattern recognition analysis, the array rendered high-throughput discrimination and sensitive quantification of 16 priority PAHs with 100% classification accuracy and detection limit as low as 57 nM. Moreover, the rapid and accurate screening of multiple environmental samples were also realized with the results consistent with high-performance liquid chromatography . This IFE-based reusable array is readily prepared, green and feasible, which exhibits great potential in environmental analysis and brings an advanced strategy to high-throughput sensing of more pollutants with similar structures and lack of recognition sites.

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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2021 ·Vol. 29 ·期 17 ·24612-24622 · IF 4.223

Characteristics and sources of environmentally persistent free radicals in PM2.5 in Dalian, Northeast China: correlation with polycyclic aromatic hydrocarbons

Li Zhansheng,Zhao Hongxia,Li Xintong,Bekele Tadiyose Girma

Environmentally persistent free radicals (EPFRs) are an emerging class of environmental hazardous contaminants that extensively, stably exist in airborne particulate matter and pose harmful effects on human health. However, there was little research about the sources of EPFRs in actual atmospheric conditions. This study reported the occurrence, characteristics, and sources of EPFRs and polycyclic aromatic hydrocarbons (PAHs) in PM 2.5 collected in Dalian, China. The concentrations of PM 2.5 -bound EPFRs ranged from 1.13 × 10 13 to 8.97 × 10 15 spins/m 3 (mean value: 1.14 × 10 15 spins/m 3 ). Carbon-centered radicals and carbon-centered radicals with adjacent oxygen atoms were detected. The concentration of ∑PAHs ranged from 1.09 to 76.24 ng/m 3 , and PAHs with high molecular weight (HMW) were predominant species in PM 2.5 . Correlation of EPFRs with SO 2 , NO 2 , O 3 , and 12 kinds of PAHs indicated that both fuel (coal and biomass) combustion and photoreaction in atmosphere influenced the concentrations of EPFR. The positive matrix factorization (PMF) model results have shown that the primary sources contributed most of the EPFRs and those of secondary sources had a little proportion. Coal combustion (52.4%) was the primary contributor of EPFRs, followed by traffic emission (22.6%), industrial sources (9.6%), and secondary sources (9.2%) during the heating period, whereas industrial emission (39.2%) was the primary contributor, followed by coal combustion (38.1%), vehicular exhaust (23.5%), and secondary sources (9.6%) during the non-heating period. The finding of the present study provides an important evidence for further study on the formation mechanism of EPFRs in actual atmospheric to control the air pollution.

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MICROCHIMICA ACTA · 2018 ·Vol. 185 ·期 9 ·1-10 · IF 5.705

A polymer monolith incorporating stellate mesoporous silica nanospheres for use in capillary electrochromatography and solid phase microextraction of polycyclic aromatic hydrocarbons and organic small molecules

Zhou Xiu-Jie,Zhang Li-Shun,Song Wen-Fang,Huang Yan-Ping,Liu Zhao-Sheng

An inorganic-organic hybrid monolith incorporated with stellated mesoporous silica nanoparticles (SMSNs) was prepared. Using binary solvents, deep eutectic solvents and room temperature ionic liquids, an SMSN-incorporated poly(butyl methacrylate- co -ethylene glycol dimethacrylate) monolith demonstrated uniform structure with good column permeability. A systematic investigation of preparation parameter was performed, including SMSN content, crosslinking monomer content, and the component of binary solvent. The optimized monoliths were characterized by field emission scanning electron microscopy, transmission electron microscopy, area scanning energy dispersive spectrometry, and nitrogen adsorption. Column performance was tested by separating four groups of analytes (alkylbenzenes, anilines, naphthalenes and phenols) by capillary electrochromatography (CEC). Baseline separation of all analytes was obtained with column efficiencies of up to 266,000 plates m −1 . The performance of the resulting monolith was further investigated in detail by separating mixtures of polycyclic aromatic hydrocarbons (PAHs), nonsteroidal antiinflammatory drugs (NSAIDs), and hydroxybenzoic acid isomers. Compared with the corresponding SMSN-free monolith, the CEC performance was improved by about six times. Successful extraction of PAHs and quinolones (QNs) were also performed using this capillary. Improved extraction efficiency (20.2%) for complex samples, lake water, was also found when the material was applied to solid phase microextraction of fluoranthene. A poly(butyl methacrylate-co-ethylene glycol dimethacrylate) monolith incorporated with stellated mesoporous silica nanoparticles was prepared. It demonstrated column efficiency up to 266,000 plates m −1 in capillary electrochromatography and ability as solid phase microextraction for organic small molecules with good column permeability.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2023 · IF 4.3

Nanoleaf-derived carbon materials as a sensitivity coating for solid‑phase microextraction of polycyclic aromatic hydrocarbons

Hu Xingru,Pang Long,Wu Mingkai,Wang Chaohai,Li Jiansheng

Metal–organic framework-derived carbon materials have shown extensive application in the sensitive extraction of polycyclic aromatic hydrocarbons (PAHs), but more active sites for its adsorption were still a tireless pursuit. In this study, ZIF-nanoleaf-derived carbon (NLCs) was synthesized and developed as a solid-phase microextraction (SPME) fiber (NLCs-F). The extraction performance was compared with ZIF-dodecahedron-derived carbon (DHCs) coated fiber (DHCs-F), which was prepared by only changing the ratio of the reactants. The unique morphology of NLCs provided abundant adsorption active sites for the selected PAHs, while the large average aperture facilitated selective extraction of high molecular weight analytes. Additionally, the high carbon content enhanced the strong enrichment capability for hydrophobic PAHs. Hence, the prepared NLCs-F coupled with GC–MS showed a good correlation coefficient (0.9975) in a wide linear range, low limits of detection (0.3–1.8 ng L −1 ), satisfactory repeatability, and reproducibility, which made it apply in the enrichment of PAHs in actual tea and coffee samples. Graphical abstract

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Arabian Journal of Chemistry · 2023 · IF 6

Theoretical insight and experimental exploration of indole extraction from wash oil with deep eutectic solvents

Lan Yi,Xiaoqin Wu,Shuguang Ouyang,Li Guo,Jialing Chen,Mario Gauthier,Wen-Ying Li

The extraction of indole from wash oil is of economic value and practical significance. In this study, deep eutectic solvents (DESs) are investigated to extract indole from wash oil. Initially, density functional theory calculations were used to explore the association of indole with aromatic compounds in wash oil, and the feasibility of indole extraction with a tetraethylammonium chloride/ p -toluenesulfonic acid (TEAC/2TsOH) DES. Then, the influence of the temperature, stirring time, DESs dose, initial indole concentration, and amount of water added were investigated, followed by discussions on the comparison with other extractants and the performance of extracting of indole from real wash oil. The results show that indole associates with aromatic compounds in wash oil through π−π interactions, but that a large electrostatic interaction energy of −52.8 kJ/mol between indole and the DESs is the main driving force for the extraction process. Under optimal conditions, TEAC/2TsOH extracts more than 63.5 ± 3% of indole from wash oil, and its extraction capacity is superior to other extractants.

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JOURNAL OF MOLECULAR LIQUIDS · 2024 · IF 5.3

Mechanism exploration of deep eutectic solvents extraction of indole in wash oil

Lan Yi,Zhihao Cheng,Shisen Lv,Hao Luo,Jialing Chen,Li Guo,Xiaoqin Wu,Wen-Ying Li

Deep eutectic solvents (DESs) have gained significant interest for extracting indole from wash oil due to their exceptional characteristics and excellent extraction performance. An in-depth comprehension of the intermolecular interactions within the DES-wash oil system is crucial for developing principles that can guide the design of highly efficient DESs for indole extraction. The intermolecular interactions, molecular associations , and density profile in the DES-wash oil system were investigated using molecular dynamics simulation and FT-IR/ 1 H NMR characterization. The DES was composed of tetraethylammonium chloride and glycerol (TEAC/GLY), which was selected based on its exceptional experimental performance. Both the simulation and spectra results show that indole has strong hydrogen bond with TEAC/GLY. The hydrogen bond promotes indole extraction while van der Waals interactions cause aromatics entrainment. The components in wash oil exhibit two distinct molecular associations before and after the extraction of indole. A well-defined interface is established between the wash oil molecules and DES components, and indole has a preference for accumulating at the interface. The results provide an insight into the mechanism of extracting indole from wash oil using DES .

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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Graphene oxide-functionalized mesoporous silica for online in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons from honey and detection by high performance liquid chromatography-diode array detector

Min Sun,Sen Han,Herman Maloko Loussala,Juanjuan Feng,Chunying Li,Xiangping Ji,Jiaqing Feng,Haili Sun

In order to develop an online detection method for polycyclic aromatic hydrocarbons (PAHs) in honey, graphene oxide-functionalized mesoporous silica was prepared and introduced as the coating in the field of in-tube solid-phase microextraction. An extraction tube was coupled to high performance liquid chromatography with diode array detector, and the online analytical system was constructed. After the main extraction and desorption conditions were optimized, a sensitive and online method based on matrix-matched calibration was established towards trace PAHs in honey. The method exhibited wide linear range from 0.8 ng g −1 to 250 ng g −1 and low detection limit of 0.25 ng g −1 , and the enrichment effect reached 2719. The proposed method was validated and successfully applied to the analysis of six honey samples. The extraction tube showed good durability and acceptable chemical stability during the experiment.

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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Porphyrin-based covalent organic framework coated stainless steel fiber for solid-phase microextraction of polycyclic aromatic hydrocarbons in water and soil samples

Chen Yu,Fengshou Wu,Xiaogang Luo,Juan Zhang

A porphyrin-based covalent organic framework (COF) was synthesized via a Schiff base reaction between tetra (4-aminophenyl) porphyrin and 4,4′-biphenyldicarboxaldehyde. The porphyrin-based COF was physically coated on stainless steel for headspace solid-phase microextraction (HS-SPME) of polycyclic aromatic hydrocarbons (PAHs) prior to their determination by gas chromatography-flame ionization detection (GC-FID). Some properties of the prepared fiber like morphology, structure and stability were tested. The effective parameters including extraction temperature, extraction time, NaCl concentration, agitation speed, desorption temperature and desorption time on the performance by HS-SPME were optimized systematically. The study of extraction mechanism revealed the π-π stacking interaction between porphyrin-based COF fiber and PAHs. Under optimum condition of the developed method, a wide linear range (1–150 ng mL −1 ) with high determination coefficient (R 2  > 0.99), low detection limit (0.25 ng mL −1 ) and low quantitation limit (0.5 ng mL −1 ) were obtained. The repeatability (one fiber, n = 3) and the reproducibility (fiber-to-fiber, n = 3) expressed as the relative standard deviations (RSDs) were in the range of 0.27%–1.75% (intra-day), 2.73%–6.69% (inter-day) and 3.34%–8.62% (fiber-to-fiber), respectively. The developed porphyrin-based COF HS-SPME method had been applied for the determination of PAHs in water and soil samples with satisfactory recoveries in the range of 67.87%–98.74%, 41.13%–104.76%, respectively.

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ANALYTICAL CHEMISTRY · 2021 · IF 6.986

Identification, Quantification, and Imaging of the Biodistribution of Soot Particles by Mass Spectral Fingerprinting

Yue Lin,Xiu Huang,Yongchun Liu,Dong Cao,Dawei Lu,Zeming Feng,Qian Liu,Zhenyu Lin,Guibin Jiang

Soot is ubiquitous and has large detrimental effects on climate, air quality, and human health. However, identification of soot in carbonaceous media is very challenging due to its nanoscale carbon nature and complex sources. Due to the shortage in the methodology, until now, the fate and health effect of soot particles after inhalation are still poorly understood. Here, we report a new method for label-free identification, quantification, and imaging of soot particles in complex media based on laser desorption/ionization mass spectrometry fingerprinting. We found that soot particles from different origins and with different morphologies showed highly consistent mass spectral fingerprints deriving from peak ratios of small carbon cluster anions (C2––C10–), which enabled both accurate quantification of soot in fine particulate matter (PM2.5) samples and label-free imaging of soot particles in biological media. By using this technique, we tracked and imaged the suborgan distribution of soot particles in mice after exposure to PM2.5. The results showed that the lung is the main target organ for short-term inhalation exposure to soot particles. This study helps to better understand the inhalation toxicology of soot and also provides a practical novel methodological platform for identification, tracing, and toxicological studies of elemental carbon-based nanomaterials.

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