Carbon fibers coated with covalent organic framework for online in-tube solid-phase microextraction of tetrabromobisphenol A derivatives in water

Carbon fibers coated with covalent organic framework for online in-tube solid-phase microextraction of tetrabromobisphenol A derivatives in water | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Carbon fibers coated with covalent organic framework for online in-tube solid-phase microextraction of tetrabromobisphenol A derivatives in water Qiong Jiang, Ziyi Xu, Ting Li, Huixia Zhang, Juanjuan Feng, Min Sun This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7904953/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 09 Apr, 2026 Read the published version in Microchimica Acta → Version 1 posted 9 You are reading this latest preprint version Abstract Tetrabromobisphenol A (TBBPA) derivatives as new pollutants attracted more and more attention. Due to the trace level of TBBPA derivatives or the complex sample matrix, sample pretreatment was often required for sensitive determination. However, sample pretreatment methods including solid-phase extraction, liquid extraction, and fiber solid-phase microextraction were complicated procedures, inefficient, and offline operation with detection techniques. A coating of covalent organic framework (COF) was grown onto carbon fibers (CFs) via a Schiff-based reaction at room temperature. The COF-coated CFs (COF-CFs) were filled into one tube for enriching TBBPA derivatives in water by in-tube solid-phase microextraction (IT-SPME). After the optimization of extraction and desorption factors, online IT-SPME-HPLC-DAD method was developed. The method exhibited a wide linear range (0.167–10.0 µg L⁻¹, 0.33–10.0 µg L⁻¹), and a low detection limit (0.05 µg L⁻¹) resulting from high enrichment factors (936–2187) within 20.0 min. The method was applied in the detection of TBBPA derivatives in water samples, demonstrating good practical applicability. Compared with other analytical methods, the method was simple, efficient, and online operation. The extraction material is expected to capture other pollutants in environmental, food, biological and other fields. Solid-phase microextraction Covalent organic frameworks Tetrabromobisphenol A derivatives High-performance liquid chromatography Online analysis Figures Figure 1 Figure 2 Figure 3 Figure 4 1 Introduction Tetrabromobisphenol A (TBBPA) is one of the most widely employed brominated flame retardant [ 1 ]. To tailor the physicochemical properties or reactivity of the flame retardant, a range of TBBPA derivatives including TBBPA dimethyl ether (TBBPA-DME), TBBPA bis(2-hydroxyethyl ether) (TBBPA-BHEE), TBBPA bis(allyl ether) (TBBPA-BAE), and TBBPA bis(2,3-dibromopropyl ether) (TBBPA-BDBPE), are applied in polymeric materials [ 2 ]. Due to their additive nature rather than covalent bonding to the polymers, they possess a high potential for leaching and migration into the environment water. Owing to their potential as endocrine disruptors, environmental persistence, long-distance migration, and bioaccumulation, the development of robust and sensitive analytical method for TBBPA derivatives in environment water is crucial [ 3 ]. Trace level of targets in the complex matrix of environment water give the challenges. While the sample preparation is often required to improve the sensitivity by removing the matrix interference and enriching the target [ 4 ]. Compared with common solid-phase extraction and liquid-liquid extraction, in-tube solid-phase microextraction (IT-SPME) has more advantages, such as efficient enrichment, free or minimal solvent, automated operation, and excellent compatibility with liquid chromatography. The extraction behavior greatly depends on the sorbent or coating in extraction tube [ 5 – 7 ]. Carbon fibers (CFs) are one special carbon material prized for its exceptional strength, stiffness, and low weight. Its applications are vast and growing in different fields. Although CFs as a sorbent displayed the enrichment potential for hydrophobic analytes in IT-SPME [ 8 ], some faults including low surface area, only hydrophobic and graphitized surface, and less functional groups seriously limited the further application. To solve above issues, some materials containing graphene [ 9 ], biochar nanospheres [ 10 ], carbon nanoparticles [ 11 ], titanium dioxide nanorods [ 12 ], and polyaniline/titanium dioxide nanorods [ 13 ], were used to functionalize CFs, achieving the effective extraction for polycyclic aromatic hydrocarbons and phthalates. Compared with these sorbents, covalent organic frameworks (COFs) are more attractive in sample preparation. Despite a class of highly porous and crystalline materials, COFs are entirely constructed from strong covalent bonds between light organic elements (C, H, O, N, et al.). Besides of gas storage and separation, catalysis, sensing, and energy storage, COFs hold great promise for IT-SPME, due to obvious advantages such as well-defined structures, high surface area, excellent stability, tunable pore size, low density, facile functionalization and so on [ 14 – 16 ]. Based on these considerations, one COF was in-situ grown onto CFs for extracting and detecting TBBPA derivatives by IT-SPME combining with HPLC. The structures and properties of the COF-coated CFs (COF-CFs) were characterized. The polyetheretherketone tube packed with COF-CFs was used as an extraction tube. The tube was connected to HPLC with diode array detection (DAD) to construct an IT-SPME-HPLC-DAD system. After optimizing extraction and desorption conditions, an analytical method was established for detecting trace levels of TBBPA derivatives in water. Subsequently, the method was applied to real water samples to verify its practical feasibility. 2 Experimental Sections 2.1–2.4 materials and reagents, apparatus, chromatographic conditions, and sample preparation were described in Supplementary Materials. 2.5 Material preparation First, 5.0 mg of 1,3,5-tris(4-aminophenyl)benzene (TAPB) was dissolved in 5.0 mL of methanol, and 70.0 cm of CF bundle was completely immersed in the solution. After the mixture was sonicated for 30 min, it was placed in the oven at 65°C for 12 h, to obtain CFs adsorbed with TAPB. Next, 11.0 mg of 1,4-phthalaldehyde and 0.5 mL of 12.0 mol L − 1 HAc were dissolved in 5.0 mL ACN, and TAPB-coated CFs were immersed in this solution. After 48 h at room temperature, the COF-CFs were obtained. Finally, the COF-CFs were loaded into the PEEK tube, to achieve the extraction tube. 3 Results and discussion 3.1 Characterization The microstructures of CFs and COF-CFs are shown in Fig. 1 . The CF had a gully surface, which helps with the adhesion of the coating. There was an uniform coating and the gully structure was weakened on the surface of COF-CFs. The thin coating and high surface area of COF are very conducive to rapid and efficient extraction. The crystal structure and surface area of COF were tested by XRD and BET. As can be seen from the Fig. 2 , there was a diffraction peak at 2.76°, which coincided with the angle of the characteristic peak of the COFs [ 17 ]. Besides, according to the adsorption and desorption curves, the substance conformed to type Ⅱ isotherms. The BET surface area of the substance was 35.33 m 2 g − 1 , and adsorption average pore diameter was 23.52 nm, desorption average pore diameter is 34.64 nm [ 18 ]. The pore size of this material is conducive to the entry of the analytes for full adsorption. 3.2 The improvement of extraction effect by the COF coating In order to display the role of COF coating, COF-CFs-filled tube was compared to the tube filled with only CFs under the same conditions (60.0 mL of sample, 1.5 mL min − 1 of sampling rate, and 2.0 min of desorption). According to the enrichment factors (EFs) of analytes in Table 1 , the introduction of COF coating presented the enhanced effect for capturing three TBBPA derivatives. The COF not only increased the adsorptive sites, but also produced a π-stacking effect with the target in the nanopores. Table 1 Enrichment factors of TBBPA derivatives on two extraction tubes. Analytes Enrichment factors Ratio CFs-filled tube COF-CFs-filled tube TBBPA-DME 145 380 2.62 TBBPA-BDBPE 1238 2191 1.77 TBBPA-BAE 413 477 1.15 3.3 Optimization of extraction and desorption factors When the extraction volume is small, the extraction effect on the target is low. As the extraction volume gradually expands, the peak area often shows a steady increase trend. As shown in Fig. 3 (a), the peak area of the three analytes was positively related with the extraction volume. In view of the detection efficiency and time cost control, 60 mL of extraction volume was finally selected. The flow rate of sample through the extraction tube affects the mass transfer process and extraction time. When the rate is low, the target can be adequately captured. When the sample flows rapidly through the extraction tube, the short test time can be obtained. If the rate is high, the extraction time is short. However, high flow rate often results in the inefficient enrichment of target and the high pressure in the tube. As shown in Fig. 3 (b), the peak area of TBBPA-DME and TBBPA-BDBPE increases with the increase of flow rate, and the peak area of the two analytes at 1.75 mL min − 1 was 2–3 times of that at 0.75 mL min − 1 , while the peak area of TBBPA-BAE presented a slow increase. Considering the extraction time and peak area, 1.50 mL min − 1 was selected as the optimal flow rate. The concentration of organic solvent in sample solution can impact the extraction efficiency of hydrophobic target. In this work, methanol was used to test the effect. As shown in Fig. 3 (c), the peak area of TBBPA-BDBPE and TBBPA-BAE reduced with the raise of methanol concentration, while the peak area of TBBPA-DME increased. Thinking about the reason, the decrease of the extraction ability of COF-CFs towards TBBPA-BDBPE and TBBPA-BAE, giving way to the more adsorption sites for TBBPA-DME. Based on the comprehensive consideration of three analytes, the methanol content of 2.0% (v/v) was finally selected as the optimal organic solvent content. When the desorption time is short, some targets will remain on the surface of sorbent, which affects the result. However, the excessive desorption time is unnecessary. As shown in Fig. 3 (d), TBBPA-BAE shows a steady trend, while the peak area of TBBPA-DME and TBBPA-BDBPE improved first with the increase of desorption time, and then was gradually stabilized after 1.0 min. In view of residual effect, 2.0 min was selected as the optimal desorption time. 3.4 Method evaluation and the application for real samples Under the optimal experimental conditions, an online IT-SPME-HPLC-DAD method was established for three TBBPA derivatives. Analytical linearities, linear coefficients (r), detection limits (LODs), enrichment factors, and repeatability results are summarized in Table 2 . The LOD of TBBPA-DME was 0.1 µg L − 1 , and the LODs of TBBPA-BDBPE and TBBPA-BAE were as low as 0.05 µg L − 1 . The linear range of TBBPA-DME was between 0.33-10.0 µg L − 1 , while the linear ranges of TBBPA-BDBPE and TBBPA-BAE were between 0.167-10.0 µg L − 1 . Their EFs were from 936 to 2187. The RSDs (n = 3) of parallel tests were in the range of 2.5%-4.2%. Based on the above results, the online method was accurate and sensitive for determining TBBPA derivatives. Table 2 Important parameters of the online analytical method for three targets. Analytes Linearities (µg L − 1 ) a LODs (µg L − 1 ) r b EFs Intra-day (RSDs, n = 3) TBBPA-DME 0.33-10.0 0.1 0.996 380 3.7% 2.5% 4.2% TBBPA-BDBPE 0.167-10.0 0.05 0.998 2191 TBBPA-BAE 0.167-10.0 0.05 0.979 477 a LODs, limits of detection, three times the signal-to-noise ratio. b EFs, enrichment factors were confirmed as the ratio of analyte concentration before and after extraction (EF = C SPME /C 0 ). Analytes: 1. TBBPA-DME, 2. TBBPA-BDBPE, 3. TBBPA-BAE. In order to verify the practical application of the method, six common water sources (drinking water, mineral water, tap water, Jiazi lake, Fengxi river, Daming lake.) were selected as real water samples. Furthermore, the method reliability was verified through spiking tests (2.0 and 10.0 µg L − 1 ). As shown in Table 3 and Fig. 4 , these targets were not found in the actual water samples. Specifically, most of the spiked recoveries were lower at a spiked concentration of 10.0 µg L − 1 . Analyzing the reasons, it may be that some impurities occupy the extraction sites, leading to a reduced extraction capacity for the target analytes, and therefore the spiked recoveries were relatively low. Table 3 Determination results and recoveries for TBBPA derivatives in actual samples. Analytes TBBPA-DME TBBPA-BDBPE TBBPA-BAE Drinking water ND ND ND Recoveries (2.0 µg L − 1 , %) 73.6 73.8 114.8 Recoveries (10.0 µg L − 1 , %) 70.9 70.8 87.8 Mineral water ND ND ND Recoveries (2.0 µg L − 1 , %) 121.0 86.8 97.6 Recoveries (10.0 µg L − 1 , %) 94.3 72.6 69.2 Tap water ND ND ND Recoveries (2.0 µg L − 1 , %) 91.8 95.0 145.3 Recoveries (10.0 µg L − 1 , %) 82.1 80.2 83.5 Jiazi lake ND ND ND Recoveries (2.0 µg L − 1 , %) 111.0 89.7 120.9 Recoveries (10.0 µg L − 1 , %) 79.5 80.2 73.4 Fengxi river ND ND ND Recoveries (2.0 µg L − 1 , %) 72.7 70.0 95.5 Recoveries (10.0 µg L − 1 , %) 73.2 88.3 77.6 Daming lake ND ND ND Recoveries (2.0 µg L − 1 , %) 74.8 75.1 101.6 Recoveries (10.0 µg L − 1 , %) 74.2 78.7 82.4 ND: not detected. 3.5 Comparison with other methods In order to comprehensively evaluate the IT-SPME-HPLC-DAD method for the detection of trace TBBPA derivatives in water, the method was compared with other analytical methods. As shown in Table 4 , the LOD (0.05 µg L − 1 ) in this work was lower than that of HPLC-ICP-MS [ 19 ] and SPE-HPLC-MS/MS [ 20 ], and the linear range (0.167-10 µg L − 1 ) was wider than that of SPE-HPLC [ 21 ]. Compared with the MS analysis method [ 19 – 20 , 22 – 25 ], the method was simple operation, less relied on expensive equipment and had high analytical efficiency for TBBPA derivatives. Besides, compared with other offline methods, the method adopted online analysis. So, the IT-SPME-HPLC-DAD method in this work shows some unique advantages in the detection of TBBPA derivatives in water. Table 4 Comparison of the proposed with other reported methods. Analytical Methods Extraction materials LODs (µg L − 1 ) Linear ranges (µg L − 1 ) RSDs References HPLC-ICP-MS/MS C18 column 0.12–0.19 5-200 1.5%-2.2% [ 19 ] SPE-HPLC-MS/MS HLB column 0.09–0.21 0.1–500 2.6%-7.1% [ 20 ] SPE-HPLC-DAD C18 0.013 0.02-5 - [ 21 ] QuEChERS/UPLC-MS/MS C18 0.04–0.16 µg kg − 1 0.5–500 - [ 22 ] SPE-HPLC-MS Silica 0.0004 0.5–100 - [ 23 ] IT-SPME-UPLC-MS/MS COF-SO 3 H 0.005 0.001-3 1.4%-9.5% [ 24 ] SPME-ESI/MS TAPB-DMTP-COF 0.03 0.1–1000 1.9%-7.4% [ 25 ] IT-SPME-HPLC-DAD COF-CFs 0.05 0.167-10 2.5%-4.2% This work 4 Conclusions The functionalization by growing COFs was one effective strategy to regulate the extraction performance of carbon fibers. The improved enrichment effect for TBBPA derivatives was attributed to the π-stacking from the COF coating on CFs. Based on the mechanisms, the IT-SPME-HPLC-DAD method was established and applied to the sensitive detection of TBBPA derivatives in water samples. Compared with other methods, the unique online analysis was accomplished besides of better sensitivity. In the future, more COFs should be introduced to modify CFs for the adsorption or enrichment of various pollutants in environmental, food, biological and other fields. Declarations Author Contributions Statement Qiong Jiang : Conceptualization, Writing-original draft, Funding acquisition. Ziyi Xu : Investigation. Qing Li : Validation. Huixia Zhang : Project administration. Juanjuan Feng : Writing-review & editing, Resources. Min Sun : Writing-review & editing, Supervision. All authors reviewed the manuscript. Declaration of Competing Interest All of the authors declare that they have no conflict of interest. Acknowledgements This work was supported by the scientific research start-up funds for openly-recuited doctors of Gansu Agricultural University (No. 2017RCZX-10). References Qu G B, Liu A F, Hu L G, et al. 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Supplementary Files SupplementaryMaterial.docx Cite Share Download PDF Status: Published Journal Publication published 09 Apr, 2026 Read the published version in Microchimica Acta → Version 1 posted Editorial decision: Revision requested 03 Dec, 2025 Reviews received at journal 23 Nov, 2025 Reviews received at journal 18 Nov, 2025 Reviewers agreed at journal 01 Nov, 2025 Reviewers agreed at journal 30 Oct, 2025 Reviewers invited by journal 30 Oct, 2025 Editor assigned by journal 24 Oct, 2025 Submission checks completed at journal 24 Oct, 2025 First submitted to journal 20 Oct, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7904953","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":542118762,"identity":"3357d5e5-a4cd-4aea-827e-20e5f157219f","order_by":0,"name":"Qiong Jiang","email":"","orcid":"","institution":"College of Plant Protection, Gansu Agricultural University/ Biocontrol Engineering Laboratory of Crop Diseases and Pests of Gansu Province","correspondingAuthor":false,"prefix":"","firstName":"Qiong","middleName":"","lastName":"Jiang","suffix":""},{"id":542118763,"identity":"e7e98ce7-31ba-4add-adc1-97c2c19774ff","order_by":1,"name":"Ziyi 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10:49:20","extension":"html","order_by":31,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":102628,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/8103b95c76fd7b967245cc16.html"},{"id":95537084,"identity":"649cdf50-3fd3-429b-83c1-687abf9fb5f1","added_by":"auto","created_at":"2025-11-10 10:49:19","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":821902,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of (a-b) the CFs and (c-d) the COF-CFs.\u003c/p\u003e","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/2b57b631734129ff36c1c2b7.png"},{"id":95537081,"identity":"df49b9cd-4d63-4123-b13b-1d9cc96b0305","added_by":"auto","created_at":"2025-11-10 10:49:19","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":171218,"visible":true,"origin":"","legend":"\u003cp\u003e(a) XRD image of the COF and (b) N\u003csub\u003e2\u003c/sub\u003e adsorbed isotherms and pore diameter distribution curve of COF.\u003c/p\u003e","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/a6e78c46984b110744ace006.png"},{"id":95537082,"identity":"596f5a08-30bb-4620-9344-2f24b5f99f95","added_by":"auto","created_at":"2025-11-10 10:49:19","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":411841,"visible":true,"origin":"","legend":"\u003cp\u003eThe optimization of experimental conditions including (a) extraction volume, (b) extraction flow rate, (c) methanol content, and (d) desorption time; concentration of sample solution, 5.0 μg L\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/99860fc18da5e2fed3742a71.png"},{"id":95653960,"identity":"3859d217-1c9c-4c35-9a2c-d1e78f337abf","added_by":"auto","created_at":"2025-11-11 16:06:46","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":694421,"visible":true,"origin":"","legend":"\u003cp\u003eThe chromatograms of actual samples including (a) drinking water, (b) mineral water, (c) tap water, (d) Jiazi lake, (e) Fengxi river, (f) Daming lake.\u003c/p\u003e\n\u003cp\u003eAnalytes: 1. TBBPA-DME, 2. TBBPA-BDBPE, 3. TBBPA-BAE.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/62aa3d478f8ef850afba95d1.png"},{"id":106808892,"identity":"bb52a82f-ce83-41f0-a7fe-343e56e96462","added_by":"auto","created_at":"2026-04-13 16:04:37","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3082019,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/d9504f41-6f5d-413d-ad87-6a301daecb1c.pdf"},{"id":95537085,"identity":"fb731c2e-c68b-4480-8267-9efd1c6c30e1","added_by":"auto","created_at":"2025-11-10 10:49:20","extension":"docx","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":24753,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-7904953/v1/5f7e08bbf4a99c97dfc21cab.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Carbon fibers coated with covalent organic framework for online in-tube solid-phase microextraction of tetrabromobisphenol A derivatives in water","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eTetrabromobisphenol A (TBBPA) is one of the most widely employed brominated flame retardant [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. To tailor the physicochemical properties or reactivity of the flame retardant, a range of TBBPA derivatives including TBBPA dimethyl ether (TBBPA-DME), TBBPA bis(2-hydroxyethyl ether) (TBBPA-BHEE), TBBPA bis(allyl ether) (TBBPA-BAE), and TBBPA bis(2,3-dibromopropyl ether) (TBBPA-BDBPE), are applied in polymeric materials [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Due to their additive nature rather than covalent bonding to the polymers, they possess a high potential for leaching and migration into the environment water. Owing to their potential as endocrine disruptors, environmental persistence, long-distance migration, and bioaccumulation, the development of robust and sensitive analytical method for TBBPA derivatives in environment water is crucial [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Trace level of targets in the complex matrix of environment water give the challenges. While the sample preparation is often required to improve the sensitivity by removing the matrix interference and enriching the target [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Compared with common solid-phase extraction and liquid-liquid extraction, in-tube solid-phase microextraction (IT-SPME) has more advantages, such as efficient enrichment, free or minimal solvent, automated operation, and excellent compatibility with liquid chromatography. The extraction behavior greatly depends on the sorbent or coating in extraction tube [\u003cspan additionalcitationids=\"CR6\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eCarbon fibers (CFs) are one special carbon material prized for its exceptional strength, stiffness, and low weight. Its applications are vast and growing in different fields. Although CFs as a sorbent displayed the enrichment potential for hydrophobic analytes in IT-SPME [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e], some faults including low surface area, only hydrophobic and graphitized surface, and less functional groups seriously limited the further application. To solve above issues, some materials containing graphene [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], biochar nanospheres [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], carbon nanoparticles [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], titanium dioxide nanorods [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], and polyaniline/titanium dioxide nanorods [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], were used to functionalize CFs, achieving the effective extraction for polycyclic aromatic hydrocarbons and phthalates. Compared with these sorbents, covalent organic frameworks (COFs) are more attractive in sample preparation. Despite a class of highly porous and crystalline materials, COFs are entirely constructed from strong covalent bonds between light organic elements (C, H, O, N, et al.). Besides of gas storage and separation, catalysis, sensing, and energy storage, COFs hold great promise for IT-SPME, due to obvious advantages such as well-defined structures, high surface area, excellent stability, tunable pore size, low density, facile functionalization and so on [\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eBased on these considerations, one COF was in-situ grown onto CFs for extracting and detecting TBBPA derivatives by IT-SPME combining with HPLC. The structures and properties of the COF-coated CFs (COF-CFs) were characterized. The polyetheretherketone tube packed with COF-CFs was used as an extraction tube. The tube was connected to HPLC with diode array detection (DAD) to construct an IT-SPME-HPLC-DAD system. After optimizing extraction and desorption conditions, an analytical method was established for detecting trace levels of TBBPA derivatives in water. Subsequently, the method was applied to real water samples to verify its practical feasibility.\u003c/p\u003e"},{"header":"2 Experimental","content":"\u003cp\u003eSections 2.1\u0026ndash;2.4 materials and reagents, apparatus, chromatographic conditions, and sample preparation were described in Supplementary Materials.\u003c/p\u003e\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.5 Material preparation\u003c/h2\u003e\u003cp\u003eFirst, 5.0 mg of 1,3,5-tris(4-aminophenyl)benzene (TAPB) was dissolved in 5.0 mL of methanol, and 70.0 cm of CF bundle was completely immersed in the solution. After the mixture was sonicated for 30 min, it was placed in the oven at 65\u0026deg;C for 12 h, to obtain CFs adsorbed with TAPB. Next, 11.0 mg of 1,4-phthalaldehyde and 0.5 mL of 12.0 mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e HAc were dissolved in 5.0 mL ACN, and TAPB-coated CFs were immersed in this solution. After 48 h at room temperature, the COF-CFs were obtained. Finally, the COF-CFs were loaded into the PEEK tube, to achieve the extraction tube.\u003c/p\u003e\u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e3.1 Characterization\u003c/h2\u003e\u003cp\u003eThe microstructures of CFs and COF-CFs are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The CF had a gully surface, which helps with the adhesion of the coating. There was an uniform coating and the gully structure was weakened on the surface of COF-CFs. The thin coating and high surface area of COF are very conducive to rapid and efficient extraction. The crystal structure and surface area of COF were tested by XRD and BET. As can be seen from the Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, there was a diffraction peak at 2.76\u0026deg;, which coincided with the angle of the characteristic peak of the COFs [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Besides, according to the adsorption and desorption curves, the substance conformed to type Ⅱ isotherms. The BET surface area of the substance was 35.33 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and adsorption average pore diameter was 23.52 nm, desorption average pore diameter is 34.64 nm [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. The pore size of this material is conducive to the entry of the analytes for full adsorption.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e\u003cb\u003e3.2 The improvement of extraction effect by the COF coating\u003c/b\u003e\u003c/h2\u003e\u003cp\u003eIn order to display the role of COF coating, COF-CFs-filled tube was compared to the tube filled with only CFs under the same conditions (60.0 mL of sample, 1.5 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of sampling rate, and 2.0 min of desorption). According to the enrichment factors (EFs) of analytes in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the introduction of COF coating presented the enhanced effect for capturing three TBBPA derivatives. The COF not only increased the adsorptive sites, but also produced a π-stacking effect with the target in the nanopores.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eEnrichment factors of TBBPA derivatives on two extraction tubes.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"4\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eAnalytes\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u003cp\u003eEnrichment factors\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eRatio\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eCFs-filled tube\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eCOF-CFs-filled tube\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-DME\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e145\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e380\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e2.62\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-BDBPE\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1238\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e2191\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e1.77\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-BAE\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e413\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e477\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e1.15\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e3.3 Optimization of extraction and desorption factors\u003c/h2\u003e\u003cp\u003eWhen the extraction volume is small, the extraction effect on the target is low. As the extraction volume gradually expands, the peak area often shows a steady increase trend. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (a), the peak area of the three analytes was positively related with the extraction volume. In view of the detection efficiency and time cost control, 60 mL of extraction volume was finally selected.\u003c/p\u003e\u003cp\u003eThe flow rate of sample through the extraction tube affects the mass transfer process and extraction time. When the rate is low, the target can be adequately captured. When the sample flows rapidly through the extraction tube, the short test time can be obtained. If the rate is high, the extraction time is short. However, high flow rate often results in the inefficient enrichment of target and the high pressure in the tube. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (b), the peak area of TBBPA-DME and TBBPA-BDBPE increases with the increase of flow rate, and the peak area of the two analytes at 1.75 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was 2\u0026ndash;3 times of that at 0.75 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, while the peak area of TBBPA-BAE presented a slow increase. Considering the extraction time and peak area, 1.50 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was selected as the optimal flow rate.\u003c/p\u003e\u003cp\u003eThe concentration of organic solvent in sample solution can impact the extraction efficiency of hydrophobic target. In this work, methanol was used to test the effect. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (c), the peak area of TBBPA-BDBPE and TBBPA-BAE reduced with the raise of methanol concentration, while the peak area of TBBPA-DME increased. Thinking about the reason, the decrease of the extraction ability of COF-CFs towards TBBPA-BDBPE and TBBPA-BAE, giving way to the more adsorption sites for TBBPA-DME. Based on the comprehensive consideration of three analytes, the methanol content of 2.0% (v/v) was finally selected as the optimal organic solvent content.\u003c/p\u003e\u003cp\u003eWhen the desorption time is short, some targets will remain on the surface of sorbent, which affects the result. However, the excessive desorption time is unnecessary. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e (d), TBBPA-BAE shows a steady trend, while the peak area of TBBPA-DME and TBBPA-BDBPE improved first with the increase of desorption time, and then was gradually stabilized after 1.0 min. In view of residual effect, 2.0 min was selected as the optimal desorption time.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\u003ch2\u003e3.4 Method evaluation and the application for real samples\u003c/h2\u003e\u003cp\u003eUnder the optimal experimental conditions, an online IT-SPME-HPLC-DAD method was established for three TBBPA derivatives. Analytical linearities, linear coefficients (r), detection limits (LODs), enrichment factors, and repeatability results are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The LOD of TBBPA-DME was 0.1 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the LODs of TBBPA-BDBPE and TBBPA-BAE were as low as 0.05 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The linear range of TBBPA-DME was between 0.33-10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, while the linear ranges of TBBPA-BDBPE and TBBPA-BAE were between 0.167-10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Their EFs were from 936 to 2187. The RSDs (n\u0026thinsp;=\u0026thinsp;3) of parallel tests were in the range of 2.5%-4.2%. Based on the above results, the online method was accurate and sensitive for determining TBBPA derivatives.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eImportant parameters of the online analytical method for three targets.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"\u0026minus;\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAnalytes\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eLinearities\u003c/p\u003e\u003cp\u003e(\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003e\u003csup\u003ea\u003c/sup\u003e LODs\u003c/p\u003e\u003cp\u003e(\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003er\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003e\u003csup\u003eb\u003c/sup\u003e EFs\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eIntra-day\u003c/p\u003e\u003cp\u003e(RSDs, n\u0026thinsp;=\u0026thinsp;3)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-DME\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e\u003cp\u003e0.33-10.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.996\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e380\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"2\" rowspan=\"3\"\u003e\u003cp\u003e3.7%\u003c/p\u003e\u003cp\u003e2.5%\u003c/p\u003e\u003cp\u003e4.2%\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-BDBPE\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e\u003cp\u003e0.167-10.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.05\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.998\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e2191\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTBBPA-BAE\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c2\"\u003e\u003cp\u003e0.167-10.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.05\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e0.979\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e477\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003csup\u003ea\u003c/sup\u003e LODs, limits of detection, three times the signal-to-noise ratio.\u003c/p\u003e\u003cp\u003e\u003csup\u003eb\u003c/sup\u003e EFs, enrichment factors were confirmed as the ratio of analyte concentration before and after extraction (EF\u0026thinsp;=\u0026thinsp;C\u003csub\u003eSPME\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eAnalytes: 1. TBBPA-DME, 2. TBBPA-BDBPE, 3. TBBPA-BAE.\u003c/p\u003e\u003cp\u003eIn order to verify the practical application of the method, six common water sources (drinking water, mineral water, tap water, Jiazi lake, Fengxi river, Daming lake.) were selected as real water samples. Furthermore, the method reliability was verified through spiking tests (2.0 and 10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). As shown in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e4\u003c/span\u003e, these targets were not found in the actual water samples. Specifically, most of the spiked recoveries were lower at a spiked concentration of 10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Analyzing the reasons, it may be that some impurities occupy the extraction sites, leading to a reduced extraction capacity for the target analytes, and therefore the spiked recoveries were relatively low.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eDetermination results and recoveries for TBBPA derivatives in actual samples.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"4\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAnalytes\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eTBBPA-DME\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eTBBPA-BDBPE\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eTBBPA-BAE\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eDrinking water\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e73.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e73.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e114.8\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e70.9\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e70.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e87.8\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMineral water\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e121.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e86.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e97.6\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e94.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e72.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e69.2\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eTap water\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e91.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e95.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e145.3\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e82.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e80.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e83.5\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eJiazi lake\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e111.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e89.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e120.9\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e79.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e80.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e73.4\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eFengxi river\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e72.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e70.0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e95.5\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e73.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e88.3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e77.6\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eDaming lake\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eND\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (2.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e74.8\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e75.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e101.6\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eRecoveries (10.0 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, %)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e74.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u003cp\u003e78.7\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e82.4\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eND: not detected.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\u003ch2\u003e3.5 Comparison with other methods\u003c/h2\u003e\u003cp\u003eIn order to comprehensively evaluate the IT-SPME-HPLC-DAD method for the detection of trace TBBPA derivatives in water, the method was compared with other analytical methods. As shown in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, the LOD (0.05 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) in this work was lower than that of HPLC-ICP-MS [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] and SPE-HPLC-MS/MS [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e], and the linear range (0.167-10 \u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) was wider than that of SPE-HPLC [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Compared with the MS analysis method [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan additionalcitationids=\"CR23 CR24\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e], the method was simple operation, less relied on expensive equipment and had high analytical efficiency for TBBPA derivatives. Besides, compared with other offline methods, the method adopted online analysis. So, the IT-SPME-HPLC-DAD method in this work shows some unique advantages in the detection of TBBPA derivatives in water.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eComparison of the proposed with other reported methods.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"\u0026minus;\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAnalytical Methods\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eExtraction\u003c/p\u003e\u003cp\u003ematerials\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eLODs\u003c/p\u003e\u003cp\u003e(\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eLinear ranges\u003c/p\u003e\u003cp\u003e(\u0026micro;g L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eRSDs\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eReferences\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eHPLC-ICP-MS/MS\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eC18 column\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.12\u0026ndash;0.19\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e5-200\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c5\"\u003e\u003cp\u003e1.5%-2.2%\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eSPE-HPLC-MS/MS\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eHLB column\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.09\u0026ndash;0.21\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.1\u0026ndash;500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c5\"\u003e\u003cp\u003e2.6%-7.1%\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eSPE-HPLC-DAD\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eC18\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.013\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.02-5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eQuEChERS/UPLC-MS/MS\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eC18\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.04\u0026ndash;0.16\u003c/p\u003e\u003cp\u003e\u0026micro;g kg\u003csup\u003e\u003cb\u003e\u0026minus;\u0026thinsp;1\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.5\u0026ndash;500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e-\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR22\" 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colname=\"c4\"\u003e\u003cp\u003e0.1\u0026ndash;1000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c5\"\u003e\u003cp\u003e1.9%-7.4%\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eIT-SPME-HPLC-DAD\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003eCOF-CFs\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e0.05\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0.167-10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\"\u0026minus;\" colname=\"c5\"\u003e\u003cp\u003e2.5%-4.2%\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003eThis work\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eThe functionalization by growing COFs was one effective strategy to regulate the extraction performance of carbon fibers. The improved enrichment effect for TBBPA derivatives was attributed to the π-stacking from the COF coating on CFs. Based on the mechanisms, the IT-SPME-HPLC-DAD method was established and applied to the sensitive detection of TBBPA derivatives in water samples. Compared with other methods, the unique online analysis was accomplished besides of better sensitivity. In the future, more COFs should be introduced to modify CFs for the adsorption or enrichment of various pollutants in environmental, food, biological and other fields.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor Contributions Statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eQiong Jiang\u003c/strong\u003e: Conceptualization, Writing-original draft, Funding acquisition.\u003cstrong\u003e\u0026nbsp;Ziyi\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eXu\u003c/strong\u003e: Investigation.\u003cstrong\u003e\u0026nbsp;Qing Li\u003c/strong\u003e: Validation.\u003cstrong\u003e\u0026nbsp;Huixia Zhang\u003c/strong\u003e: Project administration.\u003cstrong\u003e\u0026nbsp;Juanjuan Feng\u003c/strong\u003e: Writing-review \u0026amp; editing, Resources.\u003cstrong\u003e\u0026nbsp;Min Sun\u003c/strong\u003e: Writing-review \u0026amp; editing, Supervision. All authors reviewed the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of Competing Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll of the authors declare that they have no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the scientific research start-up funds for openly-recuited doctors of Gansu Agricultural University (No. 2017RCZX-10).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eQu G B, Liu A F, Hu L G, et al. Recent advances in the analysis of TBBPA/TBBPS, TBBPA/TBBPS derivatives and their transformation products[J]. \u003cem\u003eTrends in Analytical Chemistry\u003c/em\u003e, 2016, 83: 14-24.\u003c/li\u003e\n\u003cli\u003eZhang Q L, Zhu C M, Xue D, et al. 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Simultaneous determination of tetrabromobisphenol A and hexabromocyclododecane in aquatic products by QuEChERS/ultra performance liquid chromatography-tandem mass spectrometry[J]. \u003cem\u003eJournal of Instrumental Analysis\u003c/em\u003e, 2019, 38(3): 301-306.\u003c/li\u003e\n\u003cli\u003eZhu C F, Guo J, Yang W L, et al. Determination of hexabromocyclododecane and tetrabromobisphenol A in water by high performance liquid chromatography-tandem mass spectrometry[J]. \u003cem\u003eEnvironmental Chemistry\u003c/em\u003e, 2022, 41(9): 3121-3124.\u003c/li\u003e\n\u003cli\u003eCheng Y, Shan Y M, Pan T T, et al. Preparation of sulfonic acid-functionalized covalent organic framework solid-phase microextraction fiber and its application in the analysis of neurotransmitters in mouse brain[J]. \u003cem\u003eChinese Journal of Chromatography\u003c/em\u003e, 2023, 41(10): 911-920.\u003c/li\u003e\n\u003cli\u003eShi X, Xue Y, Tu Y, et al. Covalent organic framework-based solid phase microextraction coupled with electrospray ionization mass spectrometry for the quantitative assessment of abnormal bile acids by triclosan exposure in mice[J]. \u003cem\u003eTalanta\u003c/em\u003e, 2025, 285: 127398.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"microchimica-acta","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"miac","sideBox":"Learn more about [Microchimica Acta](https://link.springer.com/journal/604)","snPcode":"604","submissionUrl":"https://submission.springernature.com/new-submission/604/3","title":"Microchimica Acta","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Solid-phase microextraction, Covalent organic frameworks, Tetrabromobisphenol A derivatives, High-performance liquid chromatography, Online analysis","lastPublishedDoi":"10.21203/rs.3.rs-7904953/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7904953/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTetrabromobisphenol A (TBBPA) derivatives as new pollutants attracted more and more attention. Due to the trace level of TBBPA derivatives or the complex sample matrix, sample pretreatment was often required for sensitive determination. However, sample pretreatment methods including solid-phase extraction, liquid extraction, and fiber solid-phase microextraction were complicated procedures, inefficient, and offline operation with detection techniques. A coating of covalent organic framework (COF) was grown onto carbon fibers (CFs) via a Schiff-based reaction at room temperature. The COF-coated CFs (COF-CFs) were filled into one tube for enriching TBBPA derivatives in water by in-tube solid-phase microextraction (IT-SPME). After the optimization of extraction and desorption factors, online IT-SPME-HPLC-DAD method was developed. The method exhibited a wide linear range (0.167\u0026ndash;10.0 \u0026micro;g L⁻\u0026sup1;, 0.33\u0026ndash;10.0 \u0026micro;g L⁻\u0026sup1;), and a low detection limit (0.05 \u0026micro;g L⁻\u0026sup1;) resulting from high enrichment factors (936\u0026ndash;2187) within 20.0 min. The method was applied in the detection of TBBPA derivatives in water samples, demonstrating good practical applicability. Compared with other analytical methods, the method was simple, efficient, and online operation. The extraction material is expected to capture other pollutants in environmental, food, biological and other fields.\u003c/p\u003e","manuscriptTitle":"Carbon fibers coated with covalent organic framework for online in-tube solid-phase microextraction of tetrabromobisphenol A derivatives in water","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-11-10 10:49:15","doi":"10.21203/rs.3.rs-7904953/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-12-04T01:16:27+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-23T20:39:31+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-11-18T18:11:45+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"134080969185040654214894316112625736400","date":"2025-11-01T13:35:04+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"246293157448875150906555967679867917441","date":"2025-10-30T10:28:20+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-10-30T08:08:14+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-10-24T07:08:35+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-10-24T07:06:28+00:00","index":"","fulltext":""},{"type":"submitted","content":"Microchimica Acta","date":"2025-10-20T10:39:34+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"microchimica-acta","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"miac","sideBox":"Learn more about [Microchimica Acta](https://link.springer.com/journal/604)","snPcode":"604","submissionUrl":"https://submission.springernature.com/new-submission/604/3","title":"Microchimica Acta","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"df4697d7-551d-4335-a2c1-09535b5fcd4c","owner":[],"postedDate":"November 10th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-04-13T16:01:55+00:00","versionOfRecord":{"articleIdentity":"rs-7904953","link":"https://doi.org/10.1007/s00604-026-07948-1","journal":{"identity":"microchimica-acta","isVorOnly":false,"title":"Microchimica Acta"},"publishedOn":"2026-04-09 15:58:39","publishedOnDateReadable":"April 9th, 2026"},"versionCreatedAt":"2025-11-10 10:49:15","video":"","vorDoi":"10.1007/s00604-026-07948-1","vorDoiUrl":"https://doi.org/10.1007/s00604-026-07948-1","workflowStages":[]},"version":"v1","identity":"rs-7904953","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7904953","identity":"rs-7904953","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}