{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T11:49:43Z","timestamp":1791287383000,"version":"4.1.0"},"reference-count":45,"publisher":"MDPI AG","issue":"23","license":[{"start":{"date-parts":[[2024,12,6]],"date-time":"2024-12-06T00:00:00Z","timestamp":1733443200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China","award":["21267009"],"award-info":[{"award-number":["21267009"]}]},{"name":"National Natural Science Foundation of China","award":["21262011"],"award-info":[{"award-number":["21262011"]}]},{"name":"National Natural Science Foundation of China","award":["JB22006"],"award-info":[{"award-number":["JB22006"]}]},{"name":"Unveiling and Leading Project of Hubei Minzu University","award":["21267009"],"award-info":[{"award-number":["21267009"]}]},{"name":"Unveiling and Leading Project of Hubei Minzu University","award":["21262011"],"award-info":[{"award-number":["21262011"]}]},{"name":"Unveiling and Leading Project of Hubei Minzu University","award":["JB22006"],"award-info":[{"award-number":["JB22006"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A covalent organic framework (COF) based on imine was synthesized using 2,5-dihexoxyterephthalaldehyde (DHT) and 1,3,5-tris(4-aminophenyl) benzene (TAPB) as starting materials. The TAPB-DHT-COF exhibited satisfactory chemical stability, making it a promising adsorbing material for stir bar sorptive extraction (SBSE) of four estrogens, including estrone (E1), \u03b2-estradiol (E2), hexestrol (HES), and mestranol (MeEE2), in ambient water samples. The extracted analytes were subsequently analyzed using a high-performance liquid chromatography-diode array detector (HPLC-DAD). A series of parameters affecting the SBSE process, such as solution pH, ionic strength, extraction time, and desorption solvent, were investigated by the controlled variable method. Under optimal conditions, the limit of detection (LODs) for the four targeted estrogens ranged from 0.06 to 0.15 \u00b5g\/L, with a linear range from 0.2 to 100 \u00b5g\/L. The observed enrichment factor (EF) ranged from 39 to 49, while the theoretical EF was estimated to be 50-fold. This methodology can be applied to the identification of estrogens in three environmental water samples.<\/jats:p>","DOI":"10.3390\/molecules29235763","type":"journal-article","created":{"date-parts":[[2024,12,6]],"date-time":"2024-12-06T03:44:47Z","timestamp":1733456687000},"page":"5763","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Development and Application of a Robust Imine-Based Covalent Organic Framework for Stir Bar Sorptive Extraction of Estrogens in Environmental Water"],"prefix":"10.3390","volume":"29","author":[{"given":"Jianing","family":"Sun","sequence":"first","affiliation":[{"name":"School of Chemistry and Environmental Engineering, Hubei Minzu University, Enshi 445000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xixi","family":"Lian","sequence":"additional","affiliation":[{"name":"School of Chemistry and Environmental Engineering, Hubei Minzu University, Enshi 445000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1451-9810","authenticated-orcid":false,"given":"Lianzhi","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Environmental Engineering, Hubei Minzu University, Enshi 445000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5763-2514","authenticated-orcid":false,"given":"Zhengchao","family":"Duan","sequence":"additional","affiliation":[{"name":"School of Chemistry and Environmental Engineering, Hubei Minzu University, Enshi 445000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,12,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"114579","DOI":"10.1016\/j.jep.2021.114579","article-title":"Estrogenic activity of Sage (Salvia officinalis L.) aerial parts and its isolated ferulic acid in immature ovariectomized female rats","volume":"282","author":"Sabry","year":"2022","journal-title":"J. Ethnopharmacol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"150637","DOI":"10.1016\/j.scitotenv.2021.150637","article-title":"Environmental estrogens in surface water and their interaction with microalgae: A review","volume":"807","author":"Ma","year":"2022","journal-title":"Sci. Total Environ."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"106987","DOI":"10.1016\/j.microc.2021.106987","article-title":"Thiol-ene click synthesis of \u03b2-cyclodextrin-functionalized covalent organic framework-based magnetic nanocomposites (Fe3O4@ COF@ \u03b2-CD) for solid-phase extraction and determination of estrogens and estrogen mimics","volume":"174","author":"Liu","year":"2022","journal-title":"Microchem. J."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"808","DOI":"10.1039\/D1NJ02426D","article-title":"Metal organic framework\/chitosan\/polyethylene oxide composite columnar foam as a sorbent for the enrichment and determination of estrogens in environmental aqueous solutions","volume":"46","author":"Si","year":"2022","journal-title":"New J. Chem."},{"key":"ref_5","unstructured":"Ragi, P. (2022, May 04). Towards the Determination of Estrone and 17\u03b2-Estradiol in Dairy Cattle Waste Using Solid Phase and Stir Bar Sorptive Extractions with Liquid Chromatography-Mass Spectrometry and Gas Chromatography-Mass Spectrometry. Masters Theses & Specialist Projects. Available online: https:\/\/digitalcommons.wku.edu\/theses\/3562\/."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"128688","DOI":"10.1016\/j.jhazmat.2022.128688","article-title":"Bioremoval of estrogens by laccase immobilized onto polyacrylonitrile\/polyethersulfone material: Effect of inhibitors and mediators, process characterization and catalytic pathways determination","volume":"432","author":"Zdarta","year":"2022","journal-title":"J. Hazard. Mater."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"128013","DOI":"10.1016\/j.jhydrol.2022.128013","article-title":"Developing a quantitative framework to track the fate and transport of estrogens on a watershed scale","volume":"611","author":"Zhao","year":"2022","journal-title":"J. Hydrol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"733","DOI":"10.1007\/s10337-022-04178-4","article-title":"Development of an efficient solid-phase microextraction monolithic column for the analysis of estrogens in human urine and serum samples","volume":"85","author":"Zhang","year":"2022","journal-title":"Chromatographia"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1007\/s00604-022-05208-6","article-title":"Development of hybrid monoliths incorporating metal-organic frameworks for stir bar sorptive extraction coupled with liquid chromatography for determination of estrogen endocrine disruptors in water and human urine samples","volume":"189","author":"Lhotska","year":"2022","journal-title":"Microchim. Acta"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"14467","DOI":"10.1039\/D2RA01754G","article-title":"Novel deep eutectic solvent-based liquid phase microextraction for the extraction of estrogenic compounds from environmental samples","volume":"12","author":"Fattahi","year":"2022","journal-title":"RSC Adv."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"35","DOI":"10.30704\/http-www-jivs-net.1066060","article-title":"Determination of estrogen receptor, progesterone receptor and epidermal growth factor receptor in canine vaginal tumors and vaginal fold prolapse: A preliminary study","volume":"6","author":"Tek","year":"2022","journal-title":"J. Istanb. Vet. Sci."},{"key":"ref_12","first-page":"101789","article-title":"Development of an HPLC-DAD method for the simultaneous analysis of four xenoestrogens in water and its application for monitoring photocatalytic degradation","volume":"9","author":"Alvarez","year":"2022","journal-title":"Methods X"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"16","DOI":"10.1016\/j.chroma.2014.07.013","article-title":"Efficient analysis of selected estrogens using fabric phase sorptive extraction and high performance liquid chromatography-fluorescence detection","volume":"1359","author":"Kumar","year":"2014","journal-title":"J. Chromatogr. A"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"12374","DOI":"10.1166\/jnn.2016.12968","article-title":"Fabrication of novel stir bar sorptive extraction coating based on magnetic molecularly imprinted polymer through atom transfer radical polymerization for trace analysis of estrogens in milk","volume":"16","author":"Qiu","year":"2016","journal-title":"J. Nanosci. Nanotechno."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"342","DOI":"10.1016\/j.aca.2014.10.041","article-title":"Novel molecularly imprinted stir bar sorptive extraction based on an 8-electrode array for preconcentration of trace exogenous estrogens in meat","volume":"853","author":"Qiao","year":"2015","journal-title":"Anal. Chim. Acta"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"463139","DOI":"10.1016\/j.chroma.2022.463139","article-title":"Porous aromatic framework coated stir bar sorptive extraction coupled with gas chromatography for the analysis of 16 polycyclic aromatic hydrocarbons in atmospheric particles and environmental water samples","volume":"1673","author":"Zhang","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"111510","DOI":"10.1016\/j.foodres.2022.111510","article-title":"Enhanced multi-stir bar sorptive extraction for wine analysis: Alteration in headspace mode","volume":"158","author":"Vyviurska","year":"2022","journal-title":"Food Res. Int."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1179","DOI":"10.1007\/s00217-021-03954-0","article-title":"Application of a direct immersion-stir bar sorptive extraction (DI-SBSE) combined GC-MS method for fingerprinting alkylpyrazines in tea and tea-like infusions","volume":"248","author":"Rigling","year":"2022","journal-title":"Eur. Food Res. Technol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"462748","DOI":"10.1016\/j.chroma.2021.462748","article-title":"Weak anion-exchange mixed-mode materials to selectively extract acidic compounds by stir bar sorptive extraction from environmental waters","volume":"1663","author":"Nadal","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"462798","DOI":"10.1016\/j.chroma.2021.462798","article-title":"Covalent organic framework-V modified porous polypropylene hollow fiber with detachable dumbbell-shaped structure for stir bar sorptive extraction of benzophenones","volume":"1664","author":"Liu","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"461810","DOI":"10.1016\/j.chroma.2020.461810","article-title":"Stir bar sorptive extraction and its application","volume":"1637","author":"He","year":"2021","journal-title":"J. Chromatogr. A"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"589","DOI":"10.1080\/03067319.2020.1724986","article-title":"Application of stir-bar sorptive extraction with liquid desorption to the determination of chlorinated hydrocarbons in water samples","volume":"102","author":"Wejnerowska","year":"2022","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1002\/(SICI)1520-667X(1999)11:10<737::AID-MCS7>3.0.CO;2-4","article-title":"Stir bar sorptive extraction (SBSE), a novel extraction technique for aqueous samples: Theory and principles","volume":"11","author":"Baltussen","year":"1999","journal-title":"J. Microcolumn Sep."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"462521","DOI":"10.1016\/j.chroma.2021.462521","article-title":"Tailored amino\/hydroxyl bifunctional microporous organic network for efficient stir bar sorptive extraction of parabens and flavors from cosmetic and food samples","volume":"1655","author":"Han","year":"2021","journal-title":"J. Chromatogr. A"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"15","DOI":"10.1016\/j.chroma.2018.09.049","article-title":"In-situ growth of zeolitic imidazole framework-67 on nanoporous anodized aluminum bar as stir-bar sorptive extraction sorbent for determining caffeine","volume":"1577","author":"Ghani","year":"2018","journal-title":"J. Chromatogr. A"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"9053561","DOI":"10.1155\/2018\/9053561","article-title":"Determination of \u03b2-agonist residues in animal-derived food by a liquid chromatography-tandem mass spectrometric method combined with molecularly imprinted stir bar sorptive extraction","volume":"2018","author":"Tang","year":"2018","journal-title":"J. Anal. Methods Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"369","DOI":"10.1016\/j.talanta.2017.09.061","article-title":"Design and construction of an injection port for coupling stir-bar sorptive extraction with ion mobility spectrometry","volume":"178","author":"Jafari","year":"2018","journal-title":"Talanta"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"122332","DOI":"10.1016\/j.talanta.2021.122332","article-title":"Reduced graphene oxide coated nickel foam for stir bar sorptive extraction of benzotriazole ultraviolet absorbents from environmental water","volume":"231","author":"Zhang","year":"2021","journal-title":"Talanta"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"116741","DOI":"10.1016\/j.trac.2022.116741","article-title":"Combination of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs): Recent advances in synthesis and analytical applications of MOF\/COF composites","volume":"157","author":"Ma","year":"2022","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"122829","DOI":"10.1016\/j.talanta.2021.122829","article-title":"Controllable synthesis of uniform large-sized spherical covalent organic frameworks for facile sample pretreatment and as naked-eye indicator","volume":"236","author":"Li","year":"2022","journal-title":"Talanta"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"133785","DOI":"10.1016\/j.foodchem.2022.133785","article-title":"Porous organic framework as coating for stir bar sorptive extraction of carbamate pesticides from corn and potato samples","volume":"397","author":"Wang","year":"2022","journal-title":"Food Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"463030","DOI":"10.1016\/j.chroma.2022.463030","article-title":"Covalent organic framework-based magnetic solid phase extraction coupled with micellar electrokinetic chromatography for the analysis of trace organophosphorus pesticides in environmental water and atmospheric particulates","volume":"1673","author":"Chen","year":"2022","journal-title":"J. Chromatogr. A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"16501","DOI":"10.1002\/anie.201811250","article-title":"Flexible films of covalent organic frameworks with ultralow dielectric constants under high humidity","volume":"57","author":"Shao","year":"2018","journal-title":"Angew. Chem"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"920","DOI":"10.1016\/j.cej.2019.03.148","article-title":"Facile room-temperature synthesis of a spherical mesoporous covalent organic framework for ultrasensitive solid-phase microextraction of phenols prior to gas chromatography-tandem mass spectrometry","volume":"369","author":"Liu","year":"2019","journal-title":"Chem. Eng. J."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"2201","DOI":"10.1351\/pac198254112201","article-title":"Reporting physisorption data for gas\/solid systems with special reference to the determination of surface area and porosity (Provisional)","volume":"54","author":"Sing","year":"1982","journal-title":"Pure Appl. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1016\/j.aca.2009.03.031","article-title":"Preparation of polydimethylsiloxane\/\u03b2-cyclodextrin\/divinylbenzene coated \u201cdumbbell-shaped\u201d stir bar and its application to the analysis of polycyclic aromatic hydrocarbons and polycyclic aromatic sulfur heterocycles compounds in lake water and soil by high performance liquid chromatography","volume":"641","author":"Yu","year":"2009","journal-title":"Anal. Chim. Acta"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"35","DOI":"10.1016\/j.aca.2018.04.013","article-title":"Development and application of vortex-assisted membrane extraction based on metal-organic framework mixed-matrix membrane for the analysis of estrogens in human urine","volume":"1023","author":"Gao","year":"2018","journal-title":"Anal. Chim. Acta"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"7","DOI":"10.1016\/j.talanta.2018.10.027","article-title":"Enhanced in-out-tube solid-phase microextraction by molecularly imprinted polymers-coated capillary followed by HPLC for endocrine disrupting chemicals analysis","volume":"194","author":"Wang","year":"2019","journal-title":"Talanta"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2009","DOI":"10.1002\/bkcs.11016","article-title":"Determination of estrogens in environmental aqueous samples using dispersive liquid-liquid microextraction and HPLC\/UV\u2013Vis system","volume":"37","author":"Moon","year":"2016","journal-title":"Bull. Korean Chem. Soc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2016.03.003","article-title":"Preparation of photonic-magnetic responsive molecularly imprinted microspheres and their application to fast and selective extraction of 17\u03b2-estradiol","volume":"1442","author":"Peng","year":"2016","journal-title":"J. Chromatogr. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"10","DOI":"10.1016\/j.chroma.2014.01.016","article-title":"An automated solid-phase microextraction method based on magnetic molecularly imprinted polymer as fiber coating for detection of trace estrogens in milk powder","volume":"1331","author":"Lan","year":"2014","journal-title":"J. Chromatogr. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1016\/j.chroma.2013.08.047","article-title":"Polydimethylsiloxane\/metal-organic frameworks coated stir bar sorptive extraction coupled to high performance liquid chromatography-ultraviolet detector for the determination of estrogens in environmental water samples","volume":"1310","author":"Hu","year":"2013","journal-title":"J. Chromatogr. A"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"10494","DOI":"10.1021\/jf303269c","article-title":"Determination of estrogens in pork and chicken samples by stir bar sorptive extraction combined with high-performance liquid chromatography-ultraviolet detection","volume":"60","author":"Hu","year":"2012","journal-title":"J. Agric. Food Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1303","DOI":"10.1016\/j.jpba.2006.02.037","article-title":"Determination of steroid sex hormones in water and urine matrices by stir bar sorptive extraction and liquid chromatography with diode array detection","volume":"41","author":"Almeida","year":"2006","journal-title":"J. Pharm. Biomed. Anal."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1137","DOI":"10.1002\/jssc.201900819","article-title":"Spiral stir bar sorptive extraction with polyaniline-polydimethylsiloxane sol-gel packings for the analysis of trace estrogens in environmental water and animal-derived food samples","volume":"43","author":"Fan","year":"2020","journal-title":"J. Sep. Sci."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/23\/5763\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T16:48:15Z","timestamp":1760114895000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/23\/5763"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,12,6]]},"references-count":45,"journal-issue":{"issue":"23","published-online":{"date-parts":[[2024,12]]}},"alternative-id":["molecules29235763"],"URL":"https:\/\/doi.org\/10.3390\/molecules29235763","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,12,6]]}}}