TY - JOUR
T1 - Guanidine-based covalent organic frameworks for the highly efficient extraction of alternative per-and polyfluoroalkyl substances from environmental water samples
AU - Zhang, Jinni
AU - Su, Hang
AU - Zhong, Yanhui
AU - Lin, Zian
AU - Cai, Zongwei
N1 - Funding information:
This work was supported by National Natural Science Foundation of China (22036001, 22274021, and 22404023).
Publisher Copyright:
© 2025 Elsevier B.V.
PY - 2025/9
Y1 - 2025/9
N2 - With the increase of alternative per- and polyfluoroalkyl substances (PFASs) across various applications, the environmental and toxicological implications are emerging as critical issues of increasing scientific and public concern. Accordingly, analytical methodologies must be enhanced to accurately detect and evaluate these alternative PFASs. Herein, a cationic guanidine-based covalent organic frameworks (TG-BPY COF) was synthesized via a one-step solvothermal method for the efficient extraction of alternative PFASs. TG-BPY COF demonstrated good chemical stability and reusability. It possessed a specific surface area of 184.66 m2/g and exhibited an adsorption capacity of 185.24, 182.41, 160.97, 160.56, and 232.03 mg g−1 toward PFBA, PFBS, PFHxA, PFHxS, and 6:2 Cl-PFESA, respectively. The characterization and density functional theory (DFT) calculation revealed that the binding mechanism between the TG-BPY COF and alternative PFASs involves size effects, hydrophobic interactions, and electrostatic interactions. Under optimal conditions, a simple and highly sensitive method was established for the quantitative analysis of five alternative PFASs by combining dispersive solid-phase extraction with ultrahigh-performance liquid chromatography-tandem mass spectrometry (dSPE-UPLC-MS/MS). The established methods demonstrated excellent linearity with the alternative PFASs concentration range of 0.10 to 500 ng L−1 (r ≥ 0.9997), along with extremely low limits of detection (0.030–0.044 ng L−1), and high enrichment factors (16.2–61.4). Furthermore, the method was applied to detect trace-level alternative PFASs in environmental water samples, and satisfactory recoveries (78.7 %–122.8 %) and relative standard deviations (RSDs ≤8.7 %) were achieved. This work not only provides an application scope for cationic covalent organic frameworks, but also offers a new strategy for the extraction of alternative PFASs in wastewater.
AB - With the increase of alternative per- and polyfluoroalkyl substances (PFASs) across various applications, the environmental and toxicological implications are emerging as critical issues of increasing scientific and public concern. Accordingly, analytical methodologies must be enhanced to accurately detect and evaluate these alternative PFASs. Herein, a cationic guanidine-based covalent organic frameworks (TG-BPY COF) was synthesized via a one-step solvothermal method for the efficient extraction of alternative PFASs. TG-BPY COF demonstrated good chemical stability and reusability. It possessed a specific surface area of 184.66 m2/g and exhibited an adsorption capacity of 185.24, 182.41, 160.97, 160.56, and 232.03 mg g−1 toward PFBA, PFBS, PFHxA, PFHxS, and 6:2 Cl-PFESA, respectively. The characterization and density functional theory (DFT) calculation revealed that the binding mechanism between the TG-BPY COF and alternative PFASs involves size effects, hydrophobic interactions, and electrostatic interactions. Under optimal conditions, a simple and highly sensitive method was established for the quantitative analysis of five alternative PFASs by combining dispersive solid-phase extraction with ultrahigh-performance liquid chromatography-tandem mass spectrometry (dSPE-UPLC-MS/MS). The established methods demonstrated excellent linearity with the alternative PFASs concentration range of 0.10 to 500 ng L−1 (r ≥ 0.9997), along with extremely low limits of detection (0.030–0.044 ng L−1), and high enrichment factors (16.2–61.4). Furthermore, the method was applied to detect trace-level alternative PFASs in environmental water samples, and satisfactory recoveries (78.7 %–122.8 %) and relative standard deviations (RSDs ≤8.7 %) were achieved. This work not only provides an application scope for cationic covalent organic frameworks, but also offers a new strategy for the extraction of alternative PFASs in wastewater.
KW - Alternative per-and polyfluoroalkyl substances
KW - Dispersive solid-phase extraction
KW - Guanidine-based covalent organic frameworks
KW - Ultrahigh-performance liquid chromatography-tandem mass spectrometry
KW - Water samples
UR - https://www.scopus.com/pages/publications/105011399730
U2 - 10.1016/j.microc.2025.114650
DO - 10.1016/j.microc.2025.114650
M3 - Journal article
AN - SCOPUS:105011399730
SN - 0026-265X
VL - 216
JO - Microchemical Journal
JF - Microchemical Journal
M1 - 114650
ER -
