In-situ growth of covalent organic frameworks on 3D-printed monolithic microfluidic chips for online analysis of naphthalene and its metabolites in cells.

Authors

Qiulin Zhang, Beibei Chen, Zhen Zhou, Yong Liang, Yuning Hu, Man He

Published in

Analytica chimica acta. Volume 1416. Pages 345718. Sep 22, 2026. Epub May 27, 2026.

Abstract

Three-dimensional printing (3DP) has shown great potential in the preparation of monolithic column microextraction chips, but insufficient functional groups and low specific surface area limit its application in the field of adsorption/extraction. Although various surface functionalization strategies have been developed to overcome these drawbacks, challenges such as tedious pretreatment, pore blocking, and the need for high-concentration doping still remained. In-situ growth of covalent organic frameworks (COFs) offers an ideal solution but is limited by multi-step modification process and the availability of native functional groups. Herein, a facile and universal strategy based on catalyst pre-doping was proposed for in-situ growth of COFs on 3DP monolithic columns.
By incorporating a trace amount (1%) of scandium trifluoromethanesulfonate (catalyst) into commercial photocurable resins, a uniform COFs layer was successfully formed on 3DP monoliths through a single post-printing reaction, without compromising the printing performance or structural integrity of the monoliths. Compared with unmodified 3DP monoliths, the COFs-functionalized columns exhibited significantly enhanced adsorption efficiency (53-79% vs 3-55%) toward naphthalene and its metabolites, along with excellent reusability over 100 cycles. Furthermore, a 3DP integrated microfluidic chip, integrating on-chip cell lysis, COF-based monolithic microextraction, and PEEK interfacing, was developed and coupled with high-performance liquid chromatography-fluorescence detector (HPLC-FLD) for the online analysis of naphthalene and its metabolites in BEAS-2B cells. The detection limit ranged from 0.04 to 3.95 μg L^-1. In cells exposed to 50 μmol L^-1 of naphthalene, 2-OHNAP was detected with the concentration of 0.36 ± 0.03 μg L^-1.
A facile and universal approach for the in-situ growth of COFs on 3DP monoliths was proposed, effectively circumventing the drawbacks of traditional methods, such as high-concentration nanomaterial doping and tedious surface pre-functionalization. Subsequently, a novel method based on COFs-functionalized 3DP integrated chips coupled with HPLC was established for the online analysis of naphthalene and its metabolites in biological samples, featuring rapid prototyping, simple operation, and low cost.

PMID:
42401451
Bibliographic data and abstract were imported from PubMed on 05 Jul 2026.

Read full publication at:
Please sign in to see all details.

Stats

1-terrible, 9-excellent. How would you rate this publication? Sign in in to submit your rating.

Post a comment

You need to be signed in to post comments. You can sign in here.

Comments

There are no comments yet.