To advance biomaterial engineering: a novel pH-responsive MOF for eco-friendly modification of collagen fibers with applications in recyclable, alkali-free Knoevenagel catalysis
Source abstract
Abstract
Zirconium based MOFs demonstrate potential for ecofriendly modification of collagen fibers. However, achieving high utilization efficiency of zirconium ions remains challenging. Herein, a novel boronate ester functionalized MOF (Zr-TB) with pH-dependent structural stability is disclosed. It maintains structural integrity under neutral conditions but decomposes under acidic conditions below pH 4.0. Based on this, a novel modifier for collagen fibers is developed by loading zirconium complex (ZTA) into Zr-TB. This system enables controlled release of ZTA, thereby preventing excessive binding between zirconium ions and collagen fibers. EDS analysis confirms the uniform distribution of zirconium ions in the modified collagen fibers, resulting in excellent hydrothermal stability characterized by a shrinkage temperature of over 80 °C. DFT calculations reveal that the zirconium cluster complex generated from the decomposition of Zr-TB can also effectively bind to the -COOH of collagen fibers, thereby significantly improving the utilization efficiency of zirconium ions. Notably, after ball milling, the modified collagen fibers serve as an efficient catalyst for the Knoevenagel reaction and exhibit excellent cycling stability, maintaining a yield above 87% over five consecutive cycles, attributable to the uniform distribution of zirconium ions on the collagen support. Furthermore, the presence of -NH2 on the collagen fibers effectively eliminates the need for additional alkaline catalysts. This work presents a highly efficient strategy for modification of collagen fibers and highlights the promising potential of collagen fibers as carriers for organic synthesis catalysts.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Collagen: Extraction and Characterization · Electrospun Nanofibers in Biomedical Applications · Metal-Organic Frameworks: Synthesis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (59)
Show source-provided references
1. Koeck K, Salehi S, Humenik M, Scheibel T (2022) Processing of continuous non-crosslinked collagen fibers for microtissue formation at the muscle-tendon interface. Adv Funct Mater 32:2112238. https://doi.org/10.1002/adfm.20211223810.1002/adfm.202112238 ↗
2. Lin M, Liu H, Deng J, An R, Shen M, Li Y, Zhang X (2019) J Mater Sci Technol 35:1894. https://doi.org/10.1016/j.jmst.2019.05.01010.1016/j.jmst.2019.05.010 ↗
3. Xiao H, Wang Y, Hao B, Cao Y, Cui Y, Huang X, Shi B (2022) Collagen fiber-based advanced separation materials: recent developments and future perspectives. Adv Mater 34:2107891. https://doi.org/10.1002/adma.20210789110.1002/adma.202107891 ↗
4. Liu X, Wang Y, Wang X, Jiang H (2021) Development of hyperbranched poly-(amine-ester) based aldehyde/chrome-free tanning agents for sustainable leather resource recycling. Green Chem 23:5924. https://doi.org/10.1039/D1GC01538A10.1039/D1GC01538A ↗
5. Wang J, Huang X, Zhao P, Cao D, Li R, Zhao X, Du Y, Li K, Chen C, Liu G (2025) Nanofibrillated collagen fiber networks for enhanced air purification. Nat Commun 16:6823. https://doi.org/10.1038/s41467-025-62146-610.1038/s41467-025-62146-6 ↗
6. Ding C, Yi Y, Cheng K, Wang Y, Wang S, Zhang M (2024) Full life cycle green Preparation of collagen-based food packaging films using halocynthia Roretzi as Raw material. Food Chem 455:139943. https://doi.org/10.1016/j.foodchem.2024.13994310.1016/j.foodchem.2024.139943 ↗
7. Liu Y, Huang X, Guo P, Liao X, Shi B (2011) Skin collagen fiber-based radar absorbing materials. Sci Bull 56:202. https://doi.org/10.1007/s11434-010-4343-510.1007/s11434-010-4343-5 ↗
8. Ping H, Wagermaier W, Horbelt N, Scoppola E, Li C, Werner P, Fu Z, Fratzl P (2022) Mineralization generates megapascal contractile stresses in collagen fibrils. Science 376:188. https://doi.org/10.1126/science.abm266410.1126/science.abm2664 ↗
9. Wang P, Feng J, Bai Y, Chen X, Luo X, Zhang P, Wang X (2024) Zirconium ion ligand cross-linked carbon nanotubes and leather collagen fibers for flexible, stable, and highly efficient underwater sensors. Chem Eng J 480:148201. https://doi.org/10.1016/j.cej.2023.14820110.1016/j.cej.2023.148201 ↗
10. Ding W, Zhou J, Zeng Y, Wang Y, Shi B (2017) Preparation of oxidized sodium alginate with different molecular weights and its application for crosslinking collagen fiber. Carbohyd Polym 157:1650. https://doi.org/10.1016/j.carbpol.2016.11.04510.1016/j.carbpol.2016.11.045 ↗
11. Ding X, Yan Y, Gu Z, Shi R, Wang Y, Xu G, Hu Z, Jiang Z (2025) Bifunctional collagen fibers-based porous material for integrated purification of oily seawater. J Hazard Mater 494:138603. https://doi.org/10.1016/j.jhazmat.2025.13860310.1016/j.jhazmat.2025.138603 ↗
12. Yu R, Wang H, Wang R, Zhao P, Chen Y, Liu G, Liao X (2022) Polyphenol modified natural collagen fibrous network towards sustainable and antibacterial microfiltration membrane for efficient water disinfection. Water Res 218:118469. https://doi.org/10.1016/j.watres.2022.11846910.1016/j.watres.2022.118469 ↗
13. Zhang L, Cheng Q, Wang C, Huang C, Lin W (2024) Energy-saving and low-carbon leather production: AI-assisted Chrome tanning process optimization. J Clean Prod 457:142464. https://doi.org/10.1016/j.jclepro.2024.14246410.1016/j.jclepro.2024.142464 ↗
14. Yu L, Qiang X, Cui L, Chen B, Wang X, Wu X (2020) Preparation of a Syntan containing active Chlorine groups for chrome-free tanned leather. J Clean Prod 270:122351. https://doi.org/10.1016/j.jclepro.2020.12235110.1016/j.jclepro.2020.122351 ↗
15. Ouyang M, Hu K, Jiang Q, Yao Q, Zhou H, Deng Y, Shen Y, Li F, Zhuang L, Wang G (2022) An approach on chromium discharge reduction: effect and mechanism of ketone carboxylic acid as high exhaustion Chrome tanning agent. J Clean Prod 367:133125. https://doi.org/10.1016/j.jclepro.2022.13312510.1016/j.jclepro.2022.133125 ↗
16. Yu Y, Lin Y, Zeng Y, Wang Y, Zhang W, Zhou J, Shi B (2022) Life cycle assessment for Chrome tanning, Chrome-free metal tanning, and metal-free tanning systems. ACS Sustain Chem Eng 9:6720. https://doi.org/10.1021/acssuschemeng.1c0075310.1021/acssuschemeng.1c00753 ↗
17. Zhang J, Chen W (2020) A faster and more effective chrome tanning process assisted by microwave. RSC Adv 10:23503. https://doi.org/10.1039/d0ra04189k10.1039/d0ra04189k ↗
18. Pavithra K, Jaikumar V, Kumar P, Rajan P (2019) A review on cleaner strategies for chromium industrial wastewater: present research and future perspective. J Clean Prod 228:580. https://doi.org/10.1016/j.jclepro.2019.04.11710.1016/j.jclepro.2019.04.117 ↗
19. Marin R, Ahuja Y, Bose R (2010) Potentially deadly carcinogenic chromium redox cycle involving peroxochromium (IV) and glutathione. J Am Chem Soc 132:10617. https://doi.org/10.1021/ja102173v10.1021/ja102173v ↗
20. Chai J, Hu Q, Qiu B (2021) Conductive polyaniline improves Cr(VI) bio-reduction by anaerobic granular sludge. Adv Compos Hybrid Mater 4:1137. https://doi.org/10.1007/s42114-021-00342-w10.1007/s42114-021-00342-w ↗
21. Dhayalan K, Fathima N, Gnanamani A, Rao J, Nair B, Ramasami T (2007) Biodegradability of leathers through anaerobic pathway. Waste Manag 27:760. https://doi.org/10.1016/j.wasman.2006.03.01910.1016/j.wasman.2006.03.019 ↗
22. Li R, Ren L, Chen L, Liu H, Qiang T (2024) New materials-based on gelatin coordinated with zirconium or aluminum for ecological retanning. Int J Biol Macromol 261:129922. https://doi.org/10.1016/j.ijbiomac.2024.12992210.1016/j.ijbiomac.2024.129922 ↗
23. Zhou B, Niu L, Shi W, Zhang W, Arola D, Breschi L, Mao J, Chen J, Pashley D, Tay F (2014) Adopting the principles of collagen biomineralization for intrafibrillar infiltration of yttria-stabilized zirconia into three-dimensional collagen scaffolds. Adv Funct Mater 24:1895. https://doi.org/10.1002/adfm.20130292010.1002/adfm.201302920 ↗
24. Gao D, Li N, Li X, Zhang A, Lyu B, Ma J (2023) A green tanning method based on POSS-COONa and zirconium: achieving cleaner leather production. Prog Org Coat 183:107718. https://doi.org/10.1016/j.porgcoat.2023.10771810.1016/j.porgcoat.2023.107718 ↗
25. Baquero G, Sorolla S, Cuadros R, Ollé L, Bacardit A (2021) Analysis of the environmental impacts of waterproofing versus conventional vegetable tanning process - A life cycle analysis study. J Clean Prod 325:129344. https://doi.org/10.1016/j.jclepro.2021.12934410.1016/j.jclepro.2021.129344 ↗
26. Li K, Hu Q, Wang L, Wu C, Yang L, Liu G, Wang Y (2025) Engineering of bioprosthetic heart valves with synergistic zwitterionic surface modification and zirconium cross-linking for improved biocompatibility and durability. Acta Biomater 201:266. https://doi.org/10.1016/j.actbio.2025.06.01010.1016/j.actbio.2025.06.010 ↗
27. Zhao P, Gao D, Lyu B, Ma J, Kim K (2022) Fabrication of effective electromagnetic shielding leather with a chromium-free multi-network structure. J Clean Prod 374:133856. https://doi.org/10.1016/j.jclepro.2022.13385610.1016/j.jclepro.2022.133856 ↗
28. Feng J, Wang P, Bai Y, Chen X, Li T, Luo X, Zhang P, Wang X (2023) Design of highly conductive leather based on zirconium ion coordination for health protection in severe harsh conditions. Adv Mater Technol 21:2301304. https://doi.org/10.1002/admt.20230130410.1002/admt.202301304 ↗
29. Xue P, Yu Y, Wang H, Cao Y, Shi B, Wang Y (2024) Oxidized sodium lignosulfonate: A biobased chrome-free tanning agent for sustainable eco-leather manufacture. Ind Crop Prod 208:117916. https://doi.org/10.1016/j.indcrop.2023.11791610.1016/j.indcrop.2023.117916 ↗
30. Qiang T, Gao X, Ren J, Chen X, Wang X (2016) A chrome-free and chrome-less tanning system based on the hyperbranched polymer. ACS Sustain Chem Eng 4:701. https://doi.org/10.1021/acssuschemeng.5b0091710.1021/acssuschemeng.5b00917 ↗
31. Chen J, Ma J, Fan Q, Zhang W, Guo R (2023) A sustainable chrome-free tanning approach based on Zr-MOFs functionalized with different metals through post-synthetic modification. Chem Eng J 474:145453. https://doi.org/10.1016/j.cej.2023.14545310.1016/j.cej.2023.145453 ↗
32. Chen J, Ma J, Fan Q, Zhang W (2023) An eco-friendly metal-less tanning process: Zr-based metal-organic frameworks as novel chrome-free tanning agent. J Clean Prod 382:135263. https://doi.org/10.1016/j.jclepro.2022.13526310.1016/j.jclepro.2022.135263 ↗
33. Ma K, Cheung Y, Xie H, Wang X, Evangelopoulos M, Kirlikovali K, Su S, Wang X, Mirkin C, Xin J, Farha O (2023) Zirconium-based metal–organic frameworks as reusable antibacterial peroxide carriers for protective textiles. Chem Mater 35:2342. https://doi.org/10.1021/acs.chemmater.2c0328810.1021/acs.chemmater.2c03288 ↗
34. Rajeev S, Hasoon N, Panicker U (2025) Sodium alginate/polyvinylpyrrolidone/lapatinib-loaded Zr–metal organic framework: biocompatibility evaluation and pH-responsive in vitro drug release for oral delivery applications. J Mater Chem B 13:12205. https://doi.org/10.1039/D5TB01449B10.1039/D5TB01449B ↗
35. Ou R, Zhang H, Zhao C, Hegab H, Jiang L, Truong V, Wang H (2020) Photoresponsive styrylpyrene-modified MOFs for gated loading and release of cargo molecules. Chem Mater 32:10621. https://doi.org/10.1021/acs.chemmater.0c0372610.1021/acs.chemmater.0c03726 ↗
36. Mutruc D, Goulet-Hanssens A, Fairman S, Wahl S, Zimathies A, Knie C, Hecht S (2019) Modulating guest uptake in Core-Shell MOFs with visible light. Angew Chem Int Ed 58:12862. https://doi.org/10.1002/anie.20190660610.1002/anie.201906606 ↗
37. Hohenberg P, Kohn W (1964) Inhomogeneous electron gas. Phys Rev 136:864. https://doi.org/10.1103/PhysRev.136.B86410.1103/PhysRev.136.B864 ↗
38. Kohn W, Sham L (1965) Self-consistent equations including exchange and correlation effects. Phys Rev 140:1133. https://doi.org/10.1103/PhysRev.140.A113310.1103/PhysRev.140.A1133 ↗
39. Goedecker S, Teter M, Hutter J (1996) Separable dual-space Gaussian pseudopotentials. Phys Rev B 54:1703. https://doi.org/10.1103/PhysRevB.54.170310.1103/PhysRevB.54.1703 ↗
40. Vondele J, Hutter J (2007) Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J Chem Phys 127:114105. https://doi.org/10.1063/1.277070810.1063/1.2770708 ↗
41. Perdew J, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865. https://doi.org/10.1103/physrevlett.77.386510.1103/physrevlett.77.3865 ↗
42. Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate Ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104. https://doi.org/10.1063/1.338234410.1063/1.3382344 ↗
43. Tajbakhsh S, Hajiali F, Maric M (2021) Recyclable polymers with boronic ester dynamic bonds prepared by miniemulsion polymerization. ACS Appl Polym Mater 3:3402. https://doi.org/10.1021/acsapm.1c0036810.1021/acsapm.1c00368 ↗
44. Valenzano L, Civalleri B, Chavan S, Bordiga S, Nilsen M, Jakobsen S, Lillerud K, Lamberti C (2011) Disclosing the complex structure of UiO-66 metal organic framework: a synergic combination of experiment and theory. Chem Mater 23:1700. https://doi.org/10.1021/cm102288210.1021/cm1022882 ↗
45. Wang T, Bury W, Gómez-Gualdrón D, Vermeulen N, Mondloch J, Deria P, Zhang K, Moghadam P, Sarjeant A, Snurr R, Stoddart J, Hupp J, Farha O (2015) Ultrahigh surface area zirconium MOFs and insights into the applicability of the BET theory. J Am Chem Soc 137:3585. https://doi.org/10.1021/ja512973b10.1021/ja512973b ↗
46. Fan G, Zhan J, Luo J, Lin J, Qu F, Du B, You Y, Yan Z (2021) Fabrication of heterostructured Ag/AgCl@g-C3N4@UIO-66(NH2) nanocomposite for efficient photocatalytic inactivation of microcystis aeruginosa under visible light. J Hazard Mater 404:124062. https://doi.org/10.1016/j.jhazmat.2020.12406210.1016/j.jhazmat.2020.124062 ↗
47. Zhou B, Deng T, Yang C, Wang M, Yan H, Yang Z, Wang Z, Xue Z (2023) Self-healing and recyclable polymer electrolyte enabled with boronic ester transesterification for stabilizing ion deposition. Adv Funct Mater 33:2212005. https://doi.org/10.1002/adfm.20221200510.1002/adfm.202212005 ↗
48. Ren Y, Li T, Zhang W, Wang S, Shi M, Shan C, Zhang W, Guan X, Lv L, Hua M, Pan B (2019) MIL-PVDF blend ultrafiltration membranes with ultrahigh MOF loading for simultaneous adsorption and catalytic oxidation of methylene blue. J Hazard Mater 365:312. https://doi.org/10.1016/j.jhazmat.2018.11.01310.1016/j.jhazmat.2018.11.013 ↗
49. Bolat S, Demir S, Erer H, Pelit F, Dzingelevičienė R, Ligor T, Buszewski B, Pelit L (2024) MOF-801 based solid phase Microextraction fiber for the monitoring of indoor BTEX pollution. J Hazard Mater 466:133607. https://doi.org/10.1016/j.jhazmat.2024.13360710.1016/j.jhazmat.2024.133607 ↗
50. Hao D, Wang X, Yue O, Liang S, Bai Z, Yang J, Liu X, Dang X (2023) A wrench-like green amphoteric organic chrome-free tanning agent provides long-term and effective antibacterial protection for leather. J Clean Prod 404:136917. https://doi.org/10.1016/j.jclepro.2023.13691710.1016/j.jclepro.2023.136917 ↗
51. Yang N, Ma J, Shi J, Gao D (2020) pH-triggered MgAlZr layered double hydroxides for modification of collagen fibers with enhanced thermal stability and UV resistance. Appl Clay Sci 198:105827. https://doi.org/10.1016/j.clay.2020.10582710.1016/j.clay.2020.105827 ↗
52. Cao S, Liu B, Cheng B, Lu F, Wang Y, Li Y (2017) Mechanisms of Zn(II) binded to collagen and its effect on the capacity of eco-friendly Zn-Cr combination tanning system. J Hazard Mater 321:203. https://doi.org/10.1016/j.jhazmat.2016.09.01610.1016/j.jhazmat.2016.09.016 ↗
53. Xu Y, Xu C, Wang C, Liu Y, Wang S, Ji D, Geng D, Han Y, Deng Y, Geng Y (2024) Degradable n-type organic semiconductors based on Knoevenagel condensation reaction. Adv Funct Mater 34:2400774. https://doi.org/10.1002/adfm.20240077410.1002/adfm.202400774 ↗
54. Zhang Z, Nie X, Wang F, Chen G, Huang W, Xia L, Zhang W, Hao Z, Hong C, Wang L, You Y (2020) Rhodanine-based Knoevenagel reaction and ring-opening polymerization for efficiently constructing multicyclic polymers. Nat Commun 11:3654. https://doi.org/10.1038/s41467-020-17474-010.1038/s41467-020-17474-0 ↗
55. Qu H, Huo C, Ge J, Xue X, Gu Z, Deng R (2024) Symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction for N-C and N-N atropisomers synthesis. Angew Chem Int Ed 63:e202410012. https://doi.org/10.1002/anie.20241001210.1002/anie.202410012 ↗
56. Tauber C, Wamser R, Arkona C, Tügend M, Aziz U, Pach S, Schulz R, Jochmans D, Wolber G, Neyts J, Rademann J (2021) Chemical evolution of antivirals against enterovirus D68 through protein-templated Knoevenagel reactions. Angew Chem Int Ed 60:13294. https://doi.org/10.1002/anie.20210207410.1002/anie.202102074 ↗
57. Zhang Y, Dai T, Zhang F, Zhang J, Chu G, Quan C (2016) Fe3O4@UiO-66-NH2 core-shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation. Chin J Catal 37:2106. https://doi.org/10.1016/s1872-2067(16)62562-710.1016/s1872-2067(16)62562-7 ↗
58. Qiao Y, Zhang L, Li J, Lin W, Wang Z (2016) Switching on supramolecular catalysis via cavity mediation and electrostatic regulation. Angew Chem Int Ed 55:12778. https://doi.org/10.1002/anie.20160684710.1002/anie.201606847 ↗
59. Pan H, Han M, Li P, Wang L (2019) On water direct catalytic vinylogous aldol reaction of silyl glyoxylates. J Org Chem 84:14281. https://doi.org/10.1021/acs.joc.9b0194510.1021/acs.joc.9b01945 ↗