Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

Verma, Prince; Bannon, Mark S.; Kuenen, Mara K.; Raj, Sanoj; Dhakal, Ankit; Stone, Kevin; Nichols, Asa W.; Machan, Charles W.; Colón, Yamil J.; Letteri, Rachel A.; Giri, Gaurav

doi:10.1021/acs.chemmater.4c00112

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

Journal Article · Thu Jul 25 00:00:00 EDT 2024 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.4c00112· OSTI ID:2446771

Verma, Prince ^[1]; Bannon, Mark S. ^[2]; ^[2]; ^[3]; Dhakal, Ankit ^[2]; ^[4]; ^[2]; ^[2]; ^[3]; ^[2]; ^[2]

Univ. of Virginia, Charlottesville, VA (United States); SLAC
Univ. of Virginia, Charlottesville, VA (United States)
University of Notre Dame, IN (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; AC02-76SF00515

OSTI ID:: 2446771

Alternate ID(s):: OSTI ID: 2481576

Report Number(s):: LA-UR--24-29438

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 36; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (45)

In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes Denny, Michael S.; Cohen, Seth M. Angewandte Chemie International Edition, Vol. 54, Issue 31 https://doi.org/10.1002/anie.201504077	journal	June 2015
Metal-organic framework Uio-66 for adsorption of methylene blue dye from aqueous solutions Mohammadi, A. A.; Alinejad, A.; Kamarehie, B. International Journal of Environmental Science and Technology, Vol. 14, Issue 9 https://doi.org/10.1007/s13762-017-1289-z	journal	May 2017
Therapeutic peptides: Historical perspectives, current development trends, and future directions Lau, Jolene L.; Dunn, Michael K. Bioorganic & Medicinal Chemistry, Vol. 26, Issue 10 https://doi.org/10.1016/j.bmc.2017.06.052	journal	June 2018
Temperature sensitive polyMOF hydrogel formed by in situ open-ring polymerization for infected chronic wound treatment Nie, Wei; Huang, Yixiong; Wang, Yilin Chemical Engineering Journal, Vol. 446 https://doi.org/10.1016/j.cej.2022.136948	journal	October 2022
In-situ synthesis of MOF nanoparticles in double-network hydrogels for stretchable adsorption device Wang, Yiliang; Peng, Hui; Wang, Haomin Chemical Engineering Journal, Vol. 450 https://doi.org/10.1016/j.cej.2022.138216	journal	December 2022
LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales Thompson, Aidan P.; Aktulga, H. Metin; Berger, Richard Computer Physics Communications, Vol. 271 https://doi.org/10.1016/j.cpc.2021.108171	journal	February 2022
Peptide therapeutics: current status and future directions Fosgerau, Keld; Hoffmann, Torsten Drug Discovery Today, Vol. 20, Issue 1 https://doi.org/10.1016/j.drudis.2014.10.003	journal	January 2015
Novel derived pectin hydrogel from mandarin peel based metal-organic frameworks composite for enhanced Cr(VI) and Pb(II) ions removal Mahmoud, Mohamed E.; Mohamed, Asmaa K. International Journal of Biological Macromolecules, Vol. 164 https://doi.org/10.1016/j.ijbiomac.2020.07.090	journal	December 2020
Copper metal-organic framework embedded carboxymethyl chitosan-g-glutathione/polyacrylamide hydrogels for killing bacteria and promoting wound healing Wang, Meng; Huang, Huihua; Ma, Xiaofeng International Journal of Biological Macromolecules, Vol. 187 https://doi.org/10.1016/j.ijbiomac.2021.07.139	journal	September 2021
Carboxymethyl cellulose/tetracycline@UiO-66 nanocomposite hydrogel films as a potential antibacterial wound dressing Javanbakht, Siamak; Nabi, Mohadese; Shadi, Mehrdad International Journal of Biological Macromolecules, Vol. 188 https://doi.org/10.1016/j.ijbiomac.2021.08.061	journal	October 2021
Generalized Approach for Rapid Aqueous MOF Synthesis by Controlling Solution pH Huelsenbeck, Luke; Luo, Hongxi; Verma, Prince Crystal Growth & Design, Vol. 20, Issue 10 https://doi.org/10.1021/acs.cgd.0c00895	journal	September 2020
Controlling Polymorphism and Orientation of NU-901/NU-1000 Metal–Organic Framework Thin Films Verma, Prince K.; Huelsenbeck, Luke; Nichols, Asa W. Chemistry of Materials, Vol. 32, Issue 24 https://doi.org/10.1021/acs.chemmater.0c03539	journal	December 2020
Materials Informatics with PoreBlazer v4.0 and the CSD MOF Database Sarkisov, Lev; Bueno-Perez, Rocio; Sutharson, Mythili Chemistry of Materials, Vol. 32, Issue 23 https://doi.org/10.1021/acs.chemmater.0c03575	journal	November 2020
Strong, Ductile MOF–Poly(urethane urea) Composites Palomba, Joseph M.; Wirth, David M.; Kim, Jin Yeong Chemistry of Materials, Vol. 33, Issue 9 https://doi.org/10.1021/acs.chemmater.0c04874	journal	April 2021
MOF Channels within Porous Polymer Film: Flexible, Self-Supporting ZIF-8 Poly(ether sulfone) Composite Membrane Hess, Samuel C.; Grass, Robert N.; Stark, Wendelin J. Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b02499	journal	October 2016
Room-Temperature Synthesis of UiO-66 and Thermal Modulation of Densities of Defect Sites DeStefano, Matthew R.; Islamoglu, Timur; Garibay, Sergio J. Chemistry of Materials, Vol. 29, Issue 3 https://doi.org/10.1021/acs.chemmater.6b05115	journal	January 2017
Azobenzene Guest Molecules as Light-Switchable CO ₂ Valves in an Ultrathin UiO-67 Membrane Knebel, Alexander; Sundermann, Lion; Mohmeyer, Alexander Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00147	journal	March 2017
Polymer–MOF Hybrid Composites with High Porosity and Stability through Surface-Selective Ligand Exchange Pastore, Vincent J.; Cook, Timothy R.; Rzayev, Javid Chemistry of Materials, Vol. 30, Issue 23 https://doi.org/10.1021/acs.chemmater.8b03881	journal	November 2018
Multivariate CuBTC Metal–Organic Framework with Enhanced Selectivity, Stability, Compatibility, and Processability Peterson, Gregory W.; Au, Kathleen; Tovar, Trenton M. Chemistry of Materials, Vol. 31, Issue 20 https://doi.org/10.1021/acs.chemmater.9b02756	journal	September 2019
Force-Field Prediction of Materials Properties in Metal-Organic Frameworks Boyd, Peter G.; Moosavi, Seyed Mohamad; Witman, Matthew The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02532	journal	January 2017
Novel Metal–Organic Framework-Based Photocrosslinked Hydrogel System for Efficient Antibacterial Applications Gwon, Kihak; Han, Ihn; Lee, Seonhwa ACS Applied Materials & Interfaces, Vol. 12, Issue 18 https://doi.org/10.1021/acsami.0c03187	journal	April 2020
Gel–Print–Grow: A New Way of 3D Printing Metal–Organic Frameworks Lawson, Shane; Alwakwak, Abdo-Aslam; Rownaghi, Ali A. ACS Applied Materials & Interfaces, Vol. 12, Issue 50 https://doi.org/10.1021/acsami.0c18720	journal	December 2020
Alginate Hydrogel: A Shapeable and Versatile Platform for in Situ Preparation of Metal–Organic Framework–Polymer Composites Zhu, He; Zhang, Qi; Zhu, Shiping ACS Applied Materials & Interfaces, Vol. 8, Issue 27 https://doi.org/10.1021/acsami.6b04505	journal	June 2016
Mechanically Strong Metal–Organic Framework Nanoparticle-Based Double Network Hydrogels for Fluorescence Imaging Tang, Li; Gong, Liang; Xu, Yue ACS Applied Nano Materials, Vol. 5, Issue 1 https://doi.org/10.1021/acsanm.1c03034	journal	December 2021
Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks Morris, William; Volosskiy, Boris; Demir, Selcuk Inorganic Chemistry, Vol. 51, Issue 12, p. 6443-6445 https://doi.org/10.1021/ic300825s	journal	June 2012
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations Rappe, A. K.; Casewit, C. J.; Colwell, K. S. Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035 https://doi.org/10.1021/ja00051a040	journal	December 1992
Autocatalysis and Oriented Attachment Direct the Synthesis of a Metal–Organic Framework Dighe, Anish V.; Huelsenbeck, Luke; Bhawnani, Rajan R. JACS Au, Vol. 2, Issue 2 https://doi.org/10.1021/jacsau.1c00494	journal	January 2022
Mapping out the Aqueous Surface Chemistry of Metal Oxide Nanocrystals: Carboxylate, Phosphonate, and Catecholate Ligands Deblock, Loren; Goossens, Eline; Pokratath, Rohan JACS Au, Vol. 2, Issue 3 https://doi.org/10.1021/jacsau.1c00565	journal	March 2022
Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000 Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo Nature Protocols, Vol. 11, Issue 1 https://doi.org/10.1038/nprot.2016.001	journal	December 2015
Angiotensin-converting enzyme 2 and angiotensin 1–7: novel therapeutic targets Jiang, Fan; Yang, Jianmin; Zhang, Yongtao Nature Reviews Cardiology, Vol. 11, Issue 7 https://doi.org/10.1038/nrcardio.2014.59	journal	April 2014
Trends in peptide drug discovery Muttenthaler, Markus; King, Glenn F.; Adams, David J. Nature Reviews Drug Discovery, Vol. 20, Issue 4 https://doi.org/10.1038/s41573-020-00135-8	journal	February 2021
H ₂ storage in isostructural UiO-67 and UiO-66 MOFs Chavan, Sachin; Vitillo, Jenny G.; Gianolio, Diego Phys. Chem. Chem. Phys., Vol. 14, Issue 5 https://doi.org/10.1039/C1CP23434J	journal	January 2012
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework Islamoglu, Timur; Otake, Ken-ichi; Li, Peng CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/C8CE00455B	journal	January 2018
Novel one step preparation of a 3D alginate based MOF hydrogel for water treatment Zhuang, Yuan; Kong, Yan; Wang, Xuechun New Journal of Chemistry, Vol. 43, Issue 19 https://doi.org/10.1039/C8NJ06031B	journal	January 2019
Green synthesis of Zr-based metal–organic framework hydrogel composites and their enhanced adsorptive properties Klein, Shirell E.; Sosa, Joshua D.; Castonguay, Alexander C. Inorganic Chemistry Frontiers, Vol. 7, Issue 24 https://doi.org/10.1039/D0QI00840K	journal	January 2020
Metal–organic framework structure–property relationships for high-performance multifunctional polymer nanocomposite applications Unnikrishnan, Vishnu; Zabihi, Omid; Ahmadi, Mojtaba Journal of Materials Chemistry A, Vol. 9, Issue 8 https://doi.org/10.1039/D0TA11255K	journal	January 2021
Thermal degradation of defective high-surface-area UiO-66 in different gaseous environments Athar, Muhammad; Rzepka, Przemyslaw; Thoeny, Debora RSC Advances, Vol. 11, Issue 61 https://doi.org/10.1039/D1RA05411B	journal	January 2021
Biomineral-inspired growth of metal–organic frameworks in gelatin hydrogel matrices Garai, Ashesh; Shepherd, William; Huo, Jia Journal of Materials Chemistry B, Vol. 1, Issue 30 https://doi.org/10.1039/c3tb20814a	journal	January 2013
Adaptive biasing force method for scalar and vector free energy calculations Darve, Eric; Rodríguez-Gómez, David; Pohorille, Andrew The Journal of Chemical Physics, Vol. 128, Issue 14 https://doi.org/10.1063/1.2829861	journal	April 2008
Revisiting the finite temperature string method for the calculation of reaction tubes and free energies Vanden-Eijnden, Eric; Venturoli, Maddalena The Journal of Chemical Physics, Vol. 130, Issue 19 https://doi.org/10.1063/1.3130083	journal	May 2009
SSAGES: Software Suite for Advanced General Ensemble Simulations Sidky, Hythem; Colón, Yamil J.; Helfferich, Julian The Journal of Chemical Physics, Vol. 148, Issue 4 https://doi.org/10.1063/1.5008853	journal	January 2018
The Scherrer Formula for X-Ray Particle Size Determination Patterson, A. L. Physical Review, Vol. 56, Issue 10 https://doi.org/10.1103/PhysRev.56.978	journal	November 1939
Mercury 4.0 : from visualization to analysis, design and prediction Macrae, Clare F.; Sovago, Ioana; Cottrell, Simon J. Journal of Applied Crystallography, Vol. 53, Issue 1 https://doi.org/10.1107/S1600576719014092	journal	February 2020
Phase I and Pharmacokinetic Study of Angiotensin-(1-7), an Endogenous Antiangiogenic Hormone Petty, W. Jeffrey; Miller, Antonius A.; McCoy, Thomas P. Clinical Cancer Research, Vol. 15, Issue 23 https://doi.org/10.1158/1078-0432.CCR-09-1957	journal	November 2009
Strategic Approaches to Optimizing Peptide ADME Properties Di, Li The AAPS Journal, Vol. 17, Issue 1 https://doi.org/10.1208/s12248-014-9687-3	journal	November 2014

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Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

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