Short-Peptide Supramolecular Hydrogels for In Situ Growth of Metal–Organic Framework-Peptide Biocomposites

The development of bio-MOFs or MOF biocomposites through the combination of MOFs with biopolymers offers the possibility of expanding the potential applications of MOFs, making use of more environmentally benign processes and reagents and giving rise to a new generation of greener and more bio-oriented composite materials. Now, with the increasing use of MOFs for biotechnological applications, the development of new protocols and materials to obtain novel bio-MOFs compatible with biomedical or biotechnological uses is needed. Herein, and as a proof of concept, we have explored the possibility of using short-peptide supramolecular hydrogels as media to promote the growth of MOF particles, giving rise to a new family of bio-MOFs. Short-peptide supramolecular hydrogels are very versatile materials that have shown excellent in vitro and in vivo biomedical applications such as tissue engineering and drug delivery vehicles, among others. These peptides self-assemble by noncovalent interactions, and, as such, these hydrogels are easily reversible, being more biocompatible and biodegradable. These peptides can self-assemble by a multitude of stimuli, such as changes in pH, temperature, solvent, adding salts, enzymatic activity, and so forth. In this work, we have taken advantage of this ability to promote peptide self-assembly with some of the components required to form MOF particles, giving rise to more homogeneous and well-integrated composite materials. Hydrogel formation has been triggered using Zn2+ salts, required to form ZIF-8, and formic acid, required to form MOF-808. Two different protocols for the in situ MOF growth have been developed. Finally, the MOF-808 composite hydrogel has been tested for the decontamination of water polluted with phosphate ions as well as for the catalytic degradation of toxic organophosphate methyl paraoxon in an unbuffered solution.

[1]  J. Navarro,et al.  Oxime@Zirconium-Metal–Organic Framework Hybrid Material as a Potential Antidote for Organophosphate Poisoning , 2023, Inorganic chemistry.

[2]  Md. Wazedur Rahman,et al.  Chirality-Induced Spin Selectivity in Heterochiral Short-Peptide-Carbon-Nanotube Hybrid Networks: Role of Supramolecular Chirality. , 2022, ACS nano.

[3]  J. A. Gavira,et al.  Interactions Between Peptide Assemblies and Proteins for Medicine , 2022, Israel Journal of Chemistry.

[4]  P. Kuzhir,et al.  Injectable Magnetic-Responsive Short-Peptide Supramolecular Hydrogels: Ex Vivo and In Vivo Evaluation , 2021, ACS applied materials & interfaces.

[5]  G. Patriarche,et al.  Monodispersed MOF-808 Nanocrystals Synthesized via a Scalable Room-Temperature Approach for Efficient Heterogeneous Peptide Bond Hydrolysis , 2021, Chemistry of Materials.

[6]  O. Farha,et al.  Near-instantaneous catalytic hydrolysis of organophosphorus nerve agents with zirconium-based MOF/hydrogel composites , 2021, Chem Catalysis.

[7]  S. Lanceros‐Méndez,et al.  Chitin/Metal-Organic Framework composites as wide-range adsorbent. , 2021, ChemSusChem.

[8]  F. Conejero-Lara,et al.  Insulin Crystals Grown in Short-Peptide Supramolecular Hydrogels Show Enhanced Thermal Stability and Slower Release Profile , 2021, ACS applied materials & interfaces.

[9]  E. Gazit,et al.  Biomimetic peptide self-assembly for functional materials , 2020, Nature Reviews Chemistry.

[10]  Sytze J Buwalda Bio-based composite hydrogels for biomedical applications , 2020, Multifunctional Materials.

[11]  N. Cowieson,et al.  Controlling the properties of the micellar and gel phase by varying the counterion in functionalised-dipeptide systems. , 2020, Chemical communications.

[12]  J. Hupp,et al.  Zirconium-Based Metal-Organic Frameworks for the Catalytic Hydrolysis of Organophosphorus Nerve Agents. , 2020, ACS applied materials & interfaces.

[13]  Ruirui Xing,et al.  Nucleation and Growth of Amino-acid and Peptide Supramolecular Polymers through Liquid-liquid Phase Separation. , 2019, Angewandte Chemie.

[14]  A. El Kadib,et al.  Biopolymer@Metal-Organic Framework Hybrid Materials: A Critical Survey , 2019 .

[15]  E. Gazit,et al.  Metal-Ion Modulated Structural Transformation of Amyloid-Like Dipeptide Supramolecular Self-Assembly. , 2019, ACS nano.

[16]  C. Serre,et al.  Metal-Organic Frameworks as Efficient Oral Detoxifying Agents. , 2018, Journal of the American Chemical Society.

[17]  E. Ruiz-Hitzky,et al.  History of Organic–Inorganic Hybrid Materials: Prehistory, Art, Science, and Advanced Applications , 2018 .

[18]  M. López-López,et al.  Iron nanoparticles-based supramolecular hydrogels to originate anisotropic hybrid materials with enhanced mechanical strength , 2018 .

[19]  D. Adams,et al.  Low-Molecular-Weight Gels: The State of the Art , 2017 .

[20]  L. Adler-Abramovich,et al.  Fmoc-modified amino acids and short peptides: simple bio-inspired building blocks for the fabrication of functional materials. , 2016, Chemical Society reviews.

[21]  Qi Zhang,et al.  Alginate Hydrogel: A Shapeable and Versatile Platform for in Situ Preparation of Metal-Organic Framework-Polymer Composites. , 2016, ACS applied materials & interfaces.

[22]  Laura L. E. Mears,et al.  Linking micellar structures to hydrogelation for salt-triggered dipeptide gelators. , 2016, Soft matter.

[23]  T. Kitaoka,et al.  Ultraselective Gas Separation by Nanoporous Metal−Organic Frameworks Embedded in Gas‐Barrier Nanocellulose Films , 2016, Advanced materials.

[24]  G. Westman,et al.  Enhanced Synthesis of Metal‐Organic Frameworks on the Surface of Electrospun Cellulose Nanofibers , 2015 .

[25]  Hong‐Cai Zhou,et al.  Biomimicry in metal-organic materials , 2015 .

[26]  Christian J. Doonan,et al.  Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules , 2015, Nature Communications.

[27]  J. Qu,et al.  Water-based synthesis of zeolitic imidazolate framework-8 with high morphology level at room temperature , 2015 .

[28]  J. A. Gavira,et al.  Influence of the chirality of short peptide supramolecular hydrogels in protein crystallogenesis. , 2015, Chemical communications.

[29]  J. Hinestroza,et al.  One-step growth of isoreticular luminescent metal–organic frameworks on cotton fibers , 2015 .

[30]  Wei‐Yin Sun,et al.  Controlled synthesis of porous coordination-polymer microcrystals with definite morphologies and sizes under mild conditions. , 2014, Chemistry.

[31]  J. Hinestroza,et al.  Antibacterial activity against Escherichia coli of Cu-BTC (MOF-199) metal-organic framework immobilized onto cellulosic fibers , 2014 .

[32]  S. Kitagawa,et al.  Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale. , 2014, Chemical Society reviews.

[33]  Wei Zhu,et al.  Bio-inspired detoxification using 3D-printed hydrogel nanocomposites , 2014, Nature Communications.

[34]  Sunil Kumar Ramasahayam,et al.  A Comprehensive Review of Phosphorus Removal Technologies and Processes , 2014 .

[35]  D. Bradshaw,et al.  Biomineral-inspired growth of metal-organic frameworks in gelatin hydrogel matrices. , 2013, Journal of materials chemistry. B.

[36]  Tom O. McDonald,et al.  Salt-induced hydrogels from functionalised-dipeptides , 2013 .

[37]  Koji Kida,et al.  Formation of high crystalline ZIF-8 in an aqueous solution , 2013 .

[38]  J. Hinestroza,et al.  In situ synthesis of a Cu-BTC metal–organic framework (MOF 199) onto cellulosic fibrous substrates: cotton , 2012, Cellulose.

[39]  Jana K. Maclaren,et al.  Homochiral lanthanoid(III) mesoxalate metal–organic frameworks: synthesis, crystal growth, chirality, magnetic and luminescent properties , 2012 .

[40]  Kyle L. Morris,et al.  Salt-induced hydrogelation of functionalised-dipeptides at high pH. , 2011, Chemical communications.

[41]  Z. Lai,et al.  Rapid synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in an aqueous system. , 2011, Chemical communications.

[42]  M. Popall,et al.  Applications of advanced hybrid organic-inorganic nanomaterials: from laboratory to market. , 2011, Chemical Society reviews.

[43]  Jinxiang Dong,et al.  Synthesis of ZIF-8 and ZIF-67 by steam-assisted conversion and an investigation of their tribological behaviors. , 2011, Angewandte Chemie.

[44]  W. Frith,et al.  Relationship between molecular structure, gelation behaviour and gel properties of Fmoc-dipeptides , 2010 .

[45]  Rein V. Ulijn,et al.  Fmoc‐Diphenylalanine Self Assembles to a Hydrogel via a Novel Architecture Based on π–π Interlocked β‐Sheets , 2008 .

[46]  Michael O’Keeffe,et al.  Exceptional chemical and thermal stability of zeolitic imidazolate frameworks , 2006, Proceedings of the National Academy of Sciences.

[47]  Meital Reches,et al.  Rigid, Self‐Assembled Hydrogel Composed of a Modified Aromatic Dipeptide , 2006 .

[48]  William A. Maher,et al.  Determination of phosphorus in aqueous solution via formation of the phosphoantimonylmolybdenum blue complex re-examination of optimum conditions for the analysis of phosphate , 1995 .

[49]  J. Navarro,et al.  Green synthesis of Zirconium MOF-808 for simultaneous phosphate recovery and organophosphorous pesticide detoxification in wastewater , 2022, Journal of Materials Chemistry A.

[50]  J. M. Delgado-López,et al.  Organic/Inorganic hydrogels by simultaneous self-assembly and mineralization of aromatic short-peptides , 2022, Inorganic Chemistry Frontiers.

[51]  Christian J. Doonan,et al.  Carbohydrates@MOFs , 2019, Materials Horizons.