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Title: Versatile Surface Functionalization of Metal-Organic Frameworks through Direct Metal Coordination with a Phenolic Lipid Enables Diverse Applications

Journal Article · · Advanced Functional Materials
 [1];  [2];  [3];  [1];  [4];  [1];  [1];  [5]; ORCiD logo [6]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering
  2. Univ. of Cambridge (United Kingdom). Melville Lab. for Polymer Synthesis, Dept. of Chemistry
  3. City Univ. of Hong Kong, Hong Kong (China). Joint Lab. for Energy and Environmental Catalysis School of Energy and Environment
  4. Monash Univ., Melbourne, VIC (Australia). Dept. of Mechanical and Aerospace Engineering
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
  6. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.

Abstract A novel strategy for the versatile functionalization of the external surface of metal‐organic frameworks (MOFs) has been developed based on the direct coordination of a phenolic‐inspired lipid molecule DPGG (1,2‐dipalmitoyl‐sn‐glycero‐3‐galloyl) with metal nodes/sites surrounding MOF surface. X‐ray diffraction and Argon sorption analysis prove that the modified MOF particles retain their structural integrity and porosity after surface modification. Density functional theory calculations reveal that strong chelation strength between the metal sites and the galloyl head group of DPGG is the basic prerequisite for successful coating. Due to the pH‐responsive nature of metal‐phenol complexation, the modification process is reversible by simple washing in weak acidic water, showing an excellent regeneration ability for water‐stable MOFs. Moreover, the colloidal stability of the modified MOFs in the nonpolar solvent allows them to be further organized into 2 dimensional MOF or MOF/polymer monolayers by evaporation‐induced interfacial assembly conducted on an air/water interface. Finally, the easy fusion of a second functional layer onto DPGG‐modified MOF cores, enabled a series of MOF‐based functional nanoarchitectures, such as MOFs encapsulated within hybrid supported lipid bilayers (so‐called protocells ), polyhedral core‐shell structures, hybrid lipid‐modified‐plasmonic vesicles and multicomponent supraparticles with target functionalities, to be generated. for a wide range of applications.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1464182
Alternate ID(s):
OSTI ID: 1422236
Report Number(s):
SAND-2017-12256J; 658659; TRN: US1902370
Journal Information:
Advanced Functional Materials, Vol. 28, Issue 16; ISSN 1616-301X
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 76 works
Citation information provided by
Web of Science

References (68)

Selective Bifunctional Modification of a Non-catenated Metal−Organic Framework Material via “Click” Chemistry
  • Gadzikwa, Tendai; Farha, Omar K.; Malliakas, Christos D.
  • Journal of the American Chemical Society, Vol. 131, Issue 38, p. 13613-13615 https://doi.org/10.1021/ja904189d
journal September 2009
Applications of metal-organic frameworks featuring multi-functional sites journal January 2016
Covalent surface modification of a metal–organic framework: selective surface engineering via CuI-catalyzed Huisgen cycloaddition journal January 2008
Positioning metal-organic framework nanoparticles within the context of drug delivery – A comparison with mesoporous silica nanoparticles and dendrimers journal April 2017
Colloidal-Sized Metal–Organic Frameworks: Synthesis and Applications journal December 2013
Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging journal December 2009
Post-synthetic metalation of metal–organic frameworks journal January 2014
Rational Design, Synthesis, Purification, and Activation of Metal−Organic Framework Materials journal August 2010
Metal-Organic Framework Nanoparticles in Photodynamic Therapy: Current Status and Perspectives journal March 2017
Metal-phenolic networks as a versatile platform to engineer nanomaterials and biointerfaces journal February 2017
Nature's Other Self-Assemblers journal July 2013
Hydrogen storage in metal–organic frameworks journal January 2009
Directional Self-Assembly of a Colloidal Metal-Organic Framework journal April 2012
Methyl modified MOF-5: a water stable hydrogen storage material journal January 2011
One-Step Assembly of Coordination Complexes for Versatile Film and Particle Engineering journal July 2013
Controlled Fabrication of Functional Capsules Based on the Synergistic Interaction between Polyphenols and MOFs under Weak Basic Condition journal April 2017
Nanoscale Metal–Organic Frameworks for Biomedical Imaging and Drug Delivery journal October 2011
Beyond post-synthesis modification: evolution of metal–organic frameworks via building block replacement journal January 2014
Zr-Based MOFs Shielded with Phospholipid Bilayers: Improved Biostability and Cell Uptake for Biological Applications journal May 2017
Enantioselective catalysis with homochiral metal–organic frameworks journal January 2009
Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO 2 Hydrogenation to Methanol journal November 2016
Revealing the Interfacial Self-Assembly Pathway of Large-Scale, Highly-Ordered, Nanoparticle/Polymer Monolayer Arrays at an Air/Water Interface journal February 2013
Bio-functionalization of metal–organic frameworks by covalent protein conjugation journal January 2011
Moisture-Resistant and Superhydrophobic Metal−Organic Frameworks Obtained via Postsynthetic Modification journal April 2010
Mussel-Inspired Surface Chemistry for Multifunctional Coatings journal October 2007
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828
journal May 2013
Porous Chromium Terephthalate MIL-101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis journal May 2009
Protocells: Modular Mesoporous Silica Nanoparticle-Supported Lipid Bilayers for Drug Delivery journal January 2016
Mesoporous Silica Nanoparticle-Supported Lipid Bilayers (Protocells) for Active Targeting and Delivery to Individual Leukemia Cells journal July 2016
Metal–Organic Framework Thin Films: From Fundamentals to Applications. journal September 2011
Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804 https://doi.org/10.1021/ja408959g
journal October 2013
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications journal February 2017
Engineering Multifunctional Capsules through the Assembly of Metal-Phenolic Networks journal April 2014
Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks journal September 2011
The surface chemistry of metal–organic frameworks journal January 2015
Nucleic Acid–Metal Organic Framework (MOF) Nanoparticle Conjugates journal May 2014
Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal Encapsulation journal May 2008
Postsynthetic modification of metal–organic frameworks journal January 2009
Surface-Specific Functionalization of Nanoscale Metal-Organic Frameworks journal October 2015
Chemistry of SURMOFs: Layer-Selective Installation of Functional Groups and Post-synthetic Covalent Modification Probed by Fluorescence Microscopy journal February 2011
Liposome-Coated Iron Fumarate Metal-Organic Framework Nanoparticles for Combination Therapy journal October 2017
Modular assembly of superstructures from polyphenol-functionalized building blocks journal October 2016
Pore Surface Engineering with Controlled Loadings of Functional Groups via Click Chemistry in Highly Stable Metal–Organic Frameworks journal August 2012
Metal–Organic Frameworks for Separations journal September 2011
Coordinatively Immobilized Monolayers on Porous Coordination Polymer Crystals journal June 2010
Nanostructured metal–organic frameworks and their bio-related applications journal January 2016
Mesoporous Silica Nanoparticle Nanocarriers: Biofunctionality and Biocompatibility journal July 2012
MOF positioning technology and device fabrication journal January 2014
Imparting Functionality to MOF Nanoparticles by External Surface Selective Covalent Attachment of Polymers journal May 2016
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Exosome-Coated Metal–Organic Framework Nanoparticles: An Efficient Drug Delivery Platform journal September 2017
Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials journal August 2013
MOF nanoparticles coated by lipid bilayers and their uptake by cancer cells journal January 2015
Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites journal September 2011
Colorless Multifunctional Coatings Inspired by Polyphenols Found in Tea, Chocolate, and Wine journal August 2013
Multifunctional Nanoparticles by Coordinative Self-Assembly of His-Tagged Units with Metal–Organic Frameworks journal February 2017
Post-Synthetic Anisotropic Wet-Chemical Etching of Colloidal Sodalite ZIF Crystals journal October 2015
Nanomedicine Applications of Hybrid Nanomaterials Built from Metal–Ligand Coordination Bonds: Nanoscale Metal–Organic Frameworks and Nanoscale Coordination Polymers journal April 2015
Void Engineering in Metal-Organic Frameworks via Synergistic Etching and Surface Functionalization journal June 2016
Colorless Multifunctional Coatings Inspired by Polyphenols Found in Tea, Chocolate, and Wine journal August 2013
Coordinatively Immobilized Monolayers on Porous Coordination Polymer Crystals journal June 2010
Directional Self-Assembly of a Colloidal Metal-Organic Framework journal April 2012
Metal–Organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials text January 2013
Amine Grafting on Coordinatively Unsaturated Metal Centers of MOFs: Consequences for Catalysis and Metal Encapsulation journal May 2008
Engineering Multifunctional Capsules through the Assembly of Metal-Phenolic Networks journal April 2014
Nanoscale Metal–Organic Frameworks for Biomedical Imaging and Drug Delivery text January 2011
Surface‐Specific Functionalization of Nanoscale Metal–Organic Frameworks journal October 2015
Post-Synthetic Anisotropic Wet-Chemical Etching of Colloidal Sodalite ZIF Crystals journal October 2015

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Phenolische Bausteine für die Assemblierung von Funktionsmaterialien journal December 2018
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Figures / Tables (9)