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A "green" strategy to construct non-covalent, stable and bioactive coatings on porous MOF nanoparticles.

Agostoni V, Horcajada P, Noiray M, Malanga M, Aykaç A, Jicsinszky L, Vargas-Berenguel A, Semiramoth N, Daoud-Mahammed S, Nicolas V, Martineau C, Taulelle F, Vigneron J, Etcheberry A, Serre C, Gref R - Sci Rep (2015)

Bottom Line: Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings.The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities.The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system.

View Article: PubMed Central - PubMed

Affiliation: Institut Galien, Université Paris-Sud, UMR CNRS 8612, 92290 Chatenay Malabry, France.

ABSTRACT
Nanoparticles made of metal-organic frameworks (nanoMOFs) attract a growing interest in gas storage, separation, catalysis, sensing and more recently, biomedicine. Achieving stable, versatile coatings on highly porous nanoMOFs without altering their ability to adsorb molecules of interest represents today a major challenge. Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings. Cyclodextrin molecules bearing strong iron complexing groups (phosphates) were firmly anchored to the nanoMOFs' surface, within only a few minutes, simply by incubation with aqueous nanoMOF suspensions. The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities. The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system. These results pave the way towards the design of surface-engineered nanoMOFs of interest for applications in the field of targeted drug delivery, catalysis, separation and sensing.

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Related in: MedlinePlus

Evaluation of the nanoMOFs-CD-P interaction.(a) C1s binding energy spectra obtained by XPS for nanoMOFs (black), CD-P (blue) and CDP-modified nanoMOFs (red). (b) Thermograms obtained by ITC as the result of the nanoMOF interaction with CD (red) or CD-P aqueous solutions (black).
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f4: Evaluation of the nanoMOFs-CD-P interaction.(a) C1s binding energy spectra obtained by XPS for nanoMOFs (black), CD-P (blue) and CDP-modified nanoMOFs (red). (b) Thermograms obtained by ITC as the result of the nanoMOF interaction with CD (red) or CD-P aqueous solutions (black).

Mentions: X ray photoelectron spectroscopy (XPS) was used to ascertain the presence of CD-P within the nanoMOF top layers (~5–10 nm depth) and to determine the quantitative % atomic surface composition. After coating with CD-P, both carbon C1s “fingerprints” of the carbon skeleton of MIL-100(Fe) (284.8 and 289 eV: C-C or C-OOH, respectively) and CD-P “fingerprint” (main contribution at 286.3 eV43) were observed (Fig. 4a and Fig S1). The decrease of the % of Fe in the top layers (the C/Fe atomic ratios increased from 7.4 to 12.1 before and after coating, SI, table S2) was indicative of the presence of CD-P in this region. Chemical composition of the top layers corresponds to around one phosphate group per two iron atoms (SI, table S2).


A "green" strategy to construct non-covalent, stable and bioactive coatings on porous MOF nanoparticles.

Agostoni V, Horcajada P, Noiray M, Malanga M, Aykaç A, Jicsinszky L, Vargas-Berenguel A, Semiramoth N, Daoud-Mahammed S, Nicolas V, Martineau C, Taulelle F, Vigneron J, Etcheberry A, Serre C, Gref R - Sci Rep (2015)

Evaluation of the nanoMOFs-CD-P interaction.(a) C1s binding energy spectra obtained by XPS for nanoMOFs (black), CD-P (blue) and CDP-modified nanoMOFs (red). (b) Thermograms obtained by ITC as the result of the nanoMOF interaction with CD (red) or CD-P aqueous solutions (black).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4300503&req=5

f4: Evaluation of the nanoMOFs-CD-P interaction.(a) C1s binding energy spectra obtained by XPS for nanoMOFs (black), CD-P (blue) and CDP-modified nanoMOFs (red). (b) Thermograms obtained by ITC as the result of the nanoMOF interaction with CD (red) or CD-P aqueous solutions (black).
Mentions: X ray photoelectron spectroscopy (XPS) was used to ascertain the presence of CD-P within the nanoMOF top layers (~5–10 nm depth) and to determine the quantitative % atomic surface composition. After coating with CD-P, both carbon C1s “fingerprints” of the carbon skeleton of MIL-100(Fe) (284.8 and 289 eV: C-C or C-OOH, respectively) and CD-P “fingerprint” (main contribution at 286.3 eV43) were observed (Fig. 4a and Fig S1). The decrease of the % of Fe in the top layers (the C/Fe atomic ratios increased from 7.4 to 12.1 before and after coating, SI, table S2) was indicative of the presence of CD-P in this region. Chemical composition of the top layers corresponds to around one phosphate group per two iron atoms (SI, table S2).

Bottom Line: Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings.The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities.The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system.

View Article: PubMed Central - PubMed

Affiliation: Institut Galien, Université Paris-Sud, UMR CNRS 8612, 92290 Chatenay Malabry, France.

ABSTRACT
Nanoparticles made of metal-organic frameworks (nanoMOFs) attract a growing interest in gas storage, separation, catalysis, sensing and more recently, biomedicine. Achieving stable, versatile coatings on highly porous nanoMOFs without altering their ability to adsorb molecules of interest represents today a major challenge. Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings. Cyclodextrin molecules bearing strong iron complexing groups (phosphates) were firmly anchored to the nanoMOFs' surface, within only a few minutes, simply by incubation with aqueous nanoMOF suspensions. The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities. The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system. These results pave the way towards the design of surface-engineered nanoMOFs of interest for applications in the field of targeted drug delivery, catalysis, separation and sensing.

Show MeSH
Related in: MedlinePlus