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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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NanoMOFs shell stability under physiological conditions and its effect on the nanoparticles colloidal stability and drug release.a) Kinetics of coating detachment under physiological simulated conditions (PBS 9.5 mM, pH 7.4, 37°C) of rhodamine-labeled βCDP (red) or dextran-biotin-FITC (blue) molecules adsorbed on the nanoMOF surface, measured by fluorescence spectroscopy. b) Water stability of nanoMOFs (black) and βCDP-modified nanoMOFs, measured by DLS. c) AZT-TP release from nanoMOFs (black), βCDP-modified nanoMOFs (red) and PEG-modified nanoMOFs (green) in PBS pH 7.4 at 37°C.
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f5: NanoMOFs shell stability under physiological conditions and its effect on the nanoparticles colloidal stability and drug release.a) Kinetics of coating detachment under physiological simulated conditions (PBS 9.5 mM, pH 7.4, 37°C) of rhodamine-labeled βCDP (red) or dextran-biotin-FITC (blue) molecules adsorbed on the nanoMOF surface, measured by fluorescence spectroscopy. b) Water stability of nanoMOFs (black) and βCDP-modified nanoMOFs, measured by DLS. c) AZT-TP release from nanoMOFs (black), βCDP-modified nanoMOFs (red) and PEG-modified nanoMOFs (green) in PBS pH 7.4 at 37°C.

Mentions: The stability of the coating under physiological simulated conditions was investigated. Indeed, serum is a slightly basic medium (pH ~ 7.4) and contains phosphates that promote the biodegradation of metal carboxylates nanoMOFs13. However, whatever the incubation media (phosphate buffer solution (PBS) or cell culture media), less than 10% of the total CD-P coating was detached after 24 hours of incubation (Fig. 5a and S4). It can be concluded that the CD-P-based coating provides a sufficient stability under physiological conditions to play a biological role, knowing that nanoMOFs typically release their drug cargo in less than 24 hours and that nanoparticles generally circulate in the blood stream in shorter time frames28. The cooperative effect of the phosphate units of CD-P enables a firm anchorage of the coating, even in media containing competing phosphates. In contrast, in the absence of strong iron complexing groups, as in the case of the previously described dextran-coated nanoMOF (dextran possesses exclusively hydroxyl groups)13, a fast and substantial coating detachment was observed in PBS (52 and 81% loss after 4 and 24 h, respectively) (Fig. 5a). In conclusion, not only bulky coating agents, but also strong complexing units are required for stable coatings.


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)

NanoMOFs shell stability under physiological conditions and its effect on the nanoparticles colloidal stability and drug release.a) Kinetics of coating detachment under physiological simulated conditions (PBS 9.5 mM, pH 7.4, 37°C) of rhodamine-labeled βCDP (red) or dextran-biotin-FITC (blue) molecules adsorbed on the nanoMOF surface, measured by fluorescence spectroscopy. b) Water stability of nanoMOFs (black) and βCDP-modified nanoMOFs, measured by DLS. c) AZT-TP release from nanoMOFs (black), βCDP-modified nanoMOFs (red) and PEG-modified nanoMOFs (green) in PBS pH 7.4 at 37°C.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f5: NanoMOFs shell stability under physiological conditions and its effect on the nanoparticles colloidal stability and drug release.a) Kinetics of coating detachment under physiological simulated conditions (PBS 9.5 mM, pH 7.4, 37°C) of rhodamine-labeled βCDP (red) or dextran-biotin-FITC (blue) molecules adsorbed on the nanoMOF surface, measured by fluorescence spectroscopy. b) Water stability of nanoMOFs (black) and βCDP-modified nanoMOFs, measured by DLS. c) AZT-TP release from nanoMOFs (black), βCDP-modified nanoMOFs (red) and PEG-modified nanoMOFs (green) in PBS pH 7.4 at 37°C.
Mentions: The stability of the coating under physiological simulated conditions was investigated. Indeed, serum is a slightly basic medium (pH ~ 7.4) and contains phosphates that promote the biodegradation of metal carboxylates nanoMOFs13. However, whatever the incubation media (phosphate buffer solution (PBS) or cell culture media), less than 10% of the total CD-P coating was detached after 24 hours of incubation (Fig. 5a and S4). It can be concluded that the CD-P-based coating provides a sufficient stability under physiological conditions to play a biological role, knowing that nanoMOFs typically release their drug cargo in less than 24 hours and that nanoparticles generally circulate in the blood stream in shorter time frames28. The cooperative effect of the phosphate units of CD-P enables a firm anchorage of the coating, even in media containing competing phosphates. In contrast, in the absence of strong iron complexing groups, as in the case of the previously described dextran-coated nanoMOF (dextran possesses exclusively hydroxyl groups)13, a fast and substantial coating detachment was observed in PBS (52 and 81% loss after 4 and 24 h, respectively) (Fig. 5a). In conclusion, not only bulky coating agents, but also strong complexing units are required for stable coatings.

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