Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals

Morabito, Joseph V.; Chou, Lien‐Yang; Li, Zhehui; Manna, Cesar M.; Petroff, Christopher; Kyada, Rutvin J.; Palomba, Joseph M.; Byers, Jeffery A.; Tsung, Chia‐Kuang

doi:10.1021/ja5054779

Cited by 145 publications

(119 citation statements)

References 32 publications

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“…S17†) so these are expected to be excluded by the micropores of the capsule shell. While two recent reports suggest that oversize molecules such as caffeine 32 and Rhodamine 6G 33 can be encapsulated by ZIF-8 arising from framework expansion or dissociative linker exchange mechanisms, it is most likely that 4–6 pass through very small pin-hole defects within the dense microporous ZIF-8 outer layer which is responsible for the observed albeit very low activity.…”

Section: Resultsmentioning

confidence: 96%

Magnetic MOF microreactors for recyclable size-selective biocatalysis

et al. 2015

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Section: Resultsmentioning

confidence: 96%

Magnetic MOF microreactors for recyclable size-selective biocatalysis

et al. 2015

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“…Thus, drug-delivery systems have become one of the most promising applications for health care 4, 5, 6. A large number of strategies have been studied, but for application, drug-delivery systems must overcome issues surrounding bioavailability,7, 8 the uncontrollable release of drugs (usually due to carrier instability),9, 10, 11 loading capacities,11, 12, 13 particle size,14, 15, 16 nanoparticle cellular internalization routes,14, 17, 18 and toxicity 19, 20. The exceptional storage capacities of metal-organic frameworks (MOFs), together with their robustness and structural tailorability, have made them attractive for a wide variety of applications,21, 22 including several promising breakthroughs in biomedicine 9, 10, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33.…”

Section: Introductionmentioning

confidence: 99%

Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery

Lázaro

Haddad

Sacca

et al. 2017

Chem

300

158

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SummaryThe high storage capacities and excellent biocompatibilities of metal-organic frameworks (MOFs) have made them emerging candidates as drug-delivery vectors. Incorporation of surface functionality is a route to enhanced properties, and here we report on a surface-modification procedure—click modulation—that controls their size and surface chemistry. The zirconium terephthalate MOF UiO-66 is (1) synthesized as ∼200 nm nanoparticles coated with functionalized modulators, (2) loaded with cargo, and (3) covalently surface modified with poly(ethylene glycol) (PEG) chains through mild bioconjugate reactions. At pH 7.4, the PEG chains endow the MOF with enhanced stability toward phosphates and overcome the “burst release” phenomenon by blocking interaction with the exterior of the nanoparticles, whereas at pH 5.5, stimuli-responsive drug release is achieved. The mode of cellular internalization is also tuned by nanoparticle surface chemistry, such that PEGylated UiO-66 potentially escapes lysosomal degradation through enhanced caveolae-mediated uptake. This makes it a highly promising vector, as demonstrated for dichloroacetic-acid-loaded materials, which exhibit enhanced cytotoxicity. The versatility of the click modulation protocol will allow a wide range of MOFs to be easily surface functionalized for a number of applications.

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“…Interestingly, there is some controversy in the literature related to the incorporation of guest molecules into MOFs by diffusion. In general, the diffusion of guest molecules is limited to those that are smaller than the MOF aperture size, but it has been occasionally reported that molecules larger that both aperture and pore sizes can be successfully incorporated . Recent adsorption and diffusion studies of a series of probe molecules have demonstrated the framework flexibility of ZIF‐8, finding a molecular sieving effect in the molecular size range of 4–6 Å …”

Section: Introductionmentioning

confidence: 99%

Encapsulation of Single Plasmonic Nanoparticles within ZIF‐8 and SERS Analysis of the MOF Flexibility

Zheng

Marchi

López-Puente

et al. 2016

Small

164

141

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Hybrid nanostructures composed of metal nanoparticles and metal-organic frameworks (MOFs) have recently received increasing attention toward various applications due to the combination of optical and catalytic properties of nanometals with the large internal surface area, tunable crystal porosity and unique chemical properties of MOFs. Encapsulation of metal nanoparticles of well-defined shapes into porous MOFs in a core-shell type configuration can thus lead to enhanced stability and selectivity in applications such as sensing or catalysis. In this study, the encapsulation of single noble metal nanoparticles with arbitrary shapes within zeolitic imidazolate-based metal organic frameworks (ZIF-8) is demonstrated. The synthetic strategy is based on the enhanced interaction between ZIF-8 nanocrystals and metal nanoparticle surfaces covered by quaternary ammonium surfactants. High resolution electron microscopy and tomography confirm a complete core-shell morphology. Such a well-defined morphology allowed us to study the transport of guest molecules through the ZIF-8 porous shell by means of surface-enhanced Raman scattering by the metal cores. The results demonstrate that even molecules larger than the ZIF-8 aperture and pore size may be able to diffuse through the framework and reach the metal core.

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Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals

Cited by 145 publications

References 32 publications

Magnetic MOF microreactors for recyclable size-selective biocatalysis

Magnetic MOF microreactors for recyclable size-selective biocatalysis

Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery

Encapsulation of Single Plasmonic Nanoparticles within ZIF‐8 and SERS Analysis of the MOF Flexibility

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