Degradation Mechanism of Metal–Organic Framework Drug Nanocarriers Studied by Solid-State Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopy

Vuong, Mai Dang Le; Christodoulou, Ioanna; Porcino, Marianna; Dong, Si-Thanh; Lassalle‐Kaiser, Benedikt; Haouas, Mohamed; Gref, Ruxandra; Martineau‐Corcos, Charlotte

doi:10.1021/acs.chemmater.2c01190

Cited by 5 publications

(26 citation statements)

References 63 publications

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“…Globally, the profiles of trimesate release from both nanoMIL-100s consist of two stages: (i) a fast stage in the first 3 h after incubation in PBS and (ii) a subsequent gradual stage until the equilibrium is reached after around 24 h. Other authors, including us, also found this time-dependent release pattern. 27,28,40,41 In this investigation, we demonstrate that the phosphate-to-metal molar ratio (P/M) directly influences the extent of nanoMIL-100 degradation. When incubating nanoMIL-100 in deionized (DI) water with no phosphate, a negligible amount of trimesate was detected by lqNMR, less than 2% in the case of nanoMIL-100(Al) and nonobservable for nanoMIL-100 (Fe).…”

Section: Degradation Mechanisms Of Original Nanomil-100(al) and Nanom...mentioning

confidence: 81%

“…The triphosphate ATP is a much stronger complexing ligand toward metal(III) cations than AMP; thus, breaking the coordination between ATP and Al(III) is more difficult. As we hypothesized, 41 PBS probably attacks the Al−O−C bond with trimesate first, forming the 6coordinate Al−O−P observed at −2 to −5 ppm in the 27 Al NMR spectrum. Then, ATP is substituted by PBS and released from MIL-100(Al).…”

Section: Degradation and Drugmentioning

confidence: 81%

“…40 Our recent study reported for the first time the atomic-scale structure of degraded nanoMIL-100(Al) and nanoMIL-100 (Fe), evidenced by solid-state NMR (ssNMR) and X-ray absorption near edge structure spectroscopy, revealing a stepwise reaction process. 41 We also demonstrated the evolution of the metal coordination structure for ATP-loaded and CDP-coated nanoMIL-100(Al). Nevertheless, we have yet to prove whether our proposed mechanism is generalizable to nanoMIL-100 DDSs.…”

Section: Introductionmentioning

confidence: 91%

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Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Vuong,

Horbenko,

Frégnaux

et al. 2024

ACS Appl. Mater. Interfaces

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To make a drug work better, the active substance can be incorporated into a vehicle for optimal protection and control of the drug delivery time and space. For making the drug carrier, the porous metal−organic framework (MOF) can offer high drug-loading capacity and various designs for effective drug delivery performance, biocompatibility, and biodegradability. Nevertheless, its degradation process is complex and not easily predictable, and the toxicity concern related to the MOF degradation products remains a challenge for their clinical translation. Here, we describe an in-depth molecular and nanoscale degradation mechanism of aluminum-and iron-based nanoMIL-100 materials exposed to phosphate-buffered saline. Using a combination of analytical tools, including X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, small-angle X-ray scattering, and electron microscopy, we demonstrate qualitatively and quantitatively the formation of a new coordination bond between metal(III) and phosphate, trimesate release, and correlation between these two processes. Moreover, the extent of material erosion, i.e., bulk or surface erosion, was examined from the transformation of nanoparticles' surface, morphology, and interaction with water. Similar analyses show the impact of drug loading and surface coating on nanoMIL-100 degradation and drug release as a function of the metal−ligand binding strength. Our results indicate how the chemistry of nanoMIL-100(Al) and nanoMIL-100(Fe) drug carriers affects their degradation behaviors in a simulated physiological medium. This difference in behavior between the two nanoMIL-100s enables us to better correlate the nanoscale and atomic-scale mechanisms of the observed phenomena, thus validating the presented multiscale approach.

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Section: Degradation Mechanisms Of Original Nanomil-100(al) and Nanom...mentioning

confidence: 81%

Section: Degradation and Drugmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 91%

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Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Vuong,

Horbenko,

Frégnaux

et al. 2024

ACS Appl. Mater. Interfaces

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“…Solid-state NMR is frequently utilized to analyze the chemical composition of various MOF composites. − The relative molar ratio between MIL-53 and PDMS in a series of PDMS-coated MIL-53 is directly determined from the 1 H MAS NMR spectra, which is summarized in Table S1. The molecular formula for representing the chemical composition of MIL-53@PDMS-10, MIL-53@PDMS-20, MIL-53@PDMS-30, MIL-53@PDMS-40, and MIL-53@PDMS-60 can be described as [Al(OH)(BDC)][Si(CH 3 ) 2 O] 0.3 , [Al(OH)(BDC)][Si(CH 3 ) 2 O] 1.0 , [Al(OH)(BDC)][Si(CH 3 ) 2 O] 1.5 , [Al(OH)(BDC)][Si(CH 3 ) 2 O] 2.7 , and [Al(OH)(BDC)][Si(CH 3 ) 2 O] 3.0 , respectively (see Table S1).…”

Section: Resultsmentioning

confidence: 99%

Surface Hydrophobicity and Guest Permeability in Polydimethylsiloxane-Coated MIL-53 as Studied by Solid-State Nuclear Magnetic Resonance Spectroscopy

He,

Li,

Jiang

et al. 2023

ACS Appl. Mater. Interfaces

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Experimental characterization of the hydrophobic porous materials at the atomic and molecular levels is of great significance, but exploring their hydrophobicity characteristics and interactions with guest molecules with distinct polarity is still challenging. In this work, solid-state NMR is employed to characterize the surface hydrophobicity and explore the guest solvent permeability in polydimethylsiloxane (PDMS)-coated MIL-53. It was found that the PDMS-coated MIL-53 was hydrophobic to water and infiltrated to methanol, acetone, benzene, toluene, and ethylbenzene solvents. In addition, two types of guest solvents (methanol, acetone, benzene, toluene, and ethylbenzene), inside the pore and outside the pore of PDMS-coated MIL-53, were clearly identified using two-dimensional 1 H− 1 H homo-nuclear correlation NMR experiments. Moreover, the membrane thickness of the PDMS-coated MIL-53 could be determined from the analysis of the 1 H− 1 H spin diffusion buildup curves. Furthermore, the permeability of benzene, toluene, and ethylbenzene at different PDMS coating levels was extracted from 1 H MAS NMR. The increase of the hydrophobic PDMS layer resulted in a decrease of the penetration of aromatic guests to the internal pore of MIL-53. This work provides deep insights into the understanding of guest solvent permeability of hydrophobic layer-coated MOFs in the application fields of catalysis and separation.

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“…[44] In addition, there has been much work on the MOF degradation (e.g., ZIF-8 and MIL-100(Fe)) in phosphate-containing media. [45,46]…”

Section: Introductionmentioning

confidence: 99%

A Micrometric Transformer: Compositional Nanoshell Transformation of Fe³⁺‐Trimesic‐Acid Complex with Concomitant Payload Release in Cell‐in‐Catalytic‐Shell Nanobiohybrids

Park,

Kim,

Han

et al. 2023

Advanced Science

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Nanoencapsulation of living cells within artificial shells is a powerful approach for augmenting the inherent capacity of cells and enabling the acquisition of extrinsic functions. However, the current state of the field requires the development of nanoshells that can dynamically sense and adapt to environmental changes by undergoing transformations in form and composition. This paper reports the compositional transformation of an enzyme‐embedded nanoshell of Fe3+‐trimesic acid complex to an iron phosphate shell in phosphate‐containing media. The cytocompatible transformation allows the nanoshells to release functional molecules without loss of activities and biorecognition, while preserving the initial shell properties, such as cytoprotection. Demonstrations include the lysis and killing of Escherichia coli by lysozyme, and the secretion of interleukin‐2 by Jurkat T cells in response to paracrine stimulation by antibodies. This work on micrometric Transformers will benefit the creation of cell‐in‐shell nanobiohybrids that can interact with their surroundings in active and adaptive ways.

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Degradation Mechanism of Metal–Organic Framework Drug Nanocarriers Studied by Solid-State Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopy

Cited by 5 publications

References 63 publications

Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Surface Hydrophobicity and Guest Permeability in Polydimethylsiloxane-Coated MIL-53 as Studied by Solid-State Nuclear Magnetic Resonance Spectroscopy

A Micrometric Transformer: Compositional Nanoshell Transformation of Fe³⁺‐Trimesic‐Acid Complex with Concomitant Payload Release in Cell‐in‐Catalytic‐Shell Nanobiohybrids

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Degradation Mechanism of Metal–Organic Framework Drug Nanocarriers Studied by Solid-State Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopy

Cited by 5 publications

References 63 publications

Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Degradation and Erosion of Metal–Organic Frameworks: Comparative Study of a NanoMIL-100 Drug Delivery System

Surface Hydrophobicity and Guest Permeability in Polydimethylsiloxane-Coated MIL-53 as Studied by Solid-State Nuclear Magnetic Resonance Spectroscopy

A Micrometric Transformer: Compositional Nanoshell Transformation of Fe3+‐Trimesic‐Acid Complex with Concomitant Payload Release in Cell‐in‐Catalytic‐Shell Nanobiohybrids

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A Micrometric Transformer: Compositional Nanoshell Transformation of Fe³⁺‐Trimesic‐Acid Complex with Concomitant Payload Release in Cell‐in‐Catalytic‐Shell Nanobiohybrids