RESUMEN

Nanocomposites comprising metal-organic frameworks (MOFs) embedded in a polymeric matrix are promising carriers for drug delivery applications. While understanding the chemical and physical transformations of MOFs during the release of confined drug molecules is challenging, this is central to devising better ways for controlled release of therapeutic agents. Herein, we demonstrate the efficacy of synchrotron microspectroscopy to track the in situ release of 5-fluorouracil (5-FU) anticancer drug molecules from a drug@MOF/polymer composite (5-FU@HKUST-1/polyurethane). Using experimental time-resolved infrared spectra jointly with newly developed density functional theory calculations, we reveal the detailed dynamics of vibrational motions underpinning the dissociation of 5-FU bound to the framework of HKUST-1 upon water exposure. We discover that HKUST-1 creates hydrophilic channels within the hydrophobic polyurethane matrix hence helping to tune drug release rate. The synergy between a hydrophilic MOF with a hydrophobic polymer can be harnessed to engineer a tunable nanocomposite that alleviates the unwanted burst effect commonly encountered in drug delivery.

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RESUMEN

A facile mechanochemical method was employed to accomplish one-pot encapsulation of anti-cancer drug 5-fluorouracil (5-FU as guest) in a metal-organic framework (HKUST-1 as host). Vibrational spectroscopy via inelastic neutron scattering was applied to probe guest-host interactions arising from nanoscale confinement. We compare 5-FU@HKUST-1 derived from in situ and ex situ encapsulation.

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RESUMEN

The field of metal-organic framework (MOF) materials is rapidly advancing toward practical applications; consequently, it is urgent to achieve a better understanding and precise control of their physical properties. Yet, research on the dielectric properties of MOFs is at its infancy, where studies are confined to the static dielectric behavior or lower-frequency response (kHz-MHz) only. Herein, we present the pioneering use of synchrotron-based infrared reflectivity experiments combined with density functional theory (DFT) calculations to accurately determine the dynamic dielectric properties of zeolitic imidazolate frameworks (ZIFs, a topical family of MOFs). We show, for the first time, the frequency-dependent dielectric response of representative ZIF compounds, bridging the near-, mid-, and far-infrared (terahertz, THz) broad-band frequencies. We establish the structure-property relations as a function of framework porosity and structural change. Our comprehensive results will pave the way for novel ZIF-based terahertz applications, such as infrared optical sensors and high-speed wireless communications.

RESUMEN

Emerging nanoporous materials, such as metal-organic frameworks (MOFs), are promising low-k dielectrics central to next-generation electronics and high-speed communication. Hitherto, the dielectric characterization of MOFs is scarce, with very limited experimental data for guiding new materials design and synthesis. Herein we demonstrate the efficacy of high-resolution synchrotron infrared (IR) specular reflectance experiments to study the dynamic dielectric properties of a flexible MOF structure: bistable MIL-53(Al) that exhibits switching between a large pore (LP) and a narrow pore (NP) architecture. We show that the ratio of LP:NP content of a polycrystalline sample can be changed via increased mechanical stress applied for pelletizing the MIL-53(Al) powder. We quantify the frequency-dependent dielectric constants over ∼1 to 120 THz, identifying all dielectric transitions as a function of stress and phase mixtures, showing how porosity modifies MOF's dielectric properties.