Self‐Assembled Metal–Organic Framework Stabilized Organic Cocrystals for Biological Phototherapy

Abstract

Organic self‐assembled co‐crystals have garnered considerable attention due to their facile synthesis and intriguing properties, but supramolecular interactions restrict their stability in aqueous solution, which is especially important for biological applications. Herein, we report on the first biological application of aqueous dispersible self‐assembled organic co‐crystals via the construction of metal–organic framework (MOF) ‐stabilized co‐crystals. In particular, we built an electron‐deficient MOF with naphthalene diimide (NDI) as the ligand and biocompatible Ca2+ as the metal nodes. An electron donor molecule, pyrene, was encapsulated to form the host–guest MOF self‐assembled co‐crystal. We observed that such MOF structure leads to uniquely high‐density ordered arrangement and the close intermolecular distance (3.47 Å) of the charge transfer pairs. Hence, the concomitant superior charge transfer interaction between pyrene/NDI can be attained and the resultant photothermal conversion efficiency of Py@Ca‐NDI in aqueous solution can thus reach up to 41.8 %, which, to the best of our knowledge, is the highest value among the reported organic co‐crystal materials; it is also much higher than that of the FDA approved photothermal agent ICG as well as most of the reported MOFs. Based on this realization, as a proof of concept, we demonstrated that such a self‐assembled organic co‐crystal platform can be used in biological applications that are exemplified via highly effective long wavelength light photothermal therapy.

HKUST-1 nano metal–organic frameworks combined with ZnGa2O4:Cr3+ near-infrared persistent luminescence nanoparticles for in vivo imaging and tumor chemodynamic and photothermal synergic therapy

“…19 The calculated PTE of HSZGO was about 58.7% (Fig. 4e), which is higher than other reported NMOF materials used for cancer therapy, like Mn-ZrMOF(28.7%), 40 Cu-TCPP MOF(36.8%), 41 Cu-MOF (HKUST-1) nanoenzyme (45.7%), 9 Py@Ca-NDI (41.8%), 42 Fe( iii ) porphyrin-containing MOF(41%), 43 Zr-FeP MOF(33.7%), 44 and Zr-Fc MOF (53%). 45 The HSZGO exhibited a good and reproducible photothermal stability with slight changes in the maximum temperatures during the six light on/off cycles (Fig.…”

Organic Charge-Transfer Cocrystals toward Large-Area Nanofiber Membrane for Photothermal Conversion and Imaging

“…17 Inspired by the orbital hybridization, the cocrystal strategy could controllably narrow the bandgap for red-shifted emission/absorption, 17 which supplies a feasible avenue to rationally design and synthesize the desired photothermal materials. However, the limited successes of the CT cocrystal with excellent photothermal performance mostly concentrate on the exploration stage, with many challenges remaining for their practical applications, such as poor water dispersibility, 21 limited programmable substrates, and blurry excited state dynamics. 22 Significantly, electrospinning technology was regarded as a promising candidate to construct the nanofiber platforms combined with various multifunctional nanomaterials, on account of its precisely controllable morphology of nanofiber substrates in large-scale fabrication.…”

Metal-organic frameworks for hepatocellular carcinoma therapy and mechanism

“…The heat generated by PTT can improve blood flow and oxygen supply, thus improving the sensitivity of tumor cells to oxygen-dependent PDT. Furthermore, ROS produced by PDT can interfere with tumor physiology and change the microenvironment, thus improving the thermal sensitivity of tumor cells ( Sun X et al, 2021 ; Zeng et al, 2021 ).…”