College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934, China.
Dalton Trans. 2020 Dec 22;49(48):17772-17778. doi: 10.1039/d0dt03031g.
Two-dimensional (2D) metal-organic framework (MOF) nanosheets have emerged as a new member of 2D nanomaterials for molecular sieving, energy conversion and storage, catalysis and biomedicine. In this paper, a highly dense assembly of porphyrin achievable in porphyrin-integrated MOF nanosheets induced by an ionic liquid is obtained by sonication exfoliation of its bulk crystals. The 2D layered structure MOF, [BMI]2[Ca3(H2TCPP)2(μ2-OH2)2(H2O)2] (1), was firstly prepared by using the ionic liquid assisted synthetic method (H6TCPP = meso-tetra(carboxyphenyl) porphyrin, BMI = 1-butyl-3-methylimidazolium). The laminated layers in 1 clearly indicate a weak interlayer non-covalent interaction but a strong metal-carboxylate bonding within the layers, which facilitates the exfoliation of 1 to form 2D MOF nanosheets (1 NSs). Powder X-ray diffraction (PXRD), high-resolution transmission electron microscopy (HR-TEM) and fast Fourier transform (FFT) patterns revealed that 1 NSs could maintain their crystalline structure after exfoliation. These MOF nanosheets exhibited excellent aqueous dispersibility, biodegradability and high cytotoxicity under light irradiation against MCF-7 cells.
二维（2D）金属有机骨架（MOF）纳米片作为一种新型的 2D 纳米材料，在分子筛、能量转换和存储、催化和生物医学等领域具有广阔的应用前景。本文通过超声剥离其体相晶体，得到了一种由离子液体诱导的卟啉集成 MOF 纳米片中卟啉的高密度组装体。二维层状结构 MOF，[BMI]2[Ca3(H2TCPP)2(μ2-OH2)2(H2O)2]（1），首先通过离子液体辅助合成方法（H6TCPP=间四（羧基苯基）卟啉，BMI=1-丁基-3-甲基咪唑）制备。1 中的层明显表明层间存在较弱的非共价相互作用，但层内存在较强的金属-羧酸盐键合，这有利于 1 的剥离形成 2D MOF 纳米片（1 NSs）。粉末 X 射线衍射（PXRD）、高分辨率透射电子显微镜（HR-TEM）和快速傅里叶变换（FFT）图谱表明，1 NSs 在剥离后仍能保持其晶体结构。这些 MOF 纳米片在光照下对 MCF-7 细胞表现出优异的水分散性、生物降解性和高细胞毒性。
