A new multifunctional graphene oxide/Cu (II)-porphyrin MOF nanocomposite (CuG) comprised of Cu-TCPP MOF supported on graphene oxide (GO) nanosheets, has been fabricated by a solvothermal method at low temperature and one-pot process. Cu-TCPP MOF with universal advantages, such as high porosity, nontoxicity, large surface area, and safe biodegradation, combined with GO allows the achievement of an efficient doxorubicin loading (45.7%) and smart pH-responsive release for chemotherapy. More significantly, more than 97% of DOX was released by CuG at pH 5 which was more than that at pH 7.4 (~ 33.5%), while Cu-TCPP MOF displayed DOX release of 68.5% and 49% at pH 5 and 7.4, respectively, illustrating the effect of GO on the smart MOF construction for controllable releasing behavior in vitro. The results of in vitro anticancer experiments demonstrate that the developed nanocarrier exhibited slight or no cytotoxicity on normal cells, while the drug-loaded nanocarrier increased significant cancer cell-killing ability with higher therapeutic efficacy than free DOX, indicating the sustained release behavior of the CuG nanocarrier without any “burst effect”. Moreover, the in vivo experiments demonstrated that the CuG-DOX exhibited significantly higher anticancer efficiency compared with free DOX. High anti-cancer therapeutic efficacy of this nanoscale carrier as an efficient pH sensitive agent, has the potential to enter further biomedical investigations.

Graphic abstract

A new smart multifunctional graphene oxide–Cu (II)-porphyrin MOF nanocomposite (CuG) formed of Cu-TCPP MOF and graphene oxide (GO) has successfully fabricated and demonstrated an efficient pH-responsive drug release behavior in cancer therapy without using any targeting ligand.

中文翻译：

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Cu (II)-卟啉金属-有机骨架/氧化石墨烯：合成、表征和作为用于乳腺癌治疗的 pH 响应药物载体的应用

一种新型多功能氧化石墨烯/铜 (II)-卟啉 MOF 纳米复合材料 (CuG)，由负载在氧化石墨烯 (GO) 纳米片上的 Cu-TCPP MOF 组成，采用溶剂热法在低温和一锅法工艺下制备。具有高孔隙率、无毒、大表面积和安全生物降解等普遍优势的 Cu-TCPP MOF 与 GO 相结合，可以实现有效的阿霉素负载（45.7%）和用于化疗的智能 pH 响应释放。更重要的是，超过 97% 的 DOX 在 pH 5 下由 CuG 释放，高于 pH 7.4（~33.5%），而 Cu-TCPP MOF 在 pH 5 和 7.4 下显示出 68.5% 和 49% 的 DOX 释放，分别，示出了GO的对智能MOF构造用于体外释放可控行为的影响。体外抗癌实验结果表明，所开发的纳米载体对正常细胞表现出轻微或无细胞毒性，而载药纳米载体显着提高了癌细胞杀伤能力，治疗效果高于游离DOX，表明CuG的缓释行为没有任何“爆发效应”的纳米载体。此外，体内实验表明，与游离 DOX 相比，CuG-DOX 表现出显着更高的抗癌效率。这种纳米级载体作为一种有效的 pH 敏感剂的高抗癌治疗功效，有可能进入进一步的生物医学研究。

图形摘要

由 Cu-TCPP MOF 和氧化石墨烯 (GO) 形成的新型智能多功能氧化石墨烯-Cu (II)-卟啉 MOF 纳米复合材料 (CuG) 已成功制造并证明在癌症治疗中具有有效的 pH 响应药物释放行为，而无需使用任何靶向配体。