In this work, the covalent attachment of an amine functionalized metal‐organic framework (UiO‐66‐NH2 = Zr6O4(OH)4(bdc‐NH2)6; bdc‐NH2 = 2‐amino‐1,4‐benzenedicarboxylate) (UiO‐Universitetet i Oslo) to the basal‐plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO‐66‐NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO‐66‐NH2 acts as an effective charge storing material with a capacitance of up to 651 F g−1, significantly higher than traditional graphene‐based materials. The results suggest that the amide linkage plays a key role in the formation of a π‐conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO‐66‐NH2 positive electrode with Ti3C2TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg−1 and an energy density of up to 73 Wh kg−1, which are comparable to several commercial devices such as Pb‐acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.
Despite intensive research on the application of two-dimensional (2D) materials, including MXenes, in nanomedicine, the knowledge concerning the mechanisms responsible for their observed bio-effects is far from being understood. Here we present insight into the mechanism of toxicity in vitro of the 2D Ti3C2 MXene. The most important results of this work are that using simple, inexpensive, post-delamination treatments, such as ultrasonication or mild thermal oxidation it is possible to ‘tune’ the cytotoxicity of the Ti3C2T
z
flakes. Sonication of Ti3C2T
z
flakes, or sonication followed by mild oxidation in the water at 60 °C, renders them selectively toxic to cancer cells as compared to non-malignant ones. It relates to the appearance of superficial titanium (III) oxide (Ti2O3) layer corresponding to the type of post-treatment. The presence of surface-Ti2O3 results in a noticeably higher generation of oxidative stress compared to pristine 2D Ti3C2. Our findings give evidence that the sonication and thermal treatments were successful in changing the nature of the surface terminations on the Ti3C2T
z
surfaces. This study makes a significant contribution to the future rationalized surface-management of 2D Ti3C2 MXene as well as encourages new rationalized applications in biotechnology and nanomedicine.
Bullet points:
1. First study on 2D Ti3C2 MXene superficially oxidized to titanium (III) oxide i.e. Ti2O3.
2. By sonication Ti3C2Tz MXene flakes followed by mild thermal oxidation in the water at 60 °C for 24 h, it is possible to ‘tune’ the toxicity of the flakes to cancerous cell lines.
3. Decreases in cell viabilities were dose-dependent.
4. Highest cytotoxic effect was observed for thermally oxidized samples.
5. The thermally oxidized samples were also selectively toxic towards all cancerous cell lines up to 375 mg l−1.
6. Reactive oxygen species generation was identified as a mechanism of toxicity.
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