Abstract

Clay-based nanomaterials, especially 2:1 aluminosilicates such as vermiculite, biotite, and illite, have demonstrated great potential in various fields. However, their characteristic sandwiched structures and the lack of effective methods to exfoliate two-dimensional (2D) functional core layers (FCLs) greatly limit their future applications. Herein, we present a universal wet-chemical exfoliation method based on alkali etching that can intelligently “capture” the ultrathin and biocompatible FCLs (MgO and Fe2O3) sandwiched between two identical tetrahedral layers (SiO2 and Al2O3) from vermiculite. Without the sandwich structures that shielded their active sites, the obtained FCL nanosheets (NSs) exhibit a tunable and appropriate electron band structure (with the bandgap decreased from 2.0 eV to 1.4 eV), a conductive band that increased from −0.4 eV to −0.6 eV, and excellent light response characteristics. The great properties of 2D FCL NSs endow them with exciting potential in diverse applications including energy, photocatalysis, and biomedical engineering. This study specifically highlights their application in cancer theranostics as an example, potentially serving as a prelude to future extensive studies of 2D FCL NSs.

Highlights

  • Clay-based nanomaterials, especially 2:1 aluminosilicates such as vermiculite, biotite, and illite, have demonstrated great potential in various fields

  • Etching with a hot alkaline solution was used to corrode the “bread” SiO2 and Al2O3 layers of VMT, which are very hard to biodegrade in tumor microenvironment (TME), allowing the functional core layers (FCLs), composed of Fe2O3 and magnesium oxide (MgO), to be extracted (Fig. 2a, bottom left)

  • Several nanomedicines have been developed and demonstrated with great therapeutic effects in various cancers: 1D Fe2P nanorods acting as Fenton agents in response to NIR II Light and ultrasound for deep tumor synergetic theranostics57, 2D black phosphorus NSs used as photothermal and photodynamic agents in response to vis/NIR I Light for photonic therapies[58,59,60], and 3D FeS2 nanoparticles serving as photonic and Fenton agents in response to vis/NIR I light for photothermalenhanced chemodynamic therapy (CDT)/PDT51,61,62

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Summary

Introduction

Clay-based nanomaterials, especially 2:1 aluminosilicates such as vermiculite, biotite, and illite, have demonstrated great potential in various fields Their characteristic sandwiched structures and the lack of effective methods to exfoliate two-dimensional (2D) functional core layers (FCLs) greatly limit their future applications. We present a universal wet-chemical exfoliation method based on alkali etching that can intelligently “capture” the ultrathin and biocompatible FCLs (MgO and Fe2O3) sandwiched between two identical tetrahedral layers (SiO2 and Al2O3) from vermiculite. With the development and metamorphism seen in nature, a kind of clay such as vermiculite (VMT), biotite, flogopite, illite, etc., which belong to the 2:1 aluminosilicate family, have emerged These kinds of clays consist of an octahedral layer of magnesium oxide (MgO) and ferric oxide (Fe2O3) sandwiched between two identical tetrahedral layers of SiO2 and Al2O3. MgO is widely used in the clinic and FDA-approved for the treatment of stomach diseases[25]

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