CHEMICAL SCIENCE

Asymmetric mesoporous materials are used to construct biomimetic logic gates


On April 13, 2023, the team of Academician Dongyuan Zhao and Professor Xiaomin Li of Fudan University published a new paper entitled “Emulsion-oriented assembly for Janus double-spherical mesoporous nanoparticles as biological logic gates” in the journal Nature Chemistry. By selectively modifying and loading in different mesoporous units, the research group realized the internal series signal transmission of single particles for the first time, and constructed a single-particle level biomimetic biomass logic system. Postdoctoral fellow Zhao Tiancong is the first author, and Academician Zhao Dongyuan and Professor Li Xiaomin are co-corresponding authors.

Mesoporous materials have a wide range of application prospects in many fields due to their high specific surface and pore volume, unique and adjustable mesoporous structure, etc. One of the most unique characteristics of mesoporous materials is that the guest material can be loaded in the mesoporous pores, combined with the design of the orifice switch, to achieve the responsive release and delivery of guest molecules, which is particularly important in the field of nanomedicine.

There are many ways of information transmission in nature, among which intracellular and organelle information transmission is widely concerned by researchers because of its high specificity and selectivity. Mesoporous materials are considered to have high prospects in simulating information transmission in nature and constructing biomass logic systems because of their ability to control loading and release guest substances. However, in order to simulate the highly complex internal logic system of cells, the first condition is to construct multiple independent signal storage and conversion units similar to organelles. Traditional isotropic mesoporous nanomaterials usually contain only one set of mesopores and one mesoporous pore size, so the various guest species can only be mixed together when loaded. Such nanoparticles with a single mesoporous size and storage space do not meet the needs of complex applications such as biologic gates and multimodal drug release.

Unlike traditional isotropic mesoporous nanoparticles, multiple mesoporous units in asymmetric mesoporous nanoparticles exist independently of each other and do not interfere with or mask each other spatially. Therefore, asymmetric mesoporous nanoparticles can be used to construct a biomimetic biomass logic system, and multiple independent mesoporous units can be regarded as organelles running independently in cells, and they are constructed as signal input, internal processing and output units respectively to realize the independent existence of a variety of internal “arithmetic units”. However, the asymmetric nanomaterials reported so far are mainly non-porous or only have small mesopores (< 3 nm), and small pores cannot achieve loading of large-sized functional biomolecules. Therefore, there is an urgent need to fabricate mesoporous asymmetric nanoparticles with large pore sizes and adjustable pore sizes, but as of now, this is still a huge challenge.

In this latest study, the team of Academician Zhao Dongyuan and Professor Li Xiaomin synthesized double mesoporous asymmetric MSN&mPDA nanoparticles with adjustable macropores (MSN = mesoporous silica nanoparticles, mPDAs = mesoporous polydopamine) based on the novel emulsion-induced anisotropic assembly strategy. The resulting double mesoporous asymmetric MSN&mPDA nanoparticles have a peanut-like asymmetric morphology, each consisting of an MSN nanosphere of about 150 nm and an mPDA hemispherical shape with a diameter of about 120 nm. Unlike previously reported mesoporous Janus nanoparticles and small and non-tunable mesopores (< 3 nm), these asymmetric nanoparticles have large and tunable mesopores in both MSN and mPDA units. The size of the mesopores in the MSN cell can be adjusted from ~3 to ~25 nm, and the mPDA unit also has mesopores with variable diameter ranging from ~5 to ~50 nm. By selectively modifying and loading in different mesoporous units, the research group realized the internal series signal transmission of single particles for the first time, and constructed a single-particle level biomimetic biomass logic system.

Figure 1: Schematic diagram and morphological characterization of asymmetric MSN&mPDA nanoparticle preparation process.

Figure 2: MSN&mPDA nanoparticles with different mesoporous pore sizes.

Figure 3: Emulsion orientation-induced anisotropic assembly mechanism.

Figure 4: Biomass logic gates constructed by asymmetric bimesoporous nanoparticles.

In summary, the research group successfully synthesized asymmetric MSN&mPDA nanoparticles with double macropores and adjustable pore size by emulsion-induced directed assembly, and used them for the study of biomimetic biomass logic systems. This is the first time to construct asymmetric mesoporous nanomaterials by nano-emulsion interaction, and it is also the first time to achieve precise regulation of the mesoporous pore size of different units of double mesoporous asymmetric nanomaterials. Using the unique asymmetric structure and double large adjustable mesopores, a single-particle level tandem information transfer system was successfully established, which realized the imitation of intracellular logic signal transmission. This double mesoporous MSN&mPDA nanoparticle has dual macroporous and tunable pores, and is selectively functionalized and highly extensible, which is not only a multifunctional platform for biological logic gates, but also has great potential in the fields of catalysis, energy storage, sensing and environmental remediation. (Source: Science Network)

Related paper information:https://doi.org/10.1038/s41557-023-01183-4



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