Bioinspired Suprahelical Frameworks as Scaffolds for Artificial Photosynthesis.

Kai Tao,Linda J W Shimon,Ruth Aizen,Shuyi Han,Ehud Gazit,Bin Xue,Deqing Mei,Wei Wang,Yi Cao,Zhengyu Xu

doi:10.1021/acsami.0c13295

Abstract

Framework materials have shown promising potential in various biological applications. However, the state-of-the-art components show low biocompatibility or mechanical instability, or cannot integrate both optics and electronics, thus severely limiting their extensive applications in biological systems. Herein, we demonstrate that amide-based bioorganic building blocks, including dipeptides and dipeptide nucleic acids, can self-assemble into hydrogen-bonded suprahelix architectures of controllable handedness, which then form suprahelical frameworks with diverse cavities. Especially, the cavities can be tuned to be hydrophilic or hydrophobic, and the shortest diagonal distance can be modulated from 0.5 to 1.8 nm, with the volume proportion in the unit cell changing from 5 to 60%. Furthermore, the hydrogen bonding networks result in high mechanical rigidity and semiconductively optoelectronic properties, which allow the utilization of the suprahelical frameworks as supramolecular scaffolds for artificial photosynthesis. Our findings reveal amide-based suprahelix architectures acting as bioinspired supramolecular frameworks, thus extending the constituents portfolio and increasing the feasibility of using framework materials for biological applications.

Highlights

Framework-based materials have attracted increasing interest in diverse well-established fields, such as catalysis, separation, sorption, and storage,[1−5] as well as in the emerging ones including smart microchannels and selective screeningseparation in biological systems.[2,3,6] conventional inorganic constituents, such as zeolites, have intrinsically low biocompatibility and engineerability, severely restricting their uses, especially when interfacing complicated biological systems.[7]
We demonstrate that amide-based bioinspired components, including dipeptides and dipeptide nucleic acids, can self-assemble into suprahelices, which further associate into supramolecular frameworks with controllable cavities
The long-range and directional organization of the hydrogen bonds leads to bulky mechanical rigidity and semiconductively photoelectronic characteristics of the suprahelical frameworks, which are further demonstrated to be used as a basis for durable artificial photosynthesis scaffolds

Summary

Introduction

Framework-based materials have attracted increasing interest in diverse well-established fields, such as catalysis, separation, sorption, and storage,[1−5] as well as in the emerging ones including smart microchannels and selective screeningseparation in biological systems.[2,3,6] conventional inorganic constituents, such as zeolites, have intrinsically low biocompatibility and engineerability, severely restricting their uses, especially when interfacing complicated biological systems.[7] Hybrid architectures such as metal−organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) may ameliorate these shortcomings to some extent Their extensive applications are still limited due to several issues, including the involvement of metal ions, restricted biocompatibility, difficulty of morphological or functional modulation, and in many cases, complicated synthesis procedures and mechanical instability.[3,8−13] Recently, several reports demonstrated that biological materials could form supramolecular frameworks by coordination with transition-metal ions (mainly zinc ions).[14−16] these architectures generally have multiple conformational energy landscape minima, resulting in high sensitivity to external factors (such as solvents and adsorbates) and mechanical instability.[17,18] there is a continuing demand for frameworks that can provide flexible modulation and improved properties, along with enhanced eco-friendliness and high structural rigidity.[19−21]. Our findings establish suprahelical frameworks composed of simple bioorganic molecules, presenting a new bioinspired

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Results

Conclusion