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Self-assembling peptide semiconductors
Science ( IF 56.9 ) Pub Date : 2017-11-16 , DOI: 10.1126/science.aam9756
Kai Tao 1 , Pandeeswar Makam 1 , Ruth Aizen 1 , Ehud Gazit 1, 2
Affiliation  

Peptide-based semiconductors For semiconductors, one often thinks of inorganic materials, such as doped silicon, or aromatic organic polymers and small molecules. Tao et al. review progress in making semiconductors based on self-assembling short peptides. The structures that form show extensive π and hydrogen bonding leading to a range of semiconductor properties, which can be tuned through doping or functionalization of the peptide sequences. These materials may shed light on biological semiconductors or provide an alternative for constructing biocompatible and therapeutic materials. Science, this issue p. aam9756 BACKGROUND The increasing demand for environmentally friendly organic semiconductors that can be easily fabricated and tuned has inspired scientists to design self-assembling peptide nanostructures with enhanced semiconducting characteristics. Recently designed bioinspired peptide semiconductors display various supramolecular morphologies with diverse optical and electrical properties, including intrinsic fluorescence, which facilitates real-time detection and quantitative assessment of the self-association process without a need for external conjugation. These assemblies have also been studied for their potential use in ferroelectric-related devices and ultrasensitive electrochemical sensors. In addition to their low-cost fabrication and structural diversity, bioinspired self-assembling peptide semiconductors may serve as candidates for advanced interdisciplinary functional nanostructures. Promotion of the design principles of peptide-based supramolecular materials is thus of great interest for both scientific and engineering development. ADVANCES Short peptides, specifically those containing aromatic amino acids, can self-assemble into a wide variety of supramolecular structures that are kinetically or thermodynamically stable; the representative models are diphenylalanine and phenylalanine-tryptophan. Different assembly strategies can be used to generate specific functional organizations and nanostructural arrays, resulting in finely tunable morphologies with controllable semiconducting characteristics. Such strategies include molecular modification, microfluidics, coassembly, physical or chemical vapor deposition, and introduction of an external electromagnetic field. Density functional theory simulations have revealed that extensive, directional aromatic interactions and hydrogen-bonding networks lead to the formation of quantum confined domains within the nanostructures, underlying the molecular origin of their intrinsic semiconductivity. These computational studies provide a conceptual framework for the tunability of the semiconductivity of a peptide assembly, and also demonstrate the feasibility of theoretical probing of the mechanisms leading to band gap formation and the subsequent design of building blocks with desired electronic properties. Recent studies have further elucidated some remarkable physicochemical features of the bioinspired supramolecular semiconductors, including absorption spectra characteristic of one-dimensional quantum dots or two-dimensional quantum wells, photoluminescence emission in the visible spectrum, optical waveguiding, temperature-dependent electrical conductivity, ferroelectric (piezoelectric, pyroelectric) properties, and electrochemical properties useful in ultrasensitive detectors and ultracapacitors. OUTLOOK Semiconductive materials are at the foundation of the modern electronics and optics industries. Self-assembling peptide nanomaterials may serve as an alternative source for the semiconductor industry because they are eco-friendly, morphologically and functionally flexible, and easy to prepare, modify, and dope. Moreover, the diverse bottom-up methodologies of peptide self-assembly facilitate easy and cost-effective device fabrication, with the ability to integrate external functional moieties. For example, the coassembly of peptides and electron donors or acceptors can be used to construct n-p junctions, and vapor deposition technology can be applied to manufacture custom-designed electronics and chips on various substrates. The inherent bioinspired nature of self-assembling peptide nanostructures allows them to bridge the gap between the semiconductor world and biological systems, thus making them useful for applications in fundamental biology and health care research. Short peptide self-assemblies may shed light on the roles of protein semiconductivity in physiology and pathology. For example, research into the relationship between the semiconductive properties of misfolded polypeptides characteristic of various neurodegenerative diseases and the resulting symptoms may offer opportunities to investigate the mechanisms controlling such ailments and to develop therapeutic solutions. Finally, self-assembling short peptide semiconductors could be used to develop autonomous biomachines operating within biological systems. This would allow, for example, direct, label-free, real-time monitoring of a variety of metabolic activities, and even interference with biological systems. Peptide building blocks self-assemble into quantum confined supramolecular semiconductors. These bioinspired functional materials can serve as organic semiconductors. Their ability to connect the semiconductor field and the biological world will facilitate the incorporation of semiconductivity into fundamental biomedical and health care applications. Semiconductors are central to the modern electronics and optics industries. Conventional semiconductive materials bear inherent limitations, especially in emerging fields such as interfacing with biological systems and bottom-up fabrication. A promising candidate for bioinspired and durable nanoscale semiconductors is the family of self-assembled nanostructures comprising short peptides. The highly ordered and directional intermolecular π-π interactions and hydrogen-bonding network allow the formation of quantum confined structures within the peptide self-assemblies, thus decreasing the band gaps of the superstructures into semiconductor regions. As a result of the diverse architectures and ease of modification of peptide self-assemblies, their semiconductivity can be readily tuned, doped, and functionalized. Therefore, this family of electroactive supramolecular materials may bridge the gap between the inorganic semiconductor world and biological systems.

中文翻译:

自组装肽半导体

肽基半导体 对于半导体,人们通常会想到无机材料,例如掺杂硅,或芳香族有机聚合物和小分子。陶等人。回顾基于自组装短肽制造半导体的进展。形成的结构显示出广泛的 π 和氢键,导致一系列半导体特性,可以通过肽序列的掺杂或功能化进行调整。这些材料可能会阐明生物半导体或为构建生物相容性和治疗材料提供替代方案。科学,这个问题 p。aam9756 背景对易于制造和调整的环保有机半导体的需求不断增长,这激发了科学家们设计具有增强半导体特性的自组装肽纳米结构的灵感。最近设计的仿生肽半导体显示出具有多种光学和电学特性的各种超分子形态,包括固有荧光,这有助于实时检测和定量评估自缔合过程,而无需外部共轭。还研究了这些组件在铁电相关设备和超灵敏电化学传感器中的潜在用途。除了它们的低成本制造和结构多样性之外,仿生自组装肽半导体可以作为先进的跨学科功能纳米结构的候选者。因此,推广基于肽的超分子材料的设计原理对科学和工程发展都具有重要意义。进展 短肽,特别是那些含有芳香族氨基酸的短肽,可以自组装成各种动力学或热力学稳定的超分子结构;代表性模型是二苯丙氨酸和苯丙氨酸-色氨酸。不同的组装策略可用于生成特定的功能组织和纳米结构阵列,从而产生具有可控半导体特性的微调形态。这些策略包括分子修饰、微流体、共组装、物理或化学气相沉积,以及外部电磁场的引入。密度泛函理论模拟表明,广泛的、定向的芳香相互作用和氢键网络导致在纳米结构内形成量子限制域,这是其固有半导体的分子起源。这些计算研究为肽组装的半导体性的可调性提供了一个概念框架,并证明了对导致带隙形成的机制进行理论探索的可行性,以及随后设计具有所需电子特性的构建块的可行性。最近的研究进一步阐明了仿生超分子半导体的一些显着的物理化学特征,包括一维量子点或二维量子阱的吸收光谱特性、可见光谱中的光致发光发射、光波导、随温度变化的电导率、铁电(压电、热电)特性以及可用于超灵敏探测器和超级电容器的电化学特性. 展望 半导体材料是现代电子和光学行业的基础。自组装肽纳米材料可以作为半导体行业的替代来源,因为它们环保、形态和功能灵活、易于制备、修饰和掺杂。此外,肽自组装的各种自下而上的方法促进了简单且具有成本效益的设备制造,具有整合外部功能部分的能力。例如,肽和电子供体或受体的共组装可用于构建 np 结,气相沉积技术可用于在各种基板上制造定制设计的电子产品和芯片。自组装肽纳米结构固有的仿生性质使它们能够弥合半导体世界和生物系统之间的差距,从而使它们可用于基础生物学和医疗保健研究。短肽自组装可能阐明蛋白质半导体在生理学和病理学中的作用。例如,研究各种神经退行性疾病特有的错误折叠多肽的半导体特性与由此产生的症状之间的关系,可能为研究控制此类疾病的机制和开发治疗方案提供机会。最后,自组装短肽半导体可用于开发在生物系统内运行的自主生物机器。例如,这将允许直接、无标记、实时监测各种代谢活动,甚至干扰生物系统。肽构建块自组装成量子限制的超分子半导体。这些仿生功能材料可以用作有机半导体。它们连接半导体领域和生物世界的能力将有助于将半导体纳入基本的生物医学和医疗保健应用。半导体是现代电子和光学行业的核心。传统的半导体材料具有固有的局限性,特别是在新兴领域,例如与生物系统的接口和自下而上的制造。生物启发和耐用纳米级半导体的一个有前途的候选者是包含短肽的自组装纳米结构家族。高度有序和定向的分子间 π-π 相互作用和氢键网络允许在肽自组装内形成量子限制结构,从而将超结构的带隙降低到半导体区域。由于肽自组装的不同结构和易于修饰,它们的半导体性可以很容易地调整、掺杂和功能化。因此,这一系列电活性超分子材料可以弥合无机半导体世界与生物系统之间的差距。
更新日期:2017-11-16
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