The Impact of Single Amino Acid Insertion on the Supramolecular Assembly Pathway of Aromatic Peptide Amphiphiles

IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Ayato Higuchi, Arka Som, Rie Wakabayashi, Masahiro Goto, Noriho Kamiya, Pol Besenius
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Abstract

Understanding the mechanism of self-assembly driven by non-covalent interactions is crucial for designing supramolecular materials with desired properties. Here we investigate the self-assembly of aromatic peptide amphiphiles, Fmoc-L2QG and Fmoc-L3QG using a combination of spectroscopic, transmission electron and superresolution optical microscopy techniques. Our results show that Fmoc-L2QG leads to concentration-dependent assembly, forming fibrous assemblies at low concentrations and supramolecular droplets via liquid-liquid phase separation (LLPS) at higher concentrations. Mechanical activation using for example ultrasonication triggered the transition from metastable droplets to fibre morphologies of Fmoc-L2QG. In contrast, Fmoc-L3QG followed both on-pathway and off-pathway routes, resulting in the formation of fibrous morphologies regardless of concentration. Seeding experiments revealed that homo-seeds of the same peptide sequence accelerated the on-pathway process, while hetero-seeds of a mismatched peptide sequences accelerated the off-pathway process, highlighting the competing nature of the complex assembly profile. These findings demonstrate the significant impact of single amino acid insertion on the supramolecular assembly process of oligopeptide monomers, and highlight the potential for controlling the structure and dynamics of peptide materials. Pathway engineering of oligopeptide building blocks and multidomain supramolecular monomers will open new avenues in tailor-made and customizable supramolecular biomaterials.

Abstract Image

单个氨基酸插入对芳香族肽两亲化合物超分子组装途径的影响
了解非共价相互作用驱动的自组装机制对于设计具有理想性能的超分子材料至关重要。本文利用光谱学、透射电子和超分辨光学显微镜技术,研究了芳香肽两亲分子Fmoc-L2QG和Fmoc-L3QG的自组装过程。我们的研究结果表明,Fmoc-L2QG导致浓度依赖的组装,在低浓度下形成纤维组装,在高浓度下通过液-液相分离(LLPS)形成超分子液滴。使用超声波等机械激活触发了Fmoc-L2QG从亚稳液滴到纤维形态的转变。相比之下,Fmoc-L3QG遵循通路内和通路外两种途径,导致纤维形态的形成,无论浓度如何。播种实验表明,相同肽序列的同源种子加速了通路上的过程,而不匹配肽序列的异源种子加速了通路外的过程,突出了复杂组装谱的竞争性质。这些发现证明了单氨基酸插入对寡肽单体超分子组装过程的重大影响,并强调了控制肽材料结构和动力学的潜力。寡肽构建模块和多结构域超分子单体的途径工程将为定制和定制超分子生物材料开辟新的途径。
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来源期刊
Chemistry - A European Journal
Chemistry - A European Journal 化学-化学综合
CiteScore
7.90
自引率
4.70%
发文量
1808
审稿时长
1.8 months
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.
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