Co-Assembly between Fmoc Diphenylalanine and Diphenylalanine within a 3D Fibrous Viscous Network Confers Atypical Curvature and Branching

Co-Assembly between Fmoc Diphenylalanine and Diphenylalanine within a 3D Fibrous Viscous Network Confers Atypical Curvature and Branching
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Fmoc 二苯丙氨酸和二苯丙氨酸在 3D 纤维状粘性网络中的共组装赋予非典型曲率和分支

DOI:
10.1002/anie.202009488
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发表时间:
2020-10-15
影响因子:
16.6
通讯作者:
Gazit, Ehud
Gazit, Ehud
中科院分区:
化学1区
文献类型:
--
作者:
Chakraborty, Priyadarshi;Tang, Yiming;Gazit, Ehud

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超分子聚合物共组装是一种有效的多肽纳米结构调控方法。然而,其中一个肽构建块同时形成水凝胶的共同组装方案还有待研究。在这里,我们研究了二苯丙氨酸(FF)和Fmoc-二苯丙氨酸(FmocFF)在FmocFF水凝胶三维网络中的共组装形成。两个构建块之间的重叠肽序列导致它们在凝胶状态下共同组装,调节FF晶体的性质。我们观察到具有非典型曲率的分支微晶聚集体的形成,与从水溶液中获得的FF集合体形成对比。光学显微镜显示了这些聚集体的S型动力学生长轮廓。微流体学和ToF-SIMS实验表明,在晶体聚集体中存在Ff和FmocFf的共组装结构。采用分子动力学模拟方法对共组装的形成机理进行了解释。
Supramolecular polymer co-assembly is a useful approach to modulate peptide nanostructures. However, the co-assembly scenario where one of the peptide building blocks simultaneously forms a hydrogel is yet to be studied. Herein, we investigate the co-assembly formation of diphenylalanine (FF), and Fmoc-diphenylalanine (FmocFF) within the 3D network of FmocFF hydrogel. The overlapping peptide sequence between the two building blocks leads to their co-assembly within the gel state modulating the nature of the FF crystals. We observe the formation of branched microcrystalline aggregates with an atypical curvature, in contrast to the FF assemblies obtained from aqueous solution. Optical microscopy reveal the sigmoidal kinetic growth profile of these aggregates. Microfluidics and ToF-SIMS experiments exhibit the presence of co-assembled structures of FF and FmocFF in the crystalline aggregates. Molecular dynamics simulation was used to decipher the mechanism of co-assembly formation.