The role of aromatic residues in controlling the supramolecular chirality of short amphiphilic peptides  

作　　者：Hao Qi Kai Qi Jie Li Chunyong He Mingrui Liao Xuzhi Hu Yurong Zhao Yubin Ke Chunqiu Zhang Jun Zhang Jiqian Wang Jian R.Lu Hai Xu 

机构地区：[1]Department of Biological and Energy Chemical Engineering,China University of Petroleum(East China),Qingdao 266580,China [2]College of Life Science,Nankai University,Tianjin 300071,China [3]Spallation Neutron Source Science Center,Chinese Academy of Sciences(CAS),Dongguan 523803,China [4]Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049,China [5]Biological Physics Group,Department of Physics and Astronomy,The University of Manchester,Manchester M139PL,UK [6]School of Material Science and Engineering,China University of Petroleum(East China),Qingdao 266580,China

出　　处：《Nano Research》2023年第10期12230-12237,共8页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(Nos.22172193,22072181,and U1832108);a joint Innovate UK-Syngenta funded project under knowledge transfer partnership(No.KTP12697);an EPSRC IAA 377 grant(No.R128362)with Arxada.We acknowledge the use of the resources of the China Spallation Neutron Source in Dongguan of Guangdong Province of China.

摘　　要：Although the relationship between molecular and supramolecular chirality remains elusive,the existing results have demonstrated the vital role of hydrophilic motifs in controlling the supramolecular handedness of peptide nanofibrils compared with hydrophobic ones.However,unlike conventional hydrophobic residues,we speculate that aromatic hydrophobic residues are mostly likely to play a unique role in regulating the supramolecular handedness because theπ–πstacking interactions of their side chains are directional like hydrogen bonding and can direct high levels of self-assembly due to the geometric confining of aromatic rings.To confirm this hypothesis,we here design a series of amphiphilic short peptides,with their hydrophobic motifs being composed of aromatic residues.Their short lengths not only favor their structural stability,synthesis,and sequence variation but also enable us to readily link their molecular and supramolecular structures.Through the combination of experiments and theoretical simulations,we demonstrate that the peptides containing L-form aromatic residues form left-handed nanofibrils while those containing D-form aromatic residues assemble into right-handed ones,irrespective of the chirality of their C-terminal hydrophilic residue.Theoretical calculations revealed that the stacking of aromatic side chains betweenβ-strands directed the twisting direction of theβ-sheets formed,with L-and D-form phenylalanine side chains stacking in a clockwise and anti-clockwise way,and more ordered and stronger aromatic stacking for homochiral peptides facilitated the formation of nanofibrils with a marked tubular feature.This study has bridged the knowledge gap in our understanding of how aromatic residues affect the supramolecular chirality of short peptides.

关 键 词：amphiphilic short peptide molecular chirality supramolecular handedness aromatic residue π–πstacking 

分 类 号：O62[理学—有机化学]