Chirality Effects on Peptide Self-Assembly Unraveled from Molecules to Materials

García, Ana María; Iglesias, Daniel; Parisi, Evelina; Styan, Katie E.; Waddington, Lynne J.; Deganutti, Caterina; Zorzi, Rita De; Grassi, Mario; Melchionna, Michele; Vargiu, Attilio Vittorio; Marchesan, Silvia

doi:10.1016/j.chempr.2018.05.016

Cited by 157 publications

(198 citation statements)

References 48 publications

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“…These results thus reflect the increased diversity in product structures that accompanies the use of an expanded chiral pool. 35 Table 1. Summary of the structures observed from combinations of ligands, where enantiopure structures are colored blue.…”

Section: Discussionmentioning

confidence: 99%

Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal–Organic Assemblies

et al. 2019

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Herein we elucidate the interplay of chiral, chelate, solvent and hydrogen-bonding information in the self-assembly of a series of new three-dimensional metal-organic architectures. Enantiopure ligands, each containing H-bond donors and acceptors, form different structures depending on the ratio in which they are combined: enantiopure components form M4L4 assemblies, whereas racemic mixtures form M3L3 stacks. Chiral amplification within M3L3 enantiomers was observed when a 2:1 ratio of R and S subcomponent enantiomers was employed. Simply switching the solvent (from MeCN to MeOH) or chelating unit (from bidentate to tridentate) increased the diversity of structures that can be generated from these building blocks, leading to the selective formation of novel M2L2 and M3L2 assemblies. The addition of achiral ligand building blocks resulted in the formation of further structures: When an achiral subcomponent was combined with its R-and S-chiral congeners, a three-layer heteroleptic architecture was generated, with the achiral unit sitting at the top of the stack. When combined with the S enantiomer only, however, the achiral unit assembled in the center of the structure, thus demonstrating the selective placement of achiral units within chiral systems. Further sorting experiments revealed that combining R and S stereocenters within a single ligand led to diastereoselective product generation. These results show how geometric complementarity between different ligands impacts upon the degree of hydrogen bonding within the assembly, stabilizing specific lowsymmetry architectures from among many possible structural outcomes.

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Section: Discussionmentioning

confidence: 99%

Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal–Organic Assemblies

et al. 2019

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“…Most studies conducted so far are devoted to dipeptides of natural absolute configuration L. The influence of the L or D absolute configuration of the residues on the self‐assembly propensity of oligopeptides has been studied by electronic circular dichroism . Tripeptides based on L or D phenylalanine have been studied by circular vibrational dichroism, and γ‐turn nanostructures have been observed for L‐Phe‐L‐Phe‐D‐Phe .…”

Section: Introductionmentioning

confidence: 99%

Solid‐state synthesis of cyclo LD‐diphenylalanine: A chiral phase built from achiral subunits

2020

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The solid-state structure of LL/DD or LD/DL diphenylalanine diluted in KBr pellets is studied by infrared (IR) absorption and vibrational circular dichroism (VCD) spectroscopy. The structure depends on the absolute configuration of the residues. The natural LL diphenylalanine exists as a mixture of neutral and zwitterionic structures, depending on the humidity of the sample, while mostly the zwitterion is observed for LD diphenylalanine whatever the experimental conditions. The system undergoes spontaneous cyclization upon heating at 125 C, resulting to the formation of a diketopiperazine (DKP) dipeptide as the only product. The reaction is faster for LD than for LL diphenylalanine. As expected, LL and DD diphenylalanine react to form the LL and DD enantiomers of cyclo diphenylalanine. Interestingly, the DKP dipeptides formed from the LD or DL diphenylalanine show unexpected optical activity, with opposite VCD spectra for the products formed from the LD and DL reagents. This is explained in terms of chirality synchronization between the monomers within the crystal, which retain the symmetry of the reagent, resulting to the formation of a new chiral phase made from transiently chiral molecules. K E Y W O R D Schirality synchronization, diketopiperazine (DKP), peptides, vibrational circular dichroism (VCD), vibrational spectroscopy

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“…These changes include, but are not limited to, changes in N-terminal capping group, changes to amino acid chirality and changes to amino acid sequence. 21,22 The alteration of amino acid sequence in self-assembling short peptides has previously been used to tune peptide pK a , 23,24 enabling self-assembly under more physiologically relevant conditions. Other examples have incorporated the RGD sequence derived from bronectin to enhance cell adhesion.…”

Section: Introductionmentioning

confidence: 99%

Decoupling the effects of hydrophilic and hydrophobic moieties at the neuron–nanofibre interface

Martin

Wojciechowski

et al. 2020

Chem. Sci.

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Chirality Effects on Peptide Self-Assembly Unraveled from Molecules to Materials

Cited by 157 publications

References 48 publications

Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal–Organic Assemblies

Hydrogen-Bond-Assisted Symmetry Breaking in a Network of Chiral Metal–Organic Assemblies

Solid‐state synthesis of cyclo LD‐diphenylalanine: A chiral phase built from achiral subunits

Decoupling the effects of hydrophilic and hydrophobic moieties at the neuron–nanofibre interface

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