Citation: WANG Ji-Qian, SUN Ying-Jie, DAI Jing-Ru, ZHAO Yu-Rong, CAO Mei-Wen, WANG Dong, XU Hai. Effects of Alkyl Chain Length and Peptide Charge Distribution on Self-Assembly and Hydrogelation of Lipopeptide Amphiphiles[J]. Acta Physico-Chimica Sinica, ;2015, 31(7): 1365-1373. doi: 10.3866/PKU.WHXB201505051 shu

Effects of Alkyl Chain Length and Peptide Charge Distribution on Self-Assembly and Hydrogelation of Lipopeptide Amphiphiles

1.
Center for Bioengineering and Biotechnology, China University of Petroleum (East China), Qingdao 266580, Shandong Province, P. R. China

Received Date: 3 March 2015
Available Online: 5 May 2015
Fund Project: 中央高校基本科研业务费专项资金(14CX06036A, 14CX05040A, 14CX02126A) (14CX06036A, 14CX05040A, 14CX02126A)国家自然科学基金(21473255)资助 (21473255)

The self-assembly and hydrogelation of two series of lipopeptide amphiphiles, C_nV₃K₂ (n=12, 14, 16) and C_mKV₃K (m=14, 16), were studied to determine the effects of alkyl chain length and peptide charge distribution. Both the transmission electron microscopy (TEM) and atomic force microscopy (AFM) results showed that all lipopeptide molecules in both series self-assembled into nanotapes with a bilayer structure. The width of the nanotapes decreased with increasing alkyl chain lengths. At a given alkyl chain length, the width of the C_mKV₃K nanotapes was wider than that of the C_nV₃K₂ nanotapes. Based on the circular dichroism (CD) spectra of the nanotapes, all three C_nV₃K₂ molecules adopted a secondary structure of β sheet. In contrast, the secondary structure of the C_mKV₃K nanotapes comprised a mixture of α helix and β sheet. For C14KV3K, the content of the α helix structures was higher than that of the β sheet structures. Conversely, for C16KV3K, the content of the β sheet was higher than that of the α helix structures. The nanotapes of lipopeptides with long alkyl chains were narrower than those with short chains, suggesting that the increased alkyl chain hydrophobicity inhibited lateral stacking of β sheets. When compared with C_nV₃K₂, of which the two positive charges are arranged at the carbon terminal, the separate arrangement of the two positive charges in C_mKV₃K reduced electrostatic repulsion and favored lateral stacking of β sheets to produce wider nanotapes. The rheological data showed that all lipopeptides formed self-supporting hydrogels at 10 mmol·L^-1 and pH 8.4. The hydrogel strength of the lipopeptides with different alkyl chain lengths was nearly the same within a given series. Furthermore, the hydrogel strength of the lipopeptides in the C_mKV₃K series was higher than that of the lipopeptides in the C_nV₃K₂ series. The results indicated that the hydrogel rheological property was more influenced by charge arrangement at the peptide segment than by the alkyl chain length. Also, pH influenced to a great extent the self-assembly of the lipopeptides. The lipopeptides in the C_mKV₃K series were more sensitive to pH than those in the C_nV₃K₂ series.
- Lipopeptide amphiphile,
- Self-assembly,
- Hydrogel,
- Hydrophobic interaction,
- Charge distribution,
- Rheology
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