Citation: Liu Jin-ying, Qin Ming-gao, Y. Auphedeous Dang-i, Liu Zhi-wei, Dou Xiao-qiu, Feng Chuan-liang. Inversion of Supramolecular Chirality of Nanofibrous Structures Tuned by the Odd-Even Effects among Bis-amide and Bis-urea[J]. Acta Polymerica Sinica, ;2018, (1): 80-89. doi: 10.11777/j.issn1000-3304.2018.17179 shu

Inversion of Supramolecular Chirality of Nanofibrous Structures Tuned by the Odd-Even Effects among Bis-amide and Bis-urea

1.
State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240
2.
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Corresponding author: Feng Chuan-liang, clfeng@sjtu.edu.cn
Received Date: 10 July 2017
Revised Date: 31 July 2017

Helicity inversion of biomacromolecules (e.g., DNA or proteins) is a sophisticated ubiquitous phenomenon in many physiological processes and associated with specific bio-functions. Therefore, designing of smart systems, with tunable helical chirality and further promoting their applications in the fields of biochemistry, biology and nano-materials, has become appealing. In this regard, four novel C₂-symmetric small-molecule gelators, with L-phenylalanine and benzene ring as skeletons covalently linked by amide group (CONH) or urea group (NHCONH), are designed and synthesized. Based on the odd-even effect between the amide group (CONH) and the urea group (NHCONH), the chiral reversal of the supramolecular assembly can be regulated. The structures of the compound, a-BDFAE, u-BDFAE, a-BDFAP and u-BDFAP, were confirmed by hydrogen-1 nuclear magnetic resonance(¹H-NMR), carbon-13 nuclear magnetic resonance (¹³C-NMR) and high resolution mass spectrum (HRMS). The hydrogels were characterized using circular dichroism spectrum (CD), and they all exhibited bisignate CD effect. However, the sign and intensity were inverted between the amide and urea molecules. The microstructure of the samples was studied using the scanning electron microscopy (SEM). They all assembled into fine nanofibers with diameter in the range of tens of micrometers. The aggregation pattern of the gelators was also investigated with a UV-Vis spectroscopy in different solvents from non-gelating (ethanol) to gelating (water). Amide molecules showed a broad band at around 241 nm in ethanol, which was red-shifted to 245 nm with the solvent changed to milli-Q water. This red-shift clearly indicates the J-type aggregation pattern of the amide hydrogelators. While the UV-Vis spectroscopy of the urea molecules showed a blue-shift, suggesting that the urea molecules formed H aggregates, a different mode of self-assembly induced by the inversion of the supramolecular chirality of amide and urea hydrogels. The interaction of supramolecular aggregates at molecular level was investigated using Fourier transform infrared spectroscopy (FTIR). The results demonstrated that the inversion of the supramolecular chirality of nanofibrous structures was tuned by the odd-even effects, providing therefore a new method for the designing of the tunable supramolecular chirality system. This kind of material has the advantages of simple synthesis, good gelation performance, good biocompatibility. Further biology study of the effects of different chiral materials on cell adhesion and proliferation, and differentiation of stem cells are under way in our laboratory.
- Hydrogel,
- Odd-even effect,
- Supramolecular chirality inversion,
- Amide group,
- Urea group
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