Hierarchical charge distribution controls self-assembly process of silk <i>in vitro</i>

doi:10.1007/s11706-015-0314-8

Front. Mater. Sci.

2015, Vol. 9

Issue (4) : 382-391 https://doi.org/10.1007/s11706-015-0314-8

RESEARCH ARTICLE

Hierarchical charge distribution controls self-assembly process of silk in vitro

Yi ZHANG^1,²,Cencen ZHANG^1,^2,⁴,Lijie LIU^1,²,David L. KAPLAN^1,³,Hesun ZHU⁵,Qiang LU^1,^2,^*(

)

1. National Engineering Laboratory for Modern Silk & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, China
2. College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, China
3. Department of Biomedical Engineering, Tufts University, Medford, MA 02155, USA
4. Textile College, Henan Institute of Engineering, Zhengzhou 450007, China
5. Research Center of Materials Science, Beijing Institute of Technology, Beijing 100081, China

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Abstract

Silk materials with different nanostructures have been developed without the understanding of the inherent transformation mechanism. Here we attempt to reveal the conversion road of the various nanostructures and determine the critical regulating factors. The regulating conversion processes influenced by a hierarchical charge distribution were investigated, showing different transformations between molecules, nanoparticles and nanofibers. Various repulsion and compressive forces existed among silk fibroin molecules and aggregates due to the exterior and interior distribution of charge, which further controlled their aggregating and deaggregating behaviors and finally formed nanofibers with different sizes. Synergistic action derived from molecular mobility and concentrations could also tune the assembly process and final nanostructures. It is suggested that the complicated silk fibroin assembly processes comply a same rule based on charge distribution, offering a promising way to develop silk-based materials with designed nanostructures.

Keywords self-assembly charge nanostructure nanofiber silk

Corresponding Author(s): Qiang LU

Online First Date: 26 October 2015 Issue Date: 12 November 2015

Cite this article:

Yi ZHANG,Cencen ZHANG,Lijie LIU, et al. Hierarchical charge distribution controls self-assembly process of silk in vitro[J]. Front. Mater. Sci., 2015, 9(4): 382-391.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-015-0314-8
https://academic.hep.com.cn/foms/EN/Y2015/V9/I4/382

Fig.1 AFM images and height map of silk fibroin deposited from fresh solutions during diluting process. The concentrations of the diluted solutions were as follows: (a)(a') 0.3%; (b)(b') 0.03%; (c)(c') 0.003%; (d)(d') 0.0003%.

Fig.2 The (a) volumes, (b) zeta potentials and (c) CD curves of silk fibroin in fresh solutions during diluting process. The concentrations of the diluted solutions were as follows: 0.3%; 0.03%; 0.003%; 0.0003%.

Fig.3 Nanostructure changes of silk fibroin in diluted solution with concentration of 0.003% when cultured at 4°C for different time. The samples were as follows: (a)(a') 0 d; (b)(b') 2 d; (c)(c') 4 d; (d)(d') 8 d; (e)(e') 16 d; (f)(f') 24 d.

Fig.4 Nanostructure changes of silk fibroin when the solution with concentration of 0.003% was concentrated to 0.3% at 60°C during a concentrated process. The samples were as follows: (a)(a') silk concentration 0.003%, concentrating time 0 d; (b)(b') silk concentration 0.009%, concentrating time 0.5 d; (c)(c') silk concentration 0.03%, concentrating time 2 d; (d)(d') silk concentration 0.09%, concentrating time 2.5 d; (e)(e') silk concentration 0.3%, concentrating time 4 d.

Fig.5 AFM images and height map of the silk nanoparticle in aqueous solution during diluting process: (a)(a') silk nanoparticle solution with concentration of 0.03%, and (b)(b') the nanoparticle solution was diluted to 0.003% with distilled water. The silk nanoparticle solution was prepared by slowly concentrating the fresh solution to about 20% over 48 h at 60°C and then diluted to 0.03%.

Fig.6 Scheme 1 The negative charge-tuned self-assembly process of silk fibroin in vitro.

Fig.7 Nanostructure changes of silk fibroin in the fresh solution with concentration of 0.003% when cultured at (a)(b)(c)(d)(e)(f) 25°C and (a')(b')(c')(d')(e')(f') 60°C for different time. The samples were as follows: (a)(a') 0 d; (b)(b') 2 d; (c)(c') 4 d; (d)(d') 8 d; (e)(e') 16 d; and (f)(f') 24 d.

Fig.8 Nanostructure changes of silk fibroin in the fresh solution with concentration of 0.03% when cultured at (a)(b)(c)(d)(e)(f) 4°C, (a')(b')(c')(d')(e')(f') 25°C and (a'')(b'')(c'')(d'')(e'')(f'') 60°C for different time. The samples were as follows: (a)(a')(a'') 0 d; (b)(b')(b'') 2 d; (c)(c')(c'') 4 d; (d)(d')(d'') 8 d; (e)(e')(e'') 16 d; and (f)(f')(f'') 24 d.

Fig.9 Nanostructure changes of silk fibroin in the fresh solution with concentration of 0.3% when cultured at (a)(b)(c)(d)(e)(f) 4°C, (a')(b')(c')(d')(e')(f') 25°C and (a'')(b'')(c'')(d'')(e'')(f'') 60°C for different time. The samples were as follows: (a)(a')(a'') 0 d; (b)(b')(b'') 2 d; (c)(c')(c'') 4 d; (d)(d')(d'') 8 d; (e)(e')(e'') 16 d; and (f)(f')(f'') 24 d.

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