Directed Growth of Silk Nanofibrils on Graphene and Their Hybrid Nanocomposites
- Shengjie Ling ,
- Chaoxu Li ,
- Jozef Adamcik ,
- Suhang Wang ,
- Zhengzhong Shao ,
- Xin Chen , and
- Raffaele Mezzenga
Abstract

Combination of proteins with other nanomaterials offers a promising strategy to fabricate novel hybrids with original functions in biology, medicine, nanotechnology, and materials science. Under carefully selected experimental conditions, we show that graphene nanosheets are able to direct one-dimensional self-assembly of silk fibroin, forming an unprecedented type of nanohybrids. These silk/graphene hybrids combine physical properties of both constituents and form functional composites with well-ordered hierarchical structures. Due to the facile fabrication process and their tunable nanostructures, the resultant hybrids show promise in applications as diverse as tissue engineering, drug delivery, nanoelectronics, nanomedicine, biosensors, and functional composites.
Figure 1

Figure 1. Schematic representation of the procedure followed to prepare SF nanofibril/graphene hybrids. SF solution (5 wt %) was prepared from B. mori silkworm cocoons. Graphene oxide and SF solutions were mixed at various mass ratios and incubated at 70 °C and pH = 10–10.9 for 6 h in the presence of hydrazine.
Figure 2

Figure 2. Structural characterization of SF nanofibril/graphene hybrids. (a) AFM image of the hybrid prepared from SF/graphene (8:2) at pH 10.3. The inset shows that the hybrid solution remains stable for several months. (b) AFM image with height profiles collected along the indicated colored lines. (c) Height profile along the contour length nanofibrils prepared from SF/graphene (5:5) at pH 10.3, highlighting the necklace structure of the nanofibrils. (d) DMT moduli image of the hybrids prepared from SF/graphene (8:2) at pH 10.3. The inset refers to the DMT modulus distribution of the nanofibrils measured on top of a single graphene sheet. All scale bars in images are 500 nm.
Figure 3

Figure 3. Dependence of SF assembling behavior on both pH and SF/graphene mass ratio. Exfoliated regions and SF nanofibril/graphene hybrid regions were indicated as red and blue boxes, respectively. Photographs of final suspensions with SF/graphene ratio 1:9 (a) and 2:8 (c) ratios at pH 10.5. (b) TEM image of the suspension in (a). (d) TEM image of the hybrid with 3:7 SF/graphene ratio at pH 10.6. (e) AFM image of the hybrid with 3:7 SF/graphene ratio at pH 10.3. (f, g) AFM images of the hybrid with 5:5 SF/graphene ratio at pH 10.7 and 10.3, respectively. (h–j) AFM image of the hybrid with 8:2 SF/graphene ratio at pH 11, 10.8, and 10.3, respectively.
Figure 4

Figure 4. Physical characterization of macroscopic hybrid films. (a) Photograph of free-standing SF nanofibrils/graphene composite. (b) SEM image of the film with 8:2 SF/graphene ratio. The inset gives the dependence of the conductivity on SF/graphene ratio. The symbol * for silk stands for the insulating nature of pure SF nanofibrils whose electrical conductivity is below the detection range of 10–8 S cm–1. (c) Tensile properties of the films. (d, e) Comparison of fluorescence image of Hela cells growing for 3 days on the film with 8:2 SF nanofibrils/graphene ratio (d) and 100% graphene (e).
Experimental Section
Characterization
Supporting Information
Preparation of silk protein solution, synthesis of graphene oxide, AFM, TEM, and SEM characterization, conductivity measurements, WAXS/SAXS, and growth of Hela cells. This material is available free of charge via the Internet at http://pubs.acs.org.
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Acknowledgment
This work is supported by the China Scholarship Council, the National Natural Science Foundation of China (Nos. 20974025, 21034003), the National High Technology Research and Development Program of China (863 Program; No. 2012AA030309), and ETH Zurich. We thank Dr. Antoni Sanchez-Ferrer at ETH Zurich and Dr. Jinrong Yao, Dr. Jianchuan Wen, and Yaxian Wang at Fudan University for their valuable suggestions and discussions.
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Abstract

Figure 1

Figure 1. Schematic representation of the procedure followed to prepare SF nanofibril/graphene hybrids. SF solution (5 wt %) was prepared from B. mori silkworm cocoons. Graphene oxide and SF solutions were mixed at various mass ratios and incubated at 70 °C and pH = 10–10.9 for 6 h in the presence of hydrazine.
Figure 2

Figure 2. Structural characterization of SF nanofibril/graphene hybrids. (a) AFM image of the hybrid prepared from SF/graphene (8:2) at pH 10.3. The inset shows that the hybrid solution remains stable for several months. (b) AFM image with height profiles collected along the indicated colored lines. (c) Height profile along the contour length nanofibrils prepared from SF/graphene (5:5) at pH 10.3, highlighting the necklace structure of the nanofibrils. (d) DMT moduli image of the hybrids prepared from SF/graphene (8:2) at pH 10.3. The inset refers to the DMT modulus distribution of the nanofibrils measured on top of a single graphene sheet. All scale bars in images are 500 nm.
Figure 3

Figure 3. Dependence of SF assembling behavior on both pH and SF/graphene mass ratio. Exfoliated regions and SF nanofibril/graphene hybrid regions were indicated as red and blue boxes, respectively. Photographs of final suspensions with SF/graphene ratio 1:9 (a) and 2:8 (c) ratios at pH 10.5. (b) TEM image of the suspension in (a). (d) TEM image of the hybrid with 3:7 SF/graphene ratio at pH 10.6. (e) AFM image of the hybrid with 3:7 SF/graphene ratio at pH 10.3. (f, g) AFM images of the hybrid with 5:5 SF/graphene ratio at pH 10.7 and 10.3, respectively. (h–j) AFM image of the hybrid with 8:2 SF/graphene ratio at pH 11, 10.8, and 10.3, respectively.
Figure 4

Figure 4. Physical characterization of macroscopic hybrid films. (a) Photograph of free-standing SF nanofibrils/graphene composite. (b) SEM image of the film with 8:2 SF/graphene ratio. The inset gives the dependence of the conductivity on SF/graphene ratio. The symbol * for silk stands for the insulating nature of pure SF nanofibrils whose electrical conductivity is below the detection range of 10–8 S cm–1. (c) Tensile properties of the films. (d, e) Comparison of fluorescence image of Hela cells growing for 3 days on the film with 8:2 SF nanofibrils/graphene ratio (d) and 100% graphene (e).
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ARTICLE SECTIONSPreparation of silk protein solution, synthesis of graphene oxide, AFM, TEM, and SEM characterization, conductivity measurements, WAXS/SAXS, and growth of Hela cells. This material is available free of charge via the Internet at http://pubs.acs.org.
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