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Intrinsically reinforced silks obtained by incorporation of graphene quantum dots into silkworms

摄入石墨烯量子点的家蚕可直接吐出力学性能增强的蚕丝

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Abstract

Silkworm silks have been widely used in a variety of fields due to their sensuousness, luster and excellent mechanical properties. Researchers have paid special attention in improving the mechanical properties of silks. In this work, Bombyx mori larval silkworms are injected with graphene quantum dots (GQDs) through a vascular injection to enhance mechanical properties of the silkworm silks. The GQDs can be incorporated into the silkworm silk gland easily due to hemolymph circulation and influence the spinning process of silkworm. The breaking strength, elongation at break and toughness modulus of the silks increase by 2.74, 1.33 and 3.62 times, respectively, by injecting per individual with 0.6 μg GQDs. Wide-angle X-ray scattering indicates that the size of β-sheet nanocrystals in GQDs-silks is smaller than that in control-silks. Infrared spectra suggest that GQDs confine the conformation transition of silk fibroin to β-sheet from random coil/α-helix, and the change of the size and content of β-sheet may be the reason for the improvement of the mechanical properties. The toxicity and safety limit of GQDs incorporated into each silkworm is also evaluated, and the results show that the upmost dose of GQDs per silkworm is 30.0 μg. The successful obtainment of reinforced silks by in vivo uptake of GQDs provides a promising route to produce high-strength silks.

摘要

家蚕蚕丝具有细腻、 光鲜以及优良的力学特性, 因而在诸多领域中都有广泛应用. 许多科学家对提高家蚕蚕丝力学性能的研究非常感兴趣. 本工作中, 我们通过血管注射的方式给家蚕幼虫注入了石墨烯量子点(GQDs), 并且得到了力学性能增强的蚕丝. GQDs可通过淋巴循环进入到家蚕的丝腺器官并影响家蚕的纺丝过程. 研究发现, 当家蚕的GQDs摄入量为0.6 μg/头时, 家蚕蚕丝的断裂强度、 断裂伸长率以及韧性模量可分别增强到原来的2.74, 1.33 和3.62倍. 广角X射线散射(WAXS)结果表明GQDs-蚕丝中的β-折叠纳米晶体的尺寸比起空白蚕丝有所降低, 红外光谱结果表明GQDs限制了丝素蛋白中无规则卷曲或者α-螺旋结构向β-折叠结构的构象转变. β-折叠结构的尺寸及含量的变化可能是引起蚕丝力学性能增强的原因所在. 我们还对GQDs的毒性以及单头家蚕摄入GQDs的安全限进行了评估, 结果发现家蚕摄入GQDs的上限为30.0 μg/头. 使家蚕直接摄入GQDs获得力学性能增强的蚕丝的方法为生产高强度蚕丝提供了一种有潜力的途径.

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References

  1. Guo C, Zhang J, Wang X, et al. Comparative study of straindependent structural changes of silkworm silks: insight into the structural origin of strain-stiffening. Small, 2017, 13: 1702266

    Article  Google Scholar 

  2. Wang X, Zhao P, Li Y, et al. Modifying the mechanical properties of silk fiber by genetically disrupting the ionic environment for silk formation. Biomacromolecules, 2015, 16: 3119–3125

    Article  Google Scholar 

  3. Koh LD, Cheng Y, Teng CP, et al. Structures, mechanical properties and applications of silk fibroin materials. Prog Polymer Sci, 2015, 46: 86–110

    Article  Google Scholar 

  4. Fang G, Sapru S, Behera S, et al. Exploration of the tight structural–mechanical relationship in mulberry and non-mulberry silkworm silks. J Mater Chem B, 2016, 4: 4337–4347

    Article  Google Scholar 

  5. Li G, Li Y, Chen G, et al. Silk-based biomaterials in biomedical textiles and fiber-based implants. Adv Healthcare Mater, 2015, 4: 1134–1151

    Article  Google Scholar 

  6. Iizuka T, Sezutsu H, Tatematsu K, et al. Colored fluorescent silk made by transgenic silkworms. Adv Funct Mater, 2013, 23: 5232–5239

    Article  Google Scholar 

  7. Blamires SJ, Blackledge TA, Tso IM. Physicochemical property variation in spider silk: ecology, evolution, and synthetic production. Annu Rev Entomol, 2017, 62: 443–460

    Article  Google Scholar 

  8. Florczak A, Jastrzebska K, Mackiewicz A, et al. Blending two bioengineered spider silks to develop cancer targeting spheres. J Mater Chem B, 2017, 5: 3000–3011

    Article  Google Scholar 

  9. Teulé F, Miao YG, Sohn BH, et al. Silkworms transformed with chimeric silkworm/spider silk genes spin composite silk fibers with improved mechanical properties. Proc Natl Acad Sci USA, 2012, 109: 923–928

    Article  Google Scholar 

  10. Andersson M, Jia Q, Abella A, et al. Biomimetic spinning of artificial spider silk from a chimeric minispidroin. Nat Chem Biol, 2017, 13: 262–264

    Article  Google Scholar 

  11. Tansil NC, Koh LD, Han MY. Functional silk: colored and luminescent. Adv Mater, 2012, 24: 1388–1397

    Article  Google Scholar 

  12. Lu Z, Mao C, Meng M, et al. Fabrication of CeO2 nanoparticlemodified silk for UV protection and antibacterial applications. J Colloid Interface Sci, 2014, 435: 8–14

    Article  Google Scholar 

  13. Chang S, Kang B, Dai Y, et al. A novel route to synthesize CdS quantum dots on the surface of silk fibers via γ-radiation. Mater Lett, 2008, 62: 3447–3449

    Article  Google Scholar 

  14. Wang X, Gao W, Xu S, et al. Luminescent fibers: In situ synthesis of silver nanoclusters on silk via ultraviolet light-induced reduction and their antibacterial activity. Chem Eng J, 2012, 210: 585–589

    Article  Google Scholar 

  15. Zhang P, Lan J, Wang Y, et al. Luminescent golden silk and fabric through in situ chemically coating pristine-silk with gold nanoclusters. Biomaterials, 2015, 36: 26–32

    Article  Google Scholar 

  16. Zhang F, Lu Q, Yue X, et al. Regeneration of high-quality silk fibroin fiber by wet spinning from CaCl2–formic acid solvent. Acta Biomater, 2015, 12: 139–145

    Article  Google Scholar 

  17. Hu X, Li J, Bai Y. Fabrication of high strength graphene/regenerated silk fibroin composite fibers by wet spinning. Mater Lett, 2017, 194: 224–226

    Article  Google Scholar 

  18. Zhang C, Zhang Y, Shao H, et al. Hybrid silk fibers dry-spun from regenerated silk fibroin/graphene oxide aqueous solutions. ACS Appl Mater Interfaces, 2016, 8: 3349–3358

    Article  Google Scholar 

  19. Tamura T, Thibert C, Royer C, et al. Germline transformation of the silkworm Bombyx mori L. using a piggyBac transposon-derived vector. Nat Biotechnol, 2000, 18: 81–84

    Article  Google Scholar 

  20. Wang F, Xu H, Wang Y, et al. Advanced silk material spun by a transgenic silkworm promotes cell proliferation for biomedical application. Acta Biomater, 2014, 10: 4947–4955

    Article  Google Scholar 

  21. Wen H, Lan X, Zhang Y, et al. Transgenic silkworms (Bombyx mori) produce recombinant spider dragline silk in cocoons. Mol Biol Rep, 2010, 37: 1815–1821

    Article  Google Scholar 

  22. Nisal A, Trivedy K, Mohammad H, et al. Uptake of azo dyes into silk glands for production of colored silk cocoons using a green feeding approach. ACS Sustain Chem Eng, 2014, 2: 312–317

    Article  Google Scholar 

  23. Tansil NC, Li Y, Teng CP, et al. Intrinsically colored and luminescent silk. Adv Mater, 2011, 23: 1463–1466

    Article  Google Scholar 

  24. Teramoto H, Kojima K. Production of Bombyx mori silk fibroin incorporated with unnatural amino acids. Biomacromolecules, 2014, 15: 2682–2690

    Article  Google Scholar 

  25. Fernandes J, Nicodemo D, Oliveira JE, et al. Enhanced silk performance by enriching the silkworm diet with bordeaux mixture. J Mater Sci, 2017, 52: 2684–2693

    Article  Google Scholar 

  26. Cai L, Shao H, Hu X, et al. Reinforced and ultraviolet resistant silks from silkworms fed with titanium dioxide nanoparticles. ACS Sustain Chem Eng, 2015, 3: 2551–2557

    Article  Google Scholar 

  27. Wu GH, Song P, Zhang DY, et al. Robust composite silk fibers pulled out of silkworms directly fed with nanoparticles. Int J Biol Macromolecules, 2017, 104: 533–538

    Article  Google Scholar 

  28. Wang JT, Li LL, Feng L, et al. Directly obtaining pristine magnetic silk fibers from silkworm. Int J Biol Macromolecules, 2014, 63: 205–209

    Article  Google Scholar 

  29. Cheng L, Huang H, Chen S, et al. Characterization of silkworm larvae growth and properties of silk fibres after direct feeding of copper or silver nanoparticles. Mater Des, 2017, 129: 125–134

    Article  Google Scholar 

  30. Wang JT, Li LL, Zhang MY, et al. Directly obtaining high strength silk fiber from silkworm by feeding carbon nanotubes. Mater Sci Eng-C, 2014, 34: 417–421

    Article  Google Scholar 

  31. Wang Q, Wang C, Zhang M, et al. Feeding single-walled carbon nanotubes or graphene to silkworms for reinforced silk fibers. Nano Lett, 2016, 16: 6695–6700

    Article  Google Scholar 

  32. Hu K, Kulkarni DD, Choi I, et al. Graphene-polymer nanocomposites for structural and functional applications. Prog Polymer Sci, 2014, 39: 1934–1972

    Article  Google Scholar 

  33. Tang LC, Wan YJ, Yan D, et al. The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites. Carbon, 2013, 60: 16–27

    Article  Google Scholar 

  34. Hwang J, Yoon T, Jin SH, et al. Enhanced mechanical properties of graphene/copper nanocomposites using a molecular-level mixing process. Adv Mater, 2013, 25: 6724–6729

    Article  Google Scholar 

  35. Lepore E, Bosia F, Bonaccorso F, et al. Spider silk reinforced by graphene or carbon nanotubes. 2D Mater, 2017, 4: 031013

    Article  Google Scholar 

  36. Bacon M, Bradley SJ, Nann T. Graphene quantum dots. Part Part Syst Charact, 2014, 31: 415–428

    Article  Google Scholar 

  37. Liu WW, Feng YQ, Yan XB, et al. Superior micro-supercapacitors based on graphene quantum dots. Adv Funct Mater, 2013, 23: 4111–4122

    Article  Google Scholar 

  38. Shen J, Zhu Y, Yang X, et al. Graphene quantum dots: emergent nanolights for bioimaging, sensors, catalysis and photovoltaic devices. Chem Commun, 2012, 48: 3686–3699

    Article  Google Scholar 

  39. Tetsuka H, Nagoya A, Fukusumi T, et al. Molecularly designed, nitrogen-functionalized graphene quantum dots for optoelectronic devices. Adv Mater, 2016, 28: 4632–4638

    Article  Google Scholar 

  40. Edwards HGM, Farwell DW. Raman spectroscopic studies of silk. J Raman Spectrosc, 1995, 26: 901–909

    Article  Google Scholar 

  41. Sirichaisit J, Brookes VL, Young RJ, et al. Analysis of structure/ property relationships in silkworm (Bombyx mori) and spider dragline (Nephila edulis) silks using Raman spectroscopy. Biomacromolecules, 2003, 4: 387–394

    Article  Google Scholar 

  42. Keten S, Xu Z, Ihle B, et al. Nanoconfinement controls stiffneßs, strength and mechanical toughness of ß-sheet crystals in silk. Nat Mater, 2010, 9: 359–367

    Article  Google Scholar 

  43. Du N, Liu XY, Narayanan J, et al. Design of superior spider silk: from nanostructure to mechanical properties. BioPhys J, 2006, 91: 4528–4535

    Article  Google Scholar 

  44. Grubb DT, Ji G. Molecular chain orientation in supercontracted and re-extended spider silk. Int J Biol Macromolecules, 1999, 24: 203–210

    Article  Google Scholar 

  45. Numata K, Sato R, Yazawa K, et al. Crystal structure and physical properties of Antheraea yamamai silk fibers: Long poly(alanine) sequences are partially in the crystalline region. Polymer, 2015, 77: 87–94

    Article  Google Scholar 

  46. Sampath S, Isdebski T, Jenkins JE, et al. X-ray diffraction study of nanocrystalline and amorphous structure within major and minor ampullate dragline spider silks. Soft Matter, 2012, 8: 6713–6722

    Article  Google Scholar 

  47. Yen FS, Chen WC, Yang JM, et al. Crystallite size variations of nanosized Fe2O3 powders during γ- to a-phase transformation. Nano Lett, 2002, 2: 245–252

    Article  Google Scholar 

  48. Zhang H, Bhunia K, Munoz N, et al. Linking morphology changes to barrier properties of polymeric packaging for microwave-assisted thermal sterilized food. J Appl Polym Sci, 2017, 134: 45481

    Article  Google Scholar 

  49. Ling S, Qi Z, Knight DP, et al. Synchrotron FTIR microspectroscopy of single natural silk fibers. Biomacromolecules, 2011, 12: 3344–3349

    Article  Google Scholar 

  50. Lin N, Cao L, Huang Q, et al. Functionalization of silk fibroin materials at mesoscale. Adv Funct Mater, 2016, 26: 8885–8902

    Article  Google Scholar 

  51. Hu X, Kaplan D, Cebe P. Determining b-sheet crystallinity in fibrous proteins by thermal analysis and infrared spectroscopy. Macromolecules, 2006, 39: 6161–6170

    Article  Google Scholar 

  52. Huang S, Qiu H, Lu S, et al. Study on the molecular interaction of graphene quantum dots with human serum albumin: Combined spectroscopic and electrochemical approaches. J Hazard Mater, 2015, 285: 18–26

    Article  Google Scholar 

  53. Li L, Wu G, Yang G, et al. Focusing on luminescent graphene quantum dots: current status and future perspectives. Nanoscale, 2013, 5: 4015–4039

    Article  Google Scholar 

  54. Ling S, Li C, Adamcik J, et al. Directed growth of silk nanofibrils on graphene and their hybrid nanocomposites. ACS Macro Lett, 2014, 3: 146–152

    Article  Google Scholar 

  55. Hu K, Gupta MK, Kulkarni DD, et al. Ultra-robust graphene oxide-silk fibroin nanocomposite membranes. Adv Mater, 2013, 25: 2301–2307

    Article  Google Scholar 

  56. Nova A, Keten S, Pugno NM, et al. Molecular and nanostructural mechanisms of deformation, strength and toughness of spider silk fibrils. Nano Lett, 2010, 10: 2626–2634

    Article  Google Scholar 

  57. Lefèvre T, Rousseau ME, Pézolet M. Protein secondary structure and orientation in silk as revealed by Raman spectromicroscopy. BioPhys J, 2007, 92: 2885–2895

    Article  Google Scholar 

  58. Hernandez Cruz D, Roußseau ME, West MM, et al. Quantitative mapping of the orientation of fibroin ß-Sheets in B. mori cocoon fibers by scanning transmission X-ray microscopy. Biomacromolecules, 2006, 7: 836–843

    Article  Google Scholar 

  59. Oroudjev E, Soares J, Arcidiacono S, et al. Segmented nanofibers of spider dragline silk: Atomic force microscopy and single-molecule force spectroscopy. Proc Natl Acad Sci USA, 2002, 99: 6460–6465

    Article  Google Scholar 

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Acknowledgements

This work was supported by Young Elite Scientist Sponsorship Program by CAST (2015QNRC001) and the Earmarked Fund for Modern Agro-industry Technology Research System.

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Correspondence to Guohua Wu  (武国华) or Long Li  (李龙).

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Lin Ma is an assistant research scientist at the College of Biotechnology, Jiangsu University of Science and Technology. She received her PhD (2014) from Beijing Normal University and worked in Jiangsu University of Science and Technology from then on. In 2015, she got the “Young Elite Scientist Sponsorship Program” by CAST (China Association for Science and Technology). Her current research interests focus on the improvement of the properties of silkworm silks by using nanoparticles and the discrimination of proteins via nanoparticle-based sensor array.

Guohua Wu is a Jiangsu specially appointed professor at the College of Biotechnology in Jiangsu University of Science and Technology, and the vice director of Laboratory of Risk Assessment for Sericultural Products and Edible Insects, Ministry of Agriculture of China. His research focuses on biomaterials related with silk, especially to understand the mesoscopic structure-function relationship, and the biological effects of nanomaterials using silkworm as a model organism.

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Ma, L., Akurugu, M.A., Andoh, V. et al. Intrinsically reinforced silks obtained by incorporation of graphene quantum dots into silkworms. Sci. China Mater. 62, 245–255 (2019). https://doi.org/10.1007/s40843-018-9307-7

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  • DOI: https://doi.org/10.1007/s40843-018-9307-7

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