Preparation of Highly Crystalline Silk Nanofibrils and Their Use in the Improvement of the Mechanical Properties of Silk Films

Lee, Ji Hye; Park, Bo Kyung; Um, In Chul

doi:10.3390/ijms231911344

Title: Preparation of Highly Crystalline Silk Nanofibrils and Their Use in the Improvement of the Mechanical Properties of Silk Films

Journal Article · Mon Sep 26 00:00:00 EDT 2022 · International Journal of Molecular Sciences (Online)

DOI:https://doi.org/10.3390/ijms231911344· OSTI ID:1908054

Lee, Ji Hye ^[1];

^[2];

^[1]

Kyungpook National University, Daegu (Korea, Republic of)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Due to their commendable biocompatibility, regenerated silk fibroin (RSF) films have attracted considerable research interest. However, the poor mechanical properties of RSF films have limited their use in various biomedical applications. In this study, a novel, highly crystalline silk fibril was successfully extracted from silk by combining degumming with ultrasonication. Ultrasonication accelerated the development of silk nanofibrils measuring 130–200 nm on the surface of the over-degummed silk fibers, which was confirmed via scanning electron microscopy. Additionally, the crystallinity index of silk fibril was found to be significantly higher (~68%) than that of conventionally degummed silk (~54%), as confirmed by the Fourier-transform infrared (FTIR) spectroscopy results. Furthermore, the breaking strength and elongation of the RSF film were increased 1.6 fold and 3.4 fold, respectively, following the addition of 15% silk nanofibrils. Thus, the mechanical properties of the RSF film were remarkably improved by the addition of the silk nanofibrils, implying that it can be used as an excellent reinforcing material for RSF films.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; National Research Foundation of Korea (NRF)

Grant/Contract Number:: AC05-00OR22725; 2021R1A2C1006921

OSTI ID:: 1908054

Journal Information:: International Journal of Molecular Sciences (Online), Vol. 23, Issue 19; ISSN 1422-0067

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

References (57)

In vivo blood compatibility of regenerated silk fibroin. Sakabe, Hiroshi; Ito, Hiraku; Miyamoto, Takeaki Sen'i Gakkaishi, Vol. 45, Issue 11 https://doi.org/10.2115/fiber.45.11_487	journal	January 1989
Elastin-like polypeptide modified silk fibroin porous scaffold promotes osteochondral repair Chen, Zhuoyue; Zhang, Qiang; Li, Hongmin Bioactive Materials, Vol. 6, Issue 3 https://doi.org/10.1016/j.bioactmat.2020.09.003	journal	March 2021
Stem cell-based tissue engineering with silk biomaterials Wang, Yongzhong; Kim, Hyeon-Joo; Vunjak-Novakovic, Gordana Biomaterials, Vol. 27, Issue 36 https://doi.org/10.1016/j.biomaterials.2006.07.008	journal	December 2006
In vitro evaluation of the inflammatory potential of the silk fibroin Santin, Matteo; Motta, Antonella; Freddi, Giuliano Journal of Biomedical Materials Research, Vol. 46, Issue 3, p. 382-389 https://doi.org/10.1002/(SICI)1097-4636(19990905)46:3<382::AID-JBM11>3.0.CO;2-R	journal	September 1999
Spinning from Nature: Engineered Preparation and Application of High-Performance Bio-Based Fibers Xu, Zongpu; Wu, Mingrui; Ye, Qi Engineering, Vol. 14 https://doi.org/10.1016/j.eng.2021.06.030	journal	July 2022
A prospective cohort study of the silk fibroin patch in chronic tympanic membrane perforation Lee, Jun Ho; Kim, Dong-Kyu; Park, Hae Sang The Laryngoscope, Vol. 126, Issue 12 https://doi.org/10.1002/lary.25980	journal	June 2016
Silk Protein-Based Membrane for Guided Bone Regeneration Kwon, Kwang-Jun; Seok, Hyun Applied Sciences, Vol. 8, Issue 8 https://doi.org/10.3390/app8081214	journal	July 2018
Accelerated healing with the use of a silk fibroin membrane for the guided bone regeneration technique Song, Ji-Young; Kim, Seong-Gon; Lee, Jong-Won Oral Surgery, Oral Medicine, Oral Pathology, Oral Radiology, and Endodontology, Vol. 112, Issue 6 https://doi.org/10.1016/j.tripleo.2011.05.002	journal	December 2011
Bio-inspired anisotropic polymeric heart valves exhibiting valve-like mechanical and hemodynamic behavior Guo, Feng; Liu, Chang; Han, Rizheng Science China Materials, Vol. 63, Issue 4 https://doi.org/10.1007/s40843-019-1217-4	journal	December 2019
Functional recovery guided by an electrospun silk fibroin conduit after sciatic nerve injury in rats Park, Sook Young; Ki, Chang Seok; Park, Young Hwan Journal of Tissue Engineering and Regenerative Medicine, Vol. 9, Issue 1 https://doi.org/10.1002/term.1615	journal	October 2012
Preparation of undegraded native molecular fibroin solution from silkworm cocoons Yamada, Hiromi; Nakao, Hiroshi; Takasu, Yoko Materials Science and Engineering: C, Vol. 14, Issue 1-2 https://doi.org/10.1016/S0928-4931(01)00207-7	journal	August 2001
Molecular weight distribution and solution properties of silk fibroins with different dissolution conditions Cho, Hee Jung; Ki, Chang Seok; Oh, Hanjin International Journal of Biological Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1016/j.ijbiomac.2012.06.007	journal	October 2012
Effect of Various Dissolution Systems on the Molecular Weight of Regenerated Silk Fibroin Wang, Qin; Chen, Quan; Yang, Yuhong Biomacromolecules, Vol. 14, Issue 1 https://doi.org/10.1021/bm301741q	journal	December 2012
Effect of degumming methods on structural characteristics and properties of regenerated silk Kim, Hyun Ju; Kim, Moo Kon; Lee, Ki Hoon International Journal of Biological Macromolecules, Vol. 104 https://doi.org/10.1016/j.ijbiomac.2017.06.019	journal	November 2017
Physical properties of silk fibroin/chitosan blend films Kweon, Haeyong; Ha, Hyun Chul; Um, In Chul Journal of Applied Polymer Science, Vol. 80, Issue 7 https://doi.org/10.1002/app.1172	journal	January 2001
Structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SA) blend films Tsukada, Masuhiro; Freddi, Giuliano; Crighton, John S. Journal of Polymer Science Part B: Polymer Physics, Vol. 32, Issue 2 https://doi.org/10.1002/polb.1994.090320205	journal	January 1994
Biomaterial Films of Bombyx Mori Silk Fibroin with Poly(ethylene oxide) Jin, Hyoung-Joon; Park, Jaehyung; Valluzzi, Regina Biomacromolecules, Vol. 5, Issue 3, p. 711-717 https://doi.org/10.1021/bm0343287	journal	May 2004
The effect of casting solvent on the structural characteristics and miscibility of regenerated silk fibroin/Poly(vinyl alcohol) blends Um, In Chul; Park, Young Hwan Fibers and Polymers, Vol. 8, Issue 6 https://doi.org/10.1007/BF02875993	journal	December 2007
Biopolymer nanofibrils: Structure, modeling, preparation, and applications Ling, Shengjie; Chen, Wenshuai; Fan, Yimin Progress in Polymer Science, Vol. 85 https://doi.org/10.1016/j.progpolymsci.2018.06.004	journal	October 2018
Improvement of Starch Film Performances Using Cellulose Microfibrils Dufresne, Alain; Vignon, Michel R. Macromolecules, Vol. 31, Issue 8 https://doi.org/10.1021/ma971532b	journal	March 1998
Bioengineering Bacterial Cellulose/Poly(ethylene oxide) Nanocomposites Brown, Elvie E.; Laborie, Marie-Pierre G. Biomacromolecules, Vol. 8, Issue 10 https://doi.org/10.1021/bm700448x	journal	September 2007
Ultrasonic technique for extracting nanofibers from nature materials Zhao, Hong-Ping; Feng, Xi-Qiao; Gao, Huajian Applied Physics Letters, Vol. 90, Issue 7 https://doi.org/10.1063/1.2450666	journal	February 2007
Facile Fabrication of Robust Silk Nanofibril Films via Direct Dissolution of Silk in CaCl₂–Formic Acid Solution Zhang, Feng; You, Xinran; Dou, Hao ACS Applied Materials & Interfaces, Vol. 7, Issue 5 https://doi.org/10.1021/am508319h	journal	January 2015
Liquid Exfoliated Natural Silk Nanofibrils: Applications in Optical and Electrical Devices Ling, Shengjie; Li, Chunmei; Jin, Kai Advanced Materials, Vol. 28, Issue 35 https://doi.org/10.1002/adma.201601783	journal	June 2016
Ultrathin Free-Standing Bombyx mori Silk Nanofibril Membranes Ling, Shengjie; Jin, Kai; Kaplan, David L. Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.6b01195	journal	May 2016
Peeling and Mesoscale Dissociation of Silk Fibers for Hybridization of Electrothermic Fibrous Composites Lv, Lili; Han, Xiangsheng; Wu, Xiaochen ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 1 https://doi.org/10.1021/acssuschemeng.9b05261	journal	December 2019
Effect of degumming condition on the solution properties and electrospinnablity of regenerated silk solution Ko, Jae Sang; Yoon, Kyunghwan; Ki, Chang Seok International Journal of Biological Macromolecules, Vol. 55 https://doi.org/10.1016/j.ijbiomac.2012.12.041	journal	April 2013
Effect of degumming ratio on wet spinning and post drawing performance of regenerated silk Kim, Hyun Ju; Um, In Chul International Journal of Biological Macromolecules, Vol. 67 https://doi.org/10.1016/j.ijbiomac.2014.03.055	journal	June 2014
Structural characteristics and properties of the regenerated silk fibroin prepared from formic acid Um, In Chul; Kweon, HaeYong; Park, Young Hwan International Journal of Biological Macromolecules, Vol. 29, Issue 2 https://doi.org/10.1016/S0141-8130(01)00159-3	journal	August 2001
Preparation of new natural silk non-woven fabrics by using adhesion characteristics of sericin and their characterization Lee, Ji Hye; Bae, Yeon Su; Kim, Su Jin International Journal of Biological Macromolecules, Vol. 106 https://doi.org/10.1016/j.ijbiomac.2017.07.179	journal	January 2018
Effect of molecular weight on electro-spinning performance of regenerated silk Park, Bo Kyung; Um, In Chul International Journal of Biological Macromolecules, Vol. 106 https://doi.org/10.1016/j.ijbiomac.2017.08.115	journal	January 2018
Effects of electric field on the maximum electro-spinning rate of silk fibroin solutions Park, Bo Kyung; Um, In Chul International Journal of Biological Macromolecules, Vol. 95 https://doi.org/10.1016/j.ijbiomac.2016.11.026	journal	February 2017
Effect of Relative Humidity on the Electrospinning Performance of Regenerated Silk Solution Park, Bo Kyung; Um, In Chul Polymers, Vol. 13, Issue 15 https://doi.org/10.3390/polym13152479	journal	July 2021
The role of formic acid in solution stability and crystallization of silk protein polymer Um, In Chul; Kweon, Hae Yong; Lee, Kwang Gill International Journal of Biological Macromolecules, Vol. 33, Issue 4-5 https://doi.org/10.1016/j.ijbiomac.2003.08.004	journal	December 2003
Effect of residual sericin on the structural characteristics and properties of regenerated silk films Lee, Ji Hye; Song, Dae Woong; Park, Young Hwan International Journal of Biological Macromolecules, Vol. 89 https://doi.org/10.1016/j.ijbiomac.2016.04.073	journal	August 2016
Molecular and Nanostructural Mechanisms of Deformation, Strength and Toughness of Spider Silk Fibrils Nova, Andrea; Keten, Sinan; Pugno, Nicola M. Nano Letters, Vol. 10, Issue 7 https://doi.org/10.1021/nl101341w	journal	June 2010
Silk Fibroin Dissolution in Tetrabutylammonium Hydroxide Aqueous Solution Medronho, Bruno; Filipe, Alexandra; Napso, Sofia Biomacromolecules, Vol. 20, Issue 11 https://doi.org/10.1021/acs.biomac.9b00946	journal	October 2019
Foundation of the Outstanding Toughness in Biomimetic and Natural Spider Silk Anton, Arthur Markus; Heidebrecht, Aniela; Mahmood, Nasir Biomacromolecules, Vol. 18, Issue 12 https://doi.org/10.1021/acs.biomac.7b00990	journal	October 2017
Discerning Silk Produced by Bombyx mori from Those Produced by Wild Species Using an Enzyme-Linked Immunosorbent Assay Combined with Conventional Methods You, Qiushi; Li, Qingqing; Zheng, Hailing Journal of Agricultural and Food Chemistry, Vol. 65, Issue 35 https://doi.org/10.1021/acs.jafc.7b02789	journal	August 2017
Biomimetic Hybridization of Kevlar into Silk Fibroin: Nanofibrous Strategy for Improved Mechanic Properties of Flexible Composites and Filtration Membranes Lv, Lili; Han, Xiangsheng; Zong, Lu ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b03119	journal	July 2017
Squid Sucker Ring Teeth: Multiscale Structure–Property Relationships, Sequencing, and Protein Engineering of a Thermoplastic Biopolymer Hiew, Shu Hui; Miserez, Ali ACS Biomaterials Science & Engineering, Vol. 3, Issue 5 https://doi.org/10.1021/acsbiomaterials.6b00284	journal	August 2016
Biomechanical Design of Elastic Protein Biomaterials: A Balance of Protein Structure and Conformational Disorder Muiznieks, Lisa D.; Keeley, Fred W. ACS Biomaterials Science & Engineering, Vol. 3, Issue 5 https://doi.org/10.1021/acsbiomaterials.6b00469	journal	June 2016
Effects of different Bombyx mori silkworm varieties on the structural characteristics and properties of silk Chung, Da Eun; Kim, Hyung Hwan; Kim, Moo Kon International Journal of Biological Macromolecules, Vol. 79 https://doi.org/10.1016/j.ijbiomac.2015.06.012	journal	August 2015
Effect of molecular weight and storage time on the wet- and electro-spinning of regenerated silk fibroin Cho, Hee Jung; Yoo, Young Jin; Kim, Jong Wook Polymer Degradation and Stability, Vol. 97, Issue 6 https://doi.org/10.1016/j.polymdegradstab.2012.03.007	journal	June 2012
Effect of Sericin Content on the Structural Characteristics and Properties of Electro-spun Regenerated Silk Ko, Jae Sang; Ki, Chang Seok; Um, In Chul Fibers and Polymers, Vol. 19, Issue 3 https://doi.org/10.1007/s12221-018-7861-4	journal	March 2018
Effect of Korean Bombyx mori variety on electro-spinning performance of regenerated silk fibroin Park, Bo Kyung; Um, In Chul Fibers and Polymers, Vol. 16, Issue 9 https://doi.org/10.1007/s12221-015-5472-x	journal	September 2015
Effects of degumming conditions on electro-spinning rate of regenerated silk Yoon, Kyunghwan; Lee, Ha Ni; Ki, Chang Seok International Journal of Biological Macromolecules, Vol. 61 https://doi.org/10.1016/j.ijbiomac.2013.06.039	journal	October 2013
Effect of molecular weight and concentration on crystallinity and post drawing of wet spun silk fibroin fiber Chung, Da Eun; Um, In Chul Fibers and Polymers, Vol. 15, Issue 1 https://doi.org/10.1007/s12221-014-0153-8	journal	January 2014
Preparation, Structural Characterization, and Properties of Natural Silk Non-woven Fabrics from Different Silkworm Varieties Kim, Su Jin; Um, In Chul Fibers and Polymers, Vol. 23, Issue 4 https://doi.org/10.1007/s12221-022-4350-6	journal	April 2022
Preparation, Structural Characteristics, and Properties of Airlaid Nonwoven Silk Fabric Bae, Yeon Su; Um, In Chul Polymer Korea, Vol. 44, Issue 6 https://doi.org/10.7317/pk.2020.44.6.809	journal	November 2020
Effect of Silkworm Variety on Characteristics of Raw Sericin in Silk Kim, Su Jin; Um, In Chul Fibers and Polymers, Vol. 20, Issue 2 https://doi.org/10.1007/s12221-019-8715-4	journal	February 2019
Effect of storage and drying temperature on the gelation behavior and structural characteristics of sericin Jo, Yoon Nam; Park, Byung-Dae; Um, In Chul International Journal of Biological Macromolecules, Vol. 81 https://doi.org/10.1016/j.ijbiomac.2015.09.016	journal	November 2015
Effect of molecular weight on the structure and mechanical properties of silk sericin gel, film, and sponge Park, Chun Jin; Ryoo, Jooyeon; Ki, Chang Seok International Journal of Biological Macromolecules, Vol. 119 https://doi.org/10.1016/j.ijbiomac.2018.08.006	journal	November 2018
Effect of sericin concentration and ethanol content on gelation behavior, rheological properties, and sponge characteristics of silk sericin Jang, Mi Jin; Um, In Chul European Polymer Journal, Vol. 93 https://doi.org/10.1016/j.eurpolymj.2017.03.048	journal	August 2017
Effects of solvent on the solution properties, structural characteristics and properties of silk sericin Jo, Yoon Nam; Um, In Chul International Journal of Biological Macromolecules, Vol. 78 https://doi.org/10.1016/j.ijbiomac.2015.04.004	journal	July 2015
Effects of Fabrication Conditions on Structure and Properties of Mechanically Prepared Natural Silk Web and Non-Woven Fabrics Bae, Yeon-Su; Um, In-Chul Polymers, Vol. 13, Issue 10 https://doi.org/10.3390/polym13101578	journal	May 2021
Silk/Rayon Webs and Nonwoven Fabrics: Fabrication, Structural Characteristics, and Properties Bae, Yu Jeong; Jang, Mi Jin; Um, In Chul International Journal of Molecular Sciences, Vol. 23, Issue 14 https://doi.org/10.3390/ijms23147511	journal	July 2022

Similar Records

Silk I and Silk II studied by fast scanning calorimetry

Journal Article · Thu Jun 01 00:00:00 EDT 2017 · Acta Biomaterialia · OSTI ID:1908054

Cebe, Peggy; Partlow, Benjamin P.; Kaplan, David L.; +3 more

Silk Fibroin as an Organic Polymer for Controlled Drug Delivery

Journal Article · Sun Jan 01 00:00:00 EST 2006 · J. Controlled Release · OSTI ID:1908054

Hofmann, S; Wong Po Foo, C; Rossetti, F; +5 more

Structural Comparison of Various Silkworm Silks: An Insight into the Structure–Property Relationship

Journal Article · Fri Feb 09 00:00:00 EST 2018 · Biomacromolecules · OSTI ID:1908054

Guo, Chengchen; Zhang, Jin; Jordan, Jacob S.; +3 more

Related Subjects

36 MATERIALS SCIENCE
silk nanofibril
composite film
mechanical properties
degumming
ultrasonication

Title: Preparation of Highly Crystalline Silk Nanofibrils and Their Use in the Improvement of the Mechanical Properties of Silk Films

Citation Formats

References (57)

Similar Records

Related Subjects