Characterization of water in hydrated Bombyx mori silk fibroin fiber and films by 2H NMR relaxation and 13C solid state NMR

Publication date: Available online 5 January 2017
Source:Acta Biomaterialia
Author(s): Tetsuo Asakura, Kotaro Isobe, Shunsuke Kametani, Obehi T. Ukpebor, Moshe C. Silverstein, Gregory S. Boutis
The mechanical properties of Bombyx mori silk fibroin (SF), such as elasticity and tensile strength, change remarkably upon hydration. However, the microscopic interaction with water is not currently well understood on a molecular level. In this work, the dynamics of water molecules interacting with SF was studied by ²H solution NMR relaxation and exchange measurements. Additionally, the conformations of hydrated [3-¹³C]Ala-, [3-¹³C]Ser- and [3-¹³C]Tyr-SF fibers and films were investigated by ¹³C DD/MAS NMR. Using an inverse Laplace transform algorithm, we were able to identify four distinct components in the relaxation times for water in SF fiber. Namely, A: bulk water outside the fiber, B: water molecules trapped weakly on the surface of the fiber, C: bound water molecules located in the inner surface of the fiber and D: bound water molecules located in the inner part of the fiber were distinguishable. In addition, four components were also observed for water in the SF film immersed in methanol for 30 seconds, while only two components for the film immersed in methanol for 24 hours. The effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and non-crystalline domains of ¹³C selectively labeled SF, respectively, could be determined independently. Our measurements provide new insight relating the characteristics of water and the hydration structure of silk, which are relevant in light of current interest in the design of novel silk-based biomaterials.Statements of SignificanceThe mechanical properties of Bombyx mori silk fibroin (SF) change remarkably upon hydration. However, the microscopic interaction between SF and water is not currently well understood on a molecular level. We were able to identify four distinct components in the relaxation times for water in SF fiber by ²H solution NMR relaxation and exchange measurements. In addition, the effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and non-crystalline domains of ¹³C selectively labeled SF, respectively, could be determined independently. Thus, our measurements provide new insight relating the characteristics of water and the hydration structure of silk, which are relevant in light of current interest in the design of novel silk-based biomaterials.

Graphical abstract

http://ift.tt/2hX8k5A