Molecular mechanics of cartilage : quantification of GAG electrostatic interactions via high-resolution force spectroscopy

Intermolecular repulsion forces between negatively charged glycosaminoglycan (CS-GAG) macromolecules are a major determinant of cartilage biomechanical properties. It is thought that the electrostatic component of the total intermolecular interaction is responsible for 50-75% of the equilibrium elastic modulus of cartilage in compression, while other forces (e.g., steric, hydration, van der Waals, etc.) may also play a role. To investigate these forces, radiolabeled CS-GAG polymer chains were chemically end-grafted to a planar surface to form model biomimetic polyelectrolyte "brush" layers whose environment was varied to mimic physiological conditions. The total intersurface force (<[or equal to] nN) between the CS-GAG brushes and chemically modified probe tips (SO₃⁻ and OH) was measured as a function of tip-substrate separation distance in aqueous solution using the technique of high-resolution force spectroscopy (HRFS). These experiments showed long-range, nonlinear, purely repulsive forces that decreased in magnitude and range with increasing ionic strength and decreasing pH. In order to estimate the contribution of the electrostatic component to the total intersurface force, the data were compared to a theoretical model of electrical double layer repulsion based on the Poisson-Boltzmann formulation. The CS-GAG brush layer was approximated as either a flat surface charge density or a smoothed volume of known fixed charge density and the probe tip was modeled as a smooth hemisphere of constant surface charge density.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Mechanical Engineering.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2003

Author dc:creator

• Seog, Joonil, 1969-

Advisor dc:contributor.advisor

• Alan J. Grodzinsky.

• Mechanical Engineering.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/17641

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/17641