Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.

Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.

Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.

Author ORCID Identifier



Open Access Dissertation

Document Type


Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded


Month Degree Awarded


First Advisor

Murugappan Muthukumar

Subject Categories

Biochemical and Biomolecular Engineering | Biophysics | Physical Chemistry


The transparent vitreous, which fills the posterior cavity of the eye, is incredibly engineered. The charged polyelectrolyte hyaluronic acid (HA) network swells to maintain the pressure in the eye, while stiff collagen type II bundles help absorb any external mechanical shock. Our investigations have contributed to a few key developments related to the physical properties of the vitreous: (1) The stiff collagen network that supports the soft gel network is self-assembled from single triple-helix collagen proteins. Electrostatic interactions drive this assembly, such that the size and concentration are optimized at physiological salt concentrations. The width of the assemblies remarkably changes from 60 nm to 800 nm with only a 50 mM change in the salt concentration. (2) A soft (~ 2 - 200 Pa) negative polyelectrolyte network swells to support the microscopic and tough collagen bundles. The equilibrium swelling behavior and the response to external manipulation is driven by the charged components of the gel. We have developed a way to determine the thermodynamic quantities responsible for this phenomenon, such as the chemical miss-match parameter of the backbone, the ionizability of the network, and the Poisson ratio. We show that these parameters are enough to predict the equilibrium linear-elastic elasticity of polyelectrolyte gels for a range of strand lengths and salt concentrations. (3) Finally, using these principles, in collaboration with Dr. Paul Hamilton, and Dr. Nathan Ravi at Washington University, we have developed a new synthetic injectable vitreous substitute for use as a novel double-network therapeutic material. The vitreous can phase-separate and detach from the retina. This disease is poorly studied and has few treatment options. By studying biomimetic models of the vitreous in vitro, we hope to understand vision-related diseases, the mechanism for collagen fiber formation, intrinsic soft tissue properties, and to formulate therapeutic materials.