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Author ORCID Identifier



Open Access Dissertation

Document Type


Degree Name

Doctor of Philosophy (PhD)

Degree Program


Year Degree Awarded


Month Degree Awarded


First Advisor

Richard W. Vachet

Second Advisor

Sankaran Thayumanavan

Third Advisor

Stephen J. Eyles

Fourth Advisor

Kathleen F. Arcaro

Subject Categories

Analytical Chemistry | Chemistry | Materials Chemistry | Polymer Chemistry


Mass spectrometry (MS) has become a key and indispensable tool in the identification, characterization, and quantitative analysis of proteins owing to its universality, sensitivity, specificity, and its capability for multiplexed detection. Because biological samples containing these protein analytes are almost always complex systems, various techniques are employed in conjunction with MS to fully harness its analytical potential and enhance its detection capabilities. This dissertation explores the use of amphiphilic polymeric reverse micelles in enriching proteins and peptides from complex biological mixtures and in enhancing their mass spectrometric analysis. Fundamental studies that elucidate the molecular basis for the observed MS signal enhancement that these materials confer are described through structure-property investigations. The molecular features that influence the release of peptides after their encapsulation in these assemblies are examined, and a method for efficient guest release is devised to enable a more quantitative MS analysis. The utility of these materials in simplifying serum and its applicability in significantly enhancing the detection sensitivity in the MS analysis of protein biomarkers is demonstrated.