Poly(dimethylsiloxane) (PDMS) and similar polymers have proved to be of widespread
interest for use in microfluidic and similar microanalytical devices. Surface modification
of PDMS is required to extend the range of applications for devices made of this polymer,
however. Here we report on the grafting of perfluorooctyltriethoxysilane via hydrolysis
onto an oxidized PDMS substrate in order to form a fluorinated microchannel. Such a
fluorinated device could be used for separating fluorous tagged proteins or peptides,
similar to that which has been recently demonstrated in a capillary electrophoresis system,
or in an open tubular capillary column. The modified polymer is characterized using
chemical force titrations, contact angle measurements and X-ray photoelectron
spectroscopy (XPS). We also report on a novel means of performing electroosmotic
measurements on this material to determine the surface zeta potential. As might be
expected, contact angle and chemical force titration measurements indicate the
fluorinated surface to be highly hydrophobic. XPS indicates that fluorocarbon groups
segregate to the surface of the polymer over a period of days following the initial surface
modification, presumably driven by a lower surface free energy. One of the most
interesting results is the zeta potential measurements, which show that significant surface
charge can be maintained across a wide range of pH on this modified polymer, sufficient
to promote electroosmotic flow in a microfluidic chip. Matrix-assisted time of flight
mass spectrometry (MALDI-TOF MS) measurements show that a fluorous-tagged
peptide will selectively adsorb on the fluorinated PDMS in aqueous solution,
demonstrating that the fluorinated polymer could be used in devices designed forenrichment or enhanced detection of fluorous-labeled proteins and peptides. However,
the non-specific adsorption of other proteins may interfere with the test results. The
adsorption of four different proteins (cytochrome-C, carbonic anhydrase, insulin and
ubiquitin) onto the unmodified, oxidized and fluorinated PDMS surfaces respectively was
studied here with MALDI-TOF MS measurements. The results showed us that when
rinsed in water/methanol solutions of high methanol concentration, cytochrome-C
strongly adheres to the fluorinated surface. Carbonic anhydrase shows the opposite trend.
Retention of ubiquitin on the surface shows relatively little sensitivity to either the nature
of the substrate or the solution composition. Finally, the results using insulin
demonstrated that this protein adheres relatively strongly to the oxidized PDMS surface
as compared to the fluorinated or unmodified PDMS and showed a relative independence
on the composition of the washing solution. The influence of the hydrophilicity of the
protein, the surface and solvents, stability and size of proteins are discussed in the context
of these observations. / Thesis (Master, Chemistry) -- Queen's University, 2008-05-12 16:49:23.672
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OKQ.1974/1205 |
| Date | 01 1900 |
| Creators | Wang, Dan |
| Contributors | Queen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.)) |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English, English |
| Detected Language | English |
| Type | Other |
| Format | 1673799 bytes, application/pdf |
| Rights | This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner. |
| Relation | Canadian theses |
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