This dissertation focuses on the characterization of two surfaces: mixed self-assembled monolayers (SAMs) of hexa(ethylene glycol) and alkyl thiolates (mixed SAM) and poly(N-isopropylacrylamide) (PNIPAAm). The synthesis of hexa(ethylene gylcol) alkyl thiol (C11EG 6OH) is presented along with the mass spectrometry and nuclear magnetic resonance results. The gold substrates were imaged prior to SAM formation with atomic force micrscopy (AFM). Average surface roughness of the gold substrate was 0.44 nm, 0.67 nm, 1.65 nm for 15, 25 and 60 nm gold thickness, respectively. The height of the mixed SAM was measured by ellipsometry and varied from 13 to 28°A depending on surface mole fraction of C11EG6OH. The surface mole fraction of C11EG6OH for the mixed SAM was determined by X-ray photoelectron spectroscopy (XPS) with optimal thermal responsive behavior in the range of 0.4 to 0.6. The mixed SAM surface was confirmed to be thermally responsive by contact angle goniometry, 35° at 28°C and ∼55° at 40°C. In addition, the mixed SAM surfaces were confirmed to be thermally responsive for various aqueous mediums by tensiometry. Factors such as oxygen, age, and surface mole fraction and how they affect the thermal responsive of the mixed SAM are discussed. Lastly, rat fibroblasts were grown on the mixed SAM and imaged by phase contrast microscopy to show inhibition of attachment at temperatures below the molecular transition. Qualitative and quantitative measurements of the fibroblast adhesion data are provided that support the hypothesis of the mixed SAM exhibits a dominantly non-fouling molecular conformation at 25°C whereas it exhibits a dominantly fouling molecular conformation at 40°C.
The adhesion of six model proteins: bovine serum albumin, collagen, pyruvate kinase, cholera toxin subunit B, ribonuclease, and lysozyme to the model thermally responsive mixed SAM were examined using AFM. All six proteins possessed adhesion to the pure component alkyl thiol, in contrast possessed no adhesion to the pure component C11EG6OH SAM at both temperatures examined, 25 and 40°C. The protein adhesion data to the mixed SAM also supports the hypothesis that the mixed SAM displays a non-fouling molecular conformation at 25°C whereas it displays a dominantly fouling molecular conformation at 40°C.
Advancing contact angles obtained through tensiometry were used to find the surface free energy of the mixed SAM before and after the thermal response using the van Oss-Good-Chaudhury method. The surface tension values obtained, 42 and 38 mN/m for 22 and 40°C, respectively, are not dissimilar enough with regard to error to make conclusions. In a similar manner, the surface free energy of another mixed SAM composed of alkyl and trimethylamine thiolates was also calculated.
PNIPAAm brushes grown on a silicon substrate by atom-transfer radical polymerization (ATRP) were imaged by AFM and characterized by XPS. The height of the resulting brushes could be controlled from ∼5 to 55 nm by reaction time. A thermal response was observed for polymer brushes with a length greater than 20 nm. For polymer brush lengths greater than 20 nm, the static contact angle at 22°C was 35° and varied from 60 to 80° at 40°C. The thermal response was also observed using the captive bubble method.
Force-distance curves of the PNIPAAm brushes were taken with an unmodified silicon nitride AFM cantilever at incremental temperature steps. At room temperature the force-distance data was fit to the Alexander-de Gennes model resulting in a hydrated polymer length of 235 nm. The Young’s modulus was calculated using the Hertz model and changed from ∼80 MPa at 26°C to ∼350 MPa at 40°C. The solvent condition of the Alexander-de Gennes model was set to the case of good solvent and showed close match to the force-distance data at 26°C. The match was not as close when the solvent condition was set to theta solvent condition and compared to the force-distance data at 40°C.
Finally, the effective diffusion coefficients of a dye were obtained for the uptake, encapsulation, and release from a lipid bilayer coated mesoporous particle using a mathematical solution to the experimental system. The resulting effective diffusion coefficients are: 1*10-12 m2/s, 0.4*10-12 m2/s, and 0.7*10-12 m2/s for uptake, encapsulation, and release, respectively. The particles are characterized by scanning electron microscopy and nitrogen adsorption measurements. In contrast to our hypothesis, the lipid bilayer did not completely inhibit diffusion of the rhodamine dye from the particles when encapsulated.
|Advisor:||Lopez, Gabriel P.|
|Commitee:||Canavan, Heather, Dirk, Elizabeth, Keller, David, Whitten, David|
|School:||The University of New Mexico|
|School Location:||United States -- New Mexico|
|Source:||DAI-B 71/07, Dissertation Abstracts International|
|Subjects:||Molecular biology, Materials science|
|Keywords:||Bioadhesion, Polyisoproplyacrylamide, Self-assembled monolayers, Thermally responsive materials|
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