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Gold nanoparticles (AuNPs) with their unique sizes, shapes, and properties have generated much enthusiasm over the last two decades, and have been explored for many potential applications. The successful application of AuNPs depends critically on the ability to modify and functionalize their surface to provide stability, compatibility, and special chemical functionality. This dissertation is aimed at exploring the chemical synthesis and surface modification of AuNPs with the effort to (1) control the number of functional groups on the particle surface, and to (2) increase the colloidal stability at the physiological conditions. To control the functionality on the particle surface, a solid phase place exchange reaction strategy was developed to synthesize the 2 nm AuNPs with a single carboxylic acid group attached on the particle surface. Such monofunctional AuNPs can be treated and used as molecular nanobuilding blocks to form more complex nanomaterials with controllable structures. A "necklace"-like AuNP/polymer assembly was obtained by conjugating covalently the monofunctional AuNPs with polylysine template, and exhibited an enhanced optical limiting property due to strong electromagnetic interaction between the nanoparticles in close proximity. To improve the colloidal stability in the psychological condition, biocompatible polymers, polyacrylic acid (PAA), and polyethylene glycol (PEG) were used to surface modify the 30 nm citrate-stabilized AuNPs. These polymer-modified AuNPs are able to disperse individually in the high ionic strength solution, and offer as the promising optical probes for bioassay applications. The Prostate specific antigen (PSA) and target DNA can be detected in the low pM range by taking advantages of the large scattering cross section of AuNPs and the high sensitivity of dynamic light scattering (DLS) measurement. In addition to the large scattering cross section, AuNPs can absorb strongly the photon energy at the surface plasmon resonance wavelength and then transform efficiently to the heat energy. The efficient photon-thermal energy conversion property of AuNPs has been used to thermal ablate the Aβ peptide aggregates under laser irradiation toward Alzheimer's disease therapy.

This body of work investigates various techniques for the surface modification of food contact materials for use in food packaging and processing applications. Nanoscale changes to the surface of polymeric food packaging materials enables changes in adhesion, wettability, printability, chemical functionality, and bioactivity, while maintaining desirable bulk properties. Polymer surface modification is used in applications such as antimicrobial or non-fouling materials, biosensors, and active packaging. Non-migratory active packagings, in which bioactive components are tethered to the package, offer the potential to reduce the need for additives in food products while maintaining safety and quality. A challenge in developing non-migratory active packaging materials is the loss of biomolecular activity that can occur when biomolecules are immobilized. Polyethylene glycol (PEG), a biocompatible polymer, is grafted from the surface of ozone treated low-density polyethylene (LDPE) resulting in a surface functionalized polyethylene to which a range of amine-terminated bioactive molecules can be immobilized. The grafting of PEG onto the surface of polymer packaging films is accomplished by free radical graft polymerization, and to covalently link an amine-terminated molecule to the PEG tether, demonstrating that amine-terminated bioactive compounds (such as peptides, enzymes, and some antimicrobials) can be immobilized onto PEG-grafted LDPE in the development of non-migratory active packaging. Fouling on food contact surfaces during food processing has a significant impact on operating efficiency and can promote biofilm development. Processing raw milk on plate heat exchangers results in significant fouling of proteins as well as minerals, and is exacerbated by the wall heating effect. An electroless nickel coating is co-deposited with polytetrafluoroethylene onto stainless steel to test its ability to resist fouling on a pilot plant scale plate heat exchanger. Further work was performed to test the stability of non-fouling material after extended exposure to an alkali detergent or acid sanitizer formulated for clean-in-place procedures in dairy processing facilities. Additionally, the anti-corrosive property of the surface coating was tested on carbon steel against chlorine ions, a common corrosive agent found in the food industry. Accelerated corrosion and long-term chemical exposure studies were conducted to measure the coating stability against the harsh corrosive agents.

The challenge of demolding during the cast molding process of silicone hydrogel contact lenses can be addressed with the application of hydrophobic coatings on the surface of lens mold. In particular, the adhesion between silicone hydrogel and silicate substrates was minimized by applying silane modification on the surface of silicate substrates. Peel tests were conducted to measure the adhesive strengths between silicone hydrogel and surface modified glass substrates. Water contact angle measurement and X-ray photoelectron spectroscopy (XPS) were utilized to characterize the surface properties of silane treated glass substrates.Silicone hydrogel was obtained by curing macromer mixture under UV for 6 minutes, with UV intensity of 95.0 mW/cm2. The obtained silicone hydrogel had a modulus of 0.87±0.09 MPa, within the same range of commercial contact lenses. And the hydrogel with a UV curing time of 6 minutes was unable to be peeled off from clean glass substrates. The effects of silane type and concentration on coating effectiveness were investigated and the most effective types of silane were found to be triethoxyphenylsilane (TEPhS) and octyltriethoxysilane (OTES), with an optimal concentration of 5 wt%. The peel strength between silicone hydrogel and silicate substrates was reduced to below 15.5 N/m with the application of TEPhS and OTES coatings. However, these silane coatings were not durable enough. Silane coupling agents need to be reapplied before each curing process of silicone hydrogel. / Thesis / Master of Applied Science (MASc)

The dermestid beetle (Dermestes maculatus) has become renowned in the laboratory as an aid to skeletonization of remains, both for the zoologist and the anthropologist. However, little attention has been paid to the potential effects these insects can have on hard tissues and whether their traces may be mistaken for trauma or the effects of taphonomic processes. The use of dermestid beetles in the anthropology laboratory was tested by a choice experiment based on ASTM D3345-17, examining the behavior of D. maculatus regarding Styrofoam, wood, and two types of bone. Specifically, this project tested 1.) whether the beetles showed preference for a particular material (of wood, Styrofoam, dry bone, or green bone), 2.) whether material(s) had an impact on survivorship from the larval to adult stages, and 3.) what traces dermestids leave on skeletal remains and the variation in form of those traces. Results suggest dermestid beetles will preferentially bore pupal chambers in softer materials (Styrofoam > wood > dry bone > green bone), but preference is not absolute, as pits appear in dry bone even when softer materials are present. Preference did not appear to impact survivorship. Information on the “typical” form of dermestid trace on materials is presented, as an aid to identifying these features as resulting from taphonomic processes, as opposed to ante- or perimortem processes/events.

This report presents evidence that in-situ reduction of metal ions bound to a cross-linked polymer surface does not always result in nanoparticle formation solely at the interface, as is commonly assumed, but also as much as 40 nm deep within the polymer matrix. Tetrachloroaurate ions were bound using a variety of multi-functional amines to cured films of SU-8 -- a cross-linkable epoxide frequently used for micro- and nanofabrication -- and then treated using one of several reducing agents. The resulting gold-nanoparticle decorated films were examined by X-ray photoelectron spectroscopy and by plan-view and cross-sectional transmission electron microscopy. Reduction using sodium borohydride or sodium citrate generates bands of interspersed particles as much as 40 nm deep within the polymer, suggesting both the Au(III) complex and the reducing agent are capable of penetrating the surface and affecting reduction and formation of nanoparticles within the polymer matrix. It is shown that nanoparticle formation can be confined nearer to the polymer interface by using hydroquinone, a sterically bulkier and less flexible reducing agent, or by reacting the surface in aqueous media with high molecular-weight multifunctional amines, that presumably confine Au(III) nearer to the true interface. These finding have important implications for technologies that apply surface bound nanoparticles, including electroless metallization, catalysis, nano-structure synthesis, and surface enhanced spectroscopy.

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