A framework to compartmentalize microfluidic surfaces was developed. Substrates are separated from surface modifying agents with an intermediate binding layer (IBL). The IBL is comprised of two compounds which bind together using a non-covalent interaction; a host compound is immobilized on the substrate, and a guest compound is conjugated to the surface modifying agent. The primary benefit of the IBL architecture is adaptability: substrates and surface compounds become modular components with standard connectors. Beta-Cyclodextrin (BCD) and adamantane (AD) were selected as the model immobilized host and conjugated guest, respectively. A quartz crystal microbalance (QCM) was assembled and developed to study the BCD/AD complexation interaction. Kinetic, thermodynamic, and Langmuir isotherm data were reported for AD-derivatives binding with immobilized BCD. QCM was also used to investigate neutravidin (NA) binding onto AD-PEG and AD-PEG-biotin coatings immobilized to t-BCD surfaces. QCM was an effective platform to validate the use of BCD/AD as the IBL interaction prior to microfluidic implementation. The BCD/AD IBL was successfully demonstrated in a microfluidic environment. Microfluidic devices were fabricated using the soft-lithographic technique. Adapted surface modifications were visualized using fluorescein isothiocyanate (FITC) probes within the microfluidic device and detected using confocal laser scanning microscopy (CLSM). Surface modifications were applied to demonstrate the fundamental functions of surface passivation, specific binding, and visualization using the IBL architecture. Consistent with QCM data, AD-PEG passivated the surface and AD-PEG-biotin specifically bound NA to the BCD surface. Thus, an adaptable surface modification architecture for microfluidic applications was developed and demonstrated.

Surface Biological Modification and Cellular Interactions of Magnetic Spinel Nanoparticles Eva Liang-Huang Heintz 191 Pages Directed by Dr. Z. John Zhang The interest in magnetic nanoparticles is multi-dimensional. Fundamentally, it is important to be able to control their magnetic properties and to correlate to specific applications. In biology, magnetic nanoparticles offer promising potential as magnetic carriers or chaperones for magnetic localization and manipulation of therapeutic reagents. The synthesis of superparamagnetic CoFe2-xSmxO4 nanoparticles and the tunability of their magnetic properties by size and composition variations are discussed. An increase in size of CoSm0.19Fe1.81O4 nanoparticles produced an increase in blocking temperature and saturation magnetization, but a non-linear coercitivity response was observed with change in size. By varying the composition, the saturation magnetization of CoFe2-xSmxO4 decreased dramatically while the coercitivity increased when compared to native cobalt spinel ferrite (CoFe2O4) nanoparticles. These results demonstrate how the magnetic properties of cobalt spinel ferrite nanoparticles can be tailored to specific applications. Surface modifications of cobalt spinel ferrite nanoparticles facilitated the conjugation of oligonucleotides. Using a transfection reagent, CoFe2O4 ??igonucleotide conjugates were delivered into mammalian cells. Post transfection, synchronized movement of cells in response to an external magnetic field was observed. This demonstrated the possibility of magnetic manipulation and localization of therapeutic reagents coupled to CoFe2O4 magnetic nanoparticles. Results from this thesis demonstrate the potential role of magnetic spinel nanoparticles in cell biology and will facilitate the progress towards in vivo testing.

This study presents a simple process for producing resistance-based humidity sensors utilizing dopamine (DA) coated gold nano-particles (AuNPs) as the sensing material. The sensing material for typical humidity sensors are solid state metal oxides, graft-polymers or salt-doped polymers. However, these humidity sensors may suffer from low sensing response or slow time response since water molecules have to diffuse into the sensing materials to induce the electrical property changes. Alternatively, AuNPs have large surface area for water molecule absorption and can be potentially for high performance humidity sensing. Nevertheless, the surface property of AuNPs is hydrophobic and needs to be modified. In this regards, this work uses a highly hydrophilic molecule of dopamine to modify the surface of AuNP into hydrophilic to enhance the humidity sensing performance. Highly hydrophilic bio-molecule of dopamine is physically bonded onto 4-6 nm AuNPs to enhance the humidity sensing performance. Results show that the DA coated AuNPs have nice humidity sensing responses in the measuring range of 20-90%RH. The measured resistance response shows >1500 times greater than the sensor using the same AuNPs without DA coating. The developed humidity sensor shows rapid time responses for water absorption (13 s) and desorption (30 s), respectively. Moreover, a 3-day long-term measurement at low, medium and high humidity ranges also shows the good stability of the developed sensor. The method developed in this study provides a simple and low-cost method to produce high-performance humidity sensors with DA-coated AuNPs.

Layer-by-layer (LbL) assembly based on ionic interactions has proven to be a versatile route for surface modification and construction of ultrathin nanocomposites. Covalent LbL assembly based on facile ‘click’ covalent bond formation is an effective alternative, especially for the applications where a more robust ultrathin films or nanocomposites is desired. The subject of this dissertation focuses on the design of three different covalent LbL assemblies and their applications on conductive thin films, superhydrophobic surfaces, and solute responsive surfaces, respectively. Surface modification of PE substrates using covalent LbL assembly with PEI and Gantrez is a successful route to prepare a surface graft. The procedure is relative easy, fast and reproducible. Grafting multiple layers of PEI/Gantrez to the PE powder surface provided excellent coverage and promoted stable LbL film growth and excellent adhesion. This carbon black (CB) coated powder was compression molded into films, and their conductivity was measured, which revealed a percolation threshold below 0.01 wt % CB for the PEI-grafted system. Electrical conductivity of 0.2 S/cm was achieved with only 6 wt % CB, which is exceptional for a CB-filled PE film. Direct amination of MWNTs with PEI is a convenient and simple method leading to highly functionalized product that contains 6-8 % by weight PEI. Superhydrophobic PE films can be formed either from ionic LbL self-assembly of MWNT-NH-PEIs and poly(acrylic acid) or from covalent LbL self-assembly of MWNTNH- PEIs and Gantrez when the final graft is acrylated with octadecanoic acid. While the ionically assembled nanocomposite graft is labile under acid, the covalently assembled graft is more chemically robust. Responsive surfaces with significant, reversible, reproducible wettability changes can be prepared by covalent LbL grafting using PNIPAM-c-PNASI and aminated silica nanoparticles. A 65º ΔΘ value was observed with water vs. 1.4 M Na2SO4. The prepared film shows a high surface roughness of ~300 nm, which contributes to the large solute responsive ΔΘ values. The surfaces are reconfigurable in different solute conditions and that the changes in water contact angle are likely due to combination of change in surface roughness along with swell and intercalation of the solute ions into the PNIPAM surface.

This paper presents new bonding and surface modification methods for plastic substrates utilizing atmospheric pressure plasma (AP plasma) treatment. Three kinds of AP plasma equipments including after-glow discharge, dielectric barrier discharge and flame type are tested and evaluated for their feasibility of microfluidic device fabrication. The experimental results show that the DBD plasma equipment is the most suitable one for microfluidic applications due to its low temperature and high treating level. Three kinds of polymenr including PMMA, PC and PDMS are used as the sample substrates for evaluating the performance of AP plasma in this study. Experimental results show that the polymer surface turns into hydrophilic after AP plasma treatment. Fourier Transform Infrared Spectroscopy (FTIR) inspection indicates that a new peak corresponding to -C-OH functional group is generated at the wavenumber of 1040 cm-1 after AP plasma treatment. X-ray photoelectron spectrum investigation also shows that the O/C (atom ratio) is 3.5-fold incensement in compare with the bare sample. SEM and AFM observations are utilized to evaluate the surface morphology change after plasma treatment. The measured surface roughness is at the level of several nanometers which is acceptable for most microfluidic applications. We develop two simple and high strength bonding methods for sealing microfluidic deivices in this study. The bonding process can be achieved in 6 minutes and bonding strength of 1.69 MPa and 3.81 MPa can be obtained using direct plasma bonding and ethyl alcohol assisted bonding, respectively. The bonding strength obtained using ethyl alcohol assisted bonding technique reported in this study is the highest one that ever been reported. The feasibility of AP plasma treatment for sealing microfluidic chips are confirmed by three examples including two novel passive microfluidic mixers and one cross-type micro CE chip. Experimental result shows that the mixing performance of the micromixer can reach up to 90% at an operation condition of a low Reynolds number of 4. In addition, micro CE chip sealed with the proposed method can successfully inject and separate dye sample with a long-term stability upto 30 minutes. Separation of 100 bp standard DNA sample of 100 bp to 3000 is also successfully demonstrated with high separation efficiency. It is the author¡¦s firm believes that the proposed bonding method will give substaintial impact on the fabrication of microfluidic device in the future.

The synthesis and characterization of some phosphonic acids as well as the modification of indium tin oxide (ITO) substrates using these phosphonic acids are presented in this thesis. Phosphonic acids have been known to bind strongly to the surface of a number of metal oxides. ITO substrates were reported to be modified with a variety of surface modifiers. Herein the ITO substrates were modified with the chosen phosphonic acids with different functional groups in order to tune the work function and compare the work function changes with the functional group properties.

<p>The need for safe and functional implants has led to anincreased demand for improved biomaterials. The performance invivo depends on the interaction between the biologicalsurrounding and the surface of the material. By tailoring thesurface of a material with suitable bulk properties,biomaterials with an ability to interact with the biologicalsystem in a specific and controlled way are obtained. Siliconeelastomers have been used as biomaterials for several decades,but it is widely recognized that they are difficult to modifyby the conventional methods used for organic polymers due tothe partly inorganic structure of silicone.</p><p>This thesis presents a strategy to obtain siliconebiomaterials by covalent coupling of molecules to the surfaceusing silicon chemistry. The first step is to introduce Si-Hgroups onto the surface of silicone elastomers by plasmatreatment. The second step is to react a terminal double bondof a molecule with the formed Si-H group by a catalyzedhydrosilylation reaction. The coupled molecule may eitherprovide the desired properties itself, or have a functionalitythat is able to couple another molecule with suitablecharacteristics.</p><p>The influence of plasma treatment in hydrogen, argon andoxygen on the silicone elastomer was characterized by X-rayphotoelectron spectroscopy (XPS). To quantify the effect ofplasma treatment, the method of ternary XPS diagrams wasdeveloped. It was found that undesired silica-like layers wereformed under severe treatment conditions. Argon plasma at lowpower and short treatment time was the most suitable parametersetting. Subsequent hydrosilylation grafting ofallyltetrafluoroethylether, aminopropylvinylether andN-vinylformamide showed that it was possible to functionalizethe surface via a covalent link to the surface. The primaryamino groups introduced onto the surface were accessible forfurther coupling reactions. Heparin surfaces were obtained by acoupling reaction with the introduced amino groups.</p><p><b>Keywords:</b>Silicone elastomers, PDMS, XPS, ESCA, surfacemodification, plasma</p>

The level of risk originating from toxic (heavy) metals in the environment and ecological systems is continuously escalating due to our imprudent development of mineral resources such as coal and gold. For example, selenium as one of the major components in coal has contaminated surface and groundwater sources, and represents a threat to human and ecosystem health accumulation in organisms known as selenosis. Arsenic, like selenium, has also a negative effect to human beings, so called "arsenicosis" if it is accumulated in an organism through dietary pathways. Therefore, these elements have threatened waterways by contaminating surface and groundwater sources, and the WHO has established the drinking water quality guideline as 10 ppb for selenium and arsenic. The development of surface modified carbon nano-materials was motivated by considering how toxic metal species such as selenium and arsenic can be effectively removed from aquatic environments such as mineral tailings ponds found at mine sites. The materials design strategy employed herein hypothesizes of the incorporation of Lewis acid-base sites by the preparation of surface modified carbon nano-material with magnetite (magnetite composite). The resulting composite materials were anticipated to have variable π-π interactions and H-bonding between (non-)metals and ligands. These novel composite sorbents were evaluated for sorptive removal of selenium and arsenic species in aqueous solution at variable conditions. Selenium and arsenic have variable adsorption affinity onto the surface of magnetite (iron oxide) and its composites and goethite (iron oxyhydrate) in aqueous solution. The sorptive properties of these materials were correlated to the synthetic strategy as evidenced by the characterization of these minerals and their adsorbent properties. The adsorptive properties were evaluated by comparing the adsorption of inorganic selenium species with various adsorbents (magnetite, magnetite composites, activated carbon, and goethite) through adsorption kinetics and at equilibrium conditions. A novel “in situ” kinetic set-up for this experiment was developed using a non-magnetic stirrer device with a semi-permeable filtration barrier. The analytical measurement of selenium uptake was achieved using hydride generation atomic absorption spectroscopy. An arylarsenical (roxarsone) in aqueous solution was removed by using the same adsorbents used for selenium sorption and using a novel one-pot kinetic experiment with a non-magnetic stirrer and a dialysis-based tubing filter. Determination of roxarsone uptake was evaluated with UV-vis spectroscopy. This study showed the prepared magnetite composites might be excellent adsorbents for removing organic (aryl) and inorganic forms of Se and As chemical species in aqueous solution. The composite nature of the composite adsorbents suggests their potential as dual function sorbents due to their affinity toward organic (aryl) and inorganic anion species. In the occurrence of iron leaching, it was attenuated at low temperatures for the composite materials; whereas, greater leaching occurred above room temperature due to the increased thermal breakdown of magnetite particles in the pores or on the surface of activated carbon. In addition to the aforementioned tunable surface reactivity and surface area, magnetite composites have magnetic susceptibility properties that enable physical separation of adsorbents in water treatment processes by employing an electro-magnet to induce phase separation.

Humic-based organic compounds containing phenol or benzoic acid groups strongly compete with phosphates for specific binding sites on the surface of these colloidal particles. To study the interactions between phenol groups and the surface binding sites of unmodified or modified colloidal particles, chemical force spectrometry (CFS) was used as a tool to measure the adhesion force between an atomic force microscopy (AFM) tip terminated with a phenol self-assembled monolayer and colloidal particles under varying pH conditions. Two modification methods, co-precipitation and post-precipitation, were used to simulate the naturally-occurring phosphate and humic-acid adsorption process. The pH dependence of adhesion forces between phenol-terminated tip and colloidal particles could be explained by an interplay of electrostatic forces, the surface loading of the modifying phosphate or humic acid species and ionic hydrogen bonding. Polydimethylsiloxane (PDMS) is a widely-used polymer in microfluidic devices. PDMS surfaces are commonly modified to make it suitable for specific microfluidic devices. We studied the surface modification of PDMS using four perfluoroalkyl-triethoxysilane molecules of differing length of perfluorinated alkyl chain. The results show that the length of fluorinated alkyl chain has important effects on the density of surface modifying molecules, surface topography and surface zeta potential. The perfluorinated overlayer makes PDMS more efficient at supporting electroosmotic flow, which has potential applications in microfluidic devices. The kinetic study of RNase A, lysozyme C, α-lactalbumin and myoglobin at different concentrations adsorbed on the self-assembled monolayers of 1-octanethiol (OT-Au) and 1H, 1H, 2H, 2H-perfluorooctyl-1-thiol (FOT-Au) has been carried out. The results show a positive relationship between the lower protein concentration and the increased adsorption rate constant (ka) on both surfaces. At low concentrations, the protein adsorption on an OT-Au surface has greater ka than it on a FOT-Au surface. Comparing ka values for four proteins on OT-Au and FOT-Au surface demonstrates that hard proteins (lysozyme and RNase A) have larger ka than soft proteins (α-lactalbumin and myoglobin) on both surfaces. The discussion is based on the hydrophobicity of OT-Au and FOT-Au surfaces, as well as average superficial hydrophobicity, flexibility, size, stability, and surface induced conformation change of proteins. / Thesis (Ph.D, Chemistry) -- Queen's University, 2011-10-14 21:08:31.617

Modification of planar graphitic carbon surfaces by the attachment of molecular films has been investigated in this work. Molecular layers have been grafted to glassy carbon (GC) and pyrolyzed photoresist film (PPF) by employing a range of techniques, which involved electrochemically and photochemically assisted procedures. Modification methods involve the electrochemical reduction of aryldiazonium salt, electrochemical oxidation of arylcarboxylate and photolysis of alkene, alkyne and azide on carbon surfaces. For these methods, it is proposed that reactive species are generated by the procedures, which leads to the grafting of modifiers to the carbon surfaces. A selection of molecular species was grafted to GC and PPF by these method containing different terminal R-functional groups that include —COOH, -NO₂, -NH₂, and —NCS. The grafted R-functional groups permit for further chemical reactions on the surface. Electrochemically and photochemically grafted films were examined with a combination of water contact angle measurements, cyclic voltammetry, X-ray electron spectroscopy XPS, optical microscopy, scanning electron microscopy SEM and atomic force microscopy AFM. Film properties such as surface concentration, film thickness, wettability, chemical composition and reactivity were characterized by the above mentioned techniques. Films electrochemically prepared from aryldiazonium salts and arylcarboxylates, under the conditions applied in this work, formed loosely packed multilayers with typical film thicknesses of les than 5 nm. Photochemically grafted films prepared from alkenes and azides, in general, formed loosely packed monolayers with film thicknesses of less than 2 nm. Loosely packed multilayers were also prepared from alkene and alkyne by photochemical procedures. ii Chemical reactions on grafted films were demonstrated and analyzed by a combination of the above mentioned characterization techniques. In particular, the reduction of nitrophenyl (NP)films, amine-coupling reactions, photoactivation of grafted films with oxalyl chloride and electrostatic assembly of anionic gold nanoparticles were investigated. Selected chemical reactions permitted identification and evaluation of the grafted layers, and demonstrated the ability to control the immobilization of chemical species. Microscale chemical patterning of two different types of modifiers on carbon surfaces was demonstrated using photolithographical techniques that utilized photochemical reactions with azides. Patterns of line-arrays with line widths of hundreds of micrometers to 10 µm were formed.