Graduate Theses & Dissertations

Frequency-time and polarization considerations in spectral-focusing-based CARS microscopy
Spectral-focusing-based coherent anti-Stokes Raman scattering (SF-CARS) microscopy is a powerful imaging technique that involves temporally and spectrally stretching ultrashort laser pulses and controlling their frequency-time characteristics. However, a broader and more detailed understanding of the frequency-time characteristics of the laser pulses and signals involved, how they are related, and how they influence important aspects such as the spectral resolution is needed to understand the full potential of SF-CARS systems. In this work, I elucidate these relationships and discuss how they can be exploited to optimize SF-CARS microscopy setups. I present a theoretical analysis of the relationships between the spectral resolution, the degree of chirp-matching, and pulse bandwidth in SF-CARS. I find that, despite allowing better ultimate spectral resolution when chirp-matching is attained, the use of the broadest bandwidth pulses can significantly worsen the spectral resolution if the pulses are not chirp-matched. I demonstrate that the bandwidth of the detected anti-Stokes signal is minimized when the pump is twice as chirped as the Stokes, meaning that (perhaps counter-intuitively) a narrow anti-Stokes bandwidth does not imply good spectral resolution. I present approximate expressions that relate the bandwidths of the pump, Stokes, and anti-Stokes pulses to the degree of chirp-matching and outline how these could be used to estimate the amount of glass needed to attain chirp-matching. I develop a spectral-focusing-based polarization-resolved (SFP-CARS) setup, by modifying our existing system, to explore the merits of integrating polarization-dependent detection as an add-on to existing SF-CARS setups. By using the system to study polarization-dependent features in the CARS spectrum of benzonitrile, I assess its capabilities and demonstrate its ability to accurately determine Raman depolarization ratios. Ultimately, the detected anti-Stokes signals are more elliptically polarized than desired, hindering a complete suppression of the non-resonant background. Nevertheless, I find that the SFP-CARS setup is a useful tool for studying polarization-dependent features in the CARS spectra of various samples and is worthy of further investigation. This work clarifies several technical aspects of SF-CARS microscopy and provides researchers with valuable information to consider when working with SF-CARS microscopy systems. Author Keywords: coherent anti-Stokes Raman scattering, nonlinear microscopy, polarization, spectral focusing, spectroscopy
Extraction and Characterization of Hyaluronic Acid and Collagen from Eggshell Membrane Waste
Connecting academia to industry is one important way to advance towards meeting the United Nations (UN) Sustainability Goals (SDGs).1 Sustainability can be applied to all industrial sectors with the SDGs being implemented by 2030.2 This research contributes to the SDGs by investigating a way to remediate an industrial waste stream in the egg-breaking industry. If adopted, this would reduce the amount of eggshell membrane (ESM) waste placed in landfill where it does not decompose properly. The work described in this thesis specifically targets extraction of collagen and hyaluronic acid (HA), two components of the ESM that are of commercial value in the cosmetic, pharmaceutical, and biomedical industries3,4 . Deliverables from this research include economically viable extraction methods, developed based on green chemistry approaches, that can be transferred from lab bench to industrial scale. The extraction development process was guided by the 12 Principles of Green Chemistry5,6,7 and the 12 Principles of Green Engineering.8 HA was most successfully extracted using a sodium acetate solution on ground ESM. Filtrate was collected, exhaustively dialyzed and lyophilized. High molecular weight HA was recovered. Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and proton nuclear magnetic resonance (NMR) spectroscopy compared extracted material to reference HA identifying successful extraction. Collagen was extracted using acetic acid or pepsin enzyme digestion. Hydrophilic interaction liquid chromatography (HILIC) coupled with mass spectrometry (MS) compared amino acid composition of extracted materials to reference collagen material. FTIR-ATR spectra also supported successful extraction of collagen. This work identifies that HA and collagen can be conveniently extracted from ESM using an economical approach that can be implemented into egg-breaking facilities. This work highlights the benefits of connecting academia to industry to advance green chemical approaches while implementing sustainable practices into existing industry. Author Keywords: collagen, eggshell membrane waste, extraction, green chemistry, hyaluronic acid, sustainability
UV-Curable hybrid sol-gel materials
This thesis describes the synthesis, application and evaluation of a UV crosslinked 3-methacryloxypropyltrimethoxysilane-derived coating formulation. This is a two-component sol-gel system with 3-methacryloxypropyltrimethoxysilane (MaPTMS) and tetraethoxysilane (TEOS). Herein we show that if we change the co-solvent required for solubilizing MaPTMS from the more common methanol and ethanol to isopropanol we change the rate of hydrolysis from days or weeks to minutes. With the assistance of 2D 29Si-NMR we demonstrate that the system undergoes extensive condensation in twenty minutes. Using standard UV irradiation, the material can be extensively UV crosslinked with 70% of the methacryloxy functionality being consumed in 5 minutes upon irradiation in the presence of a photo-initiator. When this material is used to coat low carbon steel and immersed in an accelerated corrosion solution (dilute Harrison’s solution); this material affords low carbon steel 25 hours of protection when crosslinked and 17 hours of protection when uncrosslinked. The material was then used to encapsulate polyaniline (PANI), an intrinsic conductive polymer used in the corrosion protection of metal substrates. PANI has been encapsulated previously in sol-gel material, but due to the pH dependence of the solubility of PANI, it can not be encapsulated in more commonly chemically crosslinked sol-gel. As our system is UV crosslinked rather than chemically crosslinked, we were able to successfully demonstrate the inclusion of PANI into our coating system. Finally, this thesis includes a thorough computational investigation into the structure and band gap of PANI. Through the analysis of the band gap it was shown that the structure of the polymer commonly displayed in literature is not the correct structure of the polymer. Our results suggest that when PANI is made electrochemically, the oligomer contains two quinoid units next to one another instead of the more usually represented regularly alternating benzoid and quinoid units. The results also suggest that when PANI is made using the oxidant ammonium persulfate, the polymer most likely contains a Michael adduct structure somewhere in the polymer chain which dominates PANI’s electronic properties. Author Keywords: 3-Methacryloxypropyltrimethoxysilane, Computational Chemistry , Corrosion , Polyaniline, Tetraethoxysilane
Novel Aliphatic Amides from Vegetable Oils as Bio-Based Phase Change Materials
Energy storage efficiency and sustainability require advanced technologies and novel materials. Recently, bio-based phase change materials (PCMs) have received significant attention for thermal energy storage (TES) uses. Vegetable oils are versatile renewable feedstocks that are well suited for the development of sustainable, functional PCMs. PCMs derived from vegetable oil, which compares favorably with paraffin waxes, the industry standard, are currently available. However, their melting points are typically below 80 °C preventing their wider integration in TES applications, particularly those requiring higher temperatures. The present work manipulated the structural building blocks of fatty acids to advantageously affect the intermolecular forces and increase the properties relevant to TES. The polar amide functional group was incorporated into fatty moieties to take advantage of the strong hydrogen bonds that it forms to increase intermolecular attractions and hence increase the phase change temperature and enthalpy as well as to improve thermal stability and thermal conductivity. A series of carefully designed lipid-derived monoamides and four series of lipid-derived diamides were synthesized via benign and simple amidation reactions. The purity of the amides and the intermolecular hydrogen bond strength were assessed using 1H NMR and FTIR. The properties relevant to TES such as thermal transition, crystal structure and polymorphism, thermal stability and thermal conductivity were measured using DSC, XRD, TGA and a thermal conductivity analyzer, respectively. The complex roles of the PCM’s constituting molecular building blocks in the phase behavior were elucidated and correlations between structure, processing conditions and macroscopic physicochemical properties, never before elucidated, were assembled in predictive relationships, drawing a unified picture of the rules that generally govern the phase behavior of lipid-derived PCMs. Practically, the prepared amides demonstrated desirable TES properties with substantial performance improvement over current bio-based PCMs. They presented increased phase change temperatures (79 - 159 °C), enthalpies of fusion (155 - 220 J/g) and thermal stability (234 - 353 °C). More importantly, the predictive structure-function relationships established in this work will allow the straightforward engineering of lipid-derived amide PCM architectures with judicious selection of molecular building blocks to extend the range of organic PCMs and deliver thermal properties desirable for TES applications. Author Keywords: LATENT HEAT THERMAL ENERGY STORAGE, LIPID-DERIVED AMIDES, PHASE CHANGE MATERIALS, RENEWABLE, SOLID LIQUID AMIDE PCMS, THERMAL PROPERTIES
Advanced broadband CARS microscopy based on a supercontinuum-generating photonic crystal fiber
I have developed and improved a coherent anti-Stokes Raman scattering (CARS) microscope based on the spectral focusing (SF) technique. The CARS microscope uses an 800 nm oscillator and a photonic crystal fibre module to generate the supercontinuum Stokes. The photonic crystal fibre was originally designed to generate light beyond 945 nm which is useful for CARS microscopy in the CH/OH frequencies but essentially prevents access to the important fingerprint region at lower frequencies. With expert and nontraditional approaches to generating supercontinuum with sufficient power at wavelengths below 945 nm, I substantially extend the usefulness of the module for SF-CARS microscopy deep into the fingerprint region. Moreover, with the invention of a dynamic supercontinuum generation scheme we call "spectral surfing," I improve both the brightness of the CARS signal and extend the accessible CARS frequency range to frequencies as low as 350 cm$^{-1}$ and as high as 3500 cm$^{-1}$---all in a single scan-window. I demonstrate the capabilities of our broadband SF-CARS system through CARS and four-wave mixing hyperspectroscopy on samples such as astaxanthin, lily pollen and glass; liquid chemicals such as benzonitrile, nitrobenzene and dimethyl sulfoxide; and on pharmaceutical samples such as acetaminophen, ibuprofen, and cetirizine. Furthermore, In search of more useful Stokes supercontinuum sources, I compare the performance of two commercial photonic crystal fibre modules for use in SF-CARS applications, ultimately finding that one module provides better spectral characteristics for static supercontinuum use, while the other provides improved characteristics when spectral surfing is implemented. Author Keywords: coherent anti-Stokes Raman scattering, nonlinear microscopy, scanning microscopy, spectroscopy, supercontinuum generation, vibrational spectroscopy
Supercritical Water Chemistry
Supercritical water (SCW) exhibits unique properties that differentiates it from its low temperature behaviour. Hydrogen bonding is dramatically reduced, there is no phase boundary between liquid and gaseous states, heat capacity increases, and there is a drastic reduction of the dielectric constant. Efforts are underway for researchers to harness these properties in the applications of power generation and hazardous waste destruction. However, the extreme environment created by the high temperatures, pressures and oxidizing capabilities pose unique challenges in terms of corrosion not present in subcritical water systems. Molecular Dynamics (MD) simulations have been used to obtain mass transport, hydration numbers and the influence on water structure of molecular oxygen, chloride, ammonia and iron (II) cations in corrosion crevices in an iron (II) hydroxide passivation layer. Solvation regimes marking the transitions of solvation based versus charge meditated processes were explored by locating the percolation thresholds of both physically and hydrogen bonded water clusters. A SCW flow through reactor was used to study hydrogen evolution rates over metal oxide surfaces, metal release rates and the kinetics for the oxidation of hydrogen gas by oxygen in SCW. Insights into corrosion phenomena are provided from the MD results as well as the experimental determination of flow reactor water and hydrogen chemistry. Author Keywords: Flow Studies, Molecular Dynamics, Supercritical Water
silicon sol-gel approach to the development of forensic blood substitutes
The research and development of synthetic blood substitutes is a reported need within the forensic community. This work contributes to the growing body of knowledge in bloodstain pattern analysis by offering a materials science approach to designing, producing and testing synthetic forensic blood substitutes. A key deliverable from this research is the creation of a robust silicon-based material using the solution-gelation technique that has been validated for controlled passive drip and spatter simulation. The work investigates the physical properties (viscosity, surface tension and density) of forensic blood substitute formulations and describes the similarity in the spreading dynamics of the optimized material to whole human blood. It then explores how blood and other fluids behave in impact simulation using high-speed video analysis and supports the use of the optimized material for spatter simulation. Finally, the work highlights the practical value of the material as an educational tool for both basic and advanced bloodstain experimentation and training. Author Keywords: bloodstain pattern analysis, forensic blood substitutes, high-speed video analysis, silicon solution-gelation chemistry, thin-film deposition, training and education
Lipid-derived Thermoplastic Poly(ester urethane)s
Thermoplastic poly(ester urethane)s (TPEU)s derived from vegetable oils possess inferior physical properties compared to their entirely petroleum-based counterparts due to the structural limitations and lower reactivity of the precursor lipid-derived monomers. The present work shows that high molecular weight of TPEUs with enhanced performance can be obtained from lipid-derived monomers via (i) the synthesis of polyester diols with controlled molecular weights, (ii) the tuning of the functional group stoichiometry of the polyester diols and the diisocyanate during polymerization, (iii) the degree of polymerization (iv) the control of the hard segment hydrogen bond density and distribution via the use of a chain extender and (v) different polymerization protocols. Solvent-resistant TPEUs with high molecular weight displaying polyethylene-like behavior and controlled polyester and urethane segment phase separation were obtained. Structure-property investigations revealed that the thermal transition temperatures and tensile properties increased and eventually plateaued with increasing molecular weight. Novel segmented TPEUs possessed high phase separation and showed elastomeric properties such as low modulus and high elongation analogous to rubber. The response of the structurally optimized TPEUs to environmental degradation was also established by subjecting the TPEUs to hydrothermal ageing. TPEUs exhibited thermal and mechanical properties that were comparable to commercially available entirely petroleum-based counterparts, and that could be tuned in order to achieve enhanced physical properties and controlled degradability. Author Keywords: Hydrothermal degradation, Molecular weight control, Polyester diols, Renewable resources, Structure-property relationships, Thermoplastic poly(ester urethane)s
Synthesis of Lipid Based Polyols from 1-butene Metathesized Palm Oil for Use in Polyurethane Foam Applications
This thesis explores the use of 1-butene cross metathesized palm oil (PMTAG) as a feedstock for preparation of polyols which can be used to prepare rigid and flexible polyurethane foams. PMTAG is advantageous over its precursor feedstock, palm oil, for synthesizing polyols, especially for the preparation of rigid foams, because of the reduction of dangling chain effects associated with the omega unsaturated fatty acids. 1-butene cross metathesis results in shortening of the unsaturated fatty acid moieties, with approximately half of the unsaturated fatty acids assuming terminal double bonds. It was shown that the associated terminal OH groups introduced through epoxidation and hydroxylation result in rigid foams with a compressive strength approximately 2.5 times higher than that of rigid foams from palm and soybean oil polyols. Up to 1.5 times improvement in the compressive strength value of the rigid foams from the PMTAG polyol was further obtained following dry and/or solvent assisted fractionation of PMTAG in order to reduce the dangling chain effects associated with the saturated components of the PMTAG. Flexible foams with excellent recovery was achieved from the polyols of PMTAG and the high olein fraction of PMTAG indicating that these bio-derived polyurethane foams may be suitable for flexible foam applications. PMTAG polyols with controlled OH values prepared via an optimized green solvent free synthetic strategy provided flexible foams with lower compressive strength and higher recovery; i.e., better flexible foam potential compared to the PMTAG derived foams with non-controlled OH values. Overall, this study has revealed that the dangling chain issues of vegetable oils can be addressed in part using appropriate chemical and physical modification techniques such as cross metathesis and fractionation, respectively. In fact, the rigidity and the compressive strength of the polyurethane foams were in very close agreement with the percentage of terminal hydroxyl and OH value of the polyol. The results obtained from the study can be used to convert PMTAG like materials into industrially valuable materials. Author Keywords: Compressive Strength, Cross Metathesis, Fractionation, Polyols, Polyurethane Foams, Vegetable Oils
Novel Aliphatic Lipid-Based Diesters for use in Lubricant Formulations
Structure-property relationships are increasingly valued for the identification of specifically engineered materials with properties optimized for targeted application(s). In this work, linear and branched diesters for use in lubricant formulations are prepared from lipid-based oleochemicals and their structure-property relationships reported. It is shown that the branched diesters possess exceptional physical property profiles, including suppression of crystallization, and are superior alternatives for use in lubricant formulations. For the linear aliphatic diesters, both high and low temperature properties were predictable functions of total chain length, and both were differently influenced by the fatty acid versus diol chain length. Symmetry did not influence either, although thermal stability decreased and thermal transition temperatures increased with increasing saturation. All of the linear diesters demonstrated Newtonian flow behaviour. Viscosity was also predictable as a function of total chain length; any microstructural features due to structural effects were superseded by mass effects. Author Keywords: Crystallization, Phase behaviour, Rheology, Structure-Function, Thermogravimetric analysis, Vegetable Oils
Mitigating Cold Flow Problems of Biodiesel
The present thesis explores the cold flow properties of biodiesel and the effect of vegetable oil derived compounds on the crystallization path as well as the mechanisms at play at different stages and length scales. Model systems including triacylglycerol (TAG) oils and their derivatives, and a polymer were tested with biodiesel. The goal was to acquire the fundamental knowledge that would help design cold flow improver (CFI) additives that would address effectively and simultaneously the flow problems of biodiesel, particularly the cloud point (CP) and pour point (PP). The compounds were revealed to be fundamentally vegetable oil crystallization modifiers (VOCM) and the polymer was confirmed to be a pour point depressant (PPD). The results obtained with the VOCMs indicate that two cis-unsaturated moieties combined with a trans-/saturated fatty acid is a critical structural architecture for depressing the crystallization onset by a mechanism wherein while the straight chain promotes a first packing with the linear saturated FAMEs, the kinked moieties prevent further crystallization. The study of model binary systems made of a VOCM and a saturated FAME with DSC, XRD and PLM provided a complete phase diagram including the thermal transformation lines, crystal structure and microstructure that impact the phase composition along the different crystallization stages, and elicited the competing effects of molecular mass, chain length mismatch and isomerism. The liquid-solid boundary is discussed in light of a simple thermodynamic model based on the Hildebrand equation and pair interactions. In order to test for synergies, the PP and CP of a biodiesel (Soy1500) supplemented with several VOCM and PLMA binary cocktails were measured using a specially designed method inspired by ASTM standards. The results were impressive, the combination of additives depressed CP and PP better than any single additive. The PLM and DSC results suggest that the cocktail additives are most effective when the right molecular structure and optimal concentration are provided. The cocktail mixture achieves then tiny crystals that are prevented from aggregating for an extended temperature range. The results of the study can be directly used for the design of functional and economical CFI from vegetable oils and their derivatives. Author Keywords: Biodiesel, Microstructure, Polymorphism, Pour point depressants, Triacylglycerol, Vegetable Oil Based Crystal Modifier
Novel Functional Materials From Renewable Lipids
Vegetable oils represent an ideal and renewable feedstock for the synthesis of a variety of functional materials. However, without financial incentive or unique applications motivating a switch, commercial products continue to be manufactured from petrochemical resources. Two different families of high value, functional materials synthesized from vegetable oils were studied. These materials demonstrate superior and unique performance to comparable petrochemical analogues currently on the market. In the first approach, 3 amphiphilic thermoplastic polytriazoles with differing lipophilic segment lengths were synthesized in a polymerization process without solvents or catalysts. Investigation of monomer structure influence on the resultant functional behaviour of these polymers found distinctive odd/even behaviour reliant on the number of carbon atoms in the monomers. Higher concentrations of triazole groups, due to shorter CH2 chains in the monomeric dialkynes, resulted in more brittle polymers, displaying higher tensile strengths but reduced elongation to break characteristics. These polymers had similar properties to commercial petroleum derived thermoplastics. One polymer demonstrated self-assembled surface microstructuring, and displayed hydrophobic properties. Antimicrobial efficacy of the polymers were tested by applying concentrated bacterial solutions to the surfaces, and near complete inhibition was demonstrated after 4 hours. Scanning electron microscope images of killed bacteria showed extensive membrane damage, consistent with the observed impact of other amphiphilic compounds in literature. These polytriazoles are suited for applications in medical devices and implants, where major concerns over antibiotic resistance are prevalent. In the second approach, a series of symmetric, saturated diester phase change materials (PCMs) were also synthesized with superior latent heat values compared to commercial petrochemical analogues. These diesters exhibit melting temperatures between 39 °C and 77 °C, with latent heats greater than 220 J/g; much greater than paraffin waxes, which are currently the industry standard. Assessment of the trends between differing monomer lengths, in terms of number of CH2 groups of the 24 diesters synthesized exhibited structure/function dependencies in latent heat values and phase change temperatures, providing an understanding of the influence of each monomer on PCM thermal properties. A synthetic procedure was developed to produce these PCMs from a low value biodiesel feedstock. Application of these PCMs in the thermoregulation of hot beverages was demonstrated using a representative diester. This PCM cooled a freshly brewed hot beverage to a desired temperature within 1 minute, compared to 18 minutes required for the control. Furthermore, the PCM kept the beverage within the desired temperature range for 235 minutes, 40 % longer than the control. Author Keywords: Antimicrobial Surface, Click Chemistry, Green Chemistry, Phase Change Material, Polytriazole, Renewable

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