This thesis explores the use of Raman Spectroscopy to study the battery cathode material LiFePO4. Surface Enhanced Raman Spectroscopy (SERS) was incorporated into the study due to fluorescence that traditionally plagues Raman. By imaging LiFePO4 nanoparticles, an understanding can be gained of the complex chemistry taking place when the material is lithiated and delithiated at the nanoscale level and the phase changes of the material that occur during this process. The use of bimetallic (Au/Ag) SERS substrates allowed for more stable substrates with longer shelf life compared single metal Ag substrates. Further tuning of these substrates can be applied to the ever evolving science of energy storage material technology as a way to track phase changes in the material. / text

Cancer is the leading cause of death worldwide and one third of its burden can be decreased with early detection. Surface enhanced Raman spectroscopic (SERS) based imaging is a promising new technique for non-invasive detection of tumours due to its ultra-sensitivity and multiplexing capabilities. For in vivo SERS molecular imaging, a biocompatible, robust and targeted nanoparticle is required to attain high sensitivity and specificity. In this thesis, a SERS capable gold nanoparticle was rationally designed by encapsulation with a phospholipid bilayer which conferred biocompatibility, colloidal stability and versatility to changing surface chemistry. Moreover, validation of this SERS probe with a specific targeting ligand for carcinoma cells was studied through the targeting of a commonly overexpressed cancer receptor, epidermal growth factor receptor. Using this phospholipid design, optimizations with differing chemistries, targeting ligand or modifications for additional functionalities can be achieved for further development as a viable in vivo molecular imaging tool.

Cancer is the leading cause of death worldwide and one third of its burden can be decreased with early detection. Surface enhanced Raman spectroscopic (SERS) based imaging is a promising new technique for non-invasive detection of tumours due to its ultra-sensitivity and multiplexing capabilities. For in vivo SERS molecular imaging, a biocompatible, robust and targeted nanoparticle is required to attain high sensitivity and specificity. In this thesis, a SERS capable gold nanoparticle was rationally designed by encapsulation with a phospholipid bilayer which conferred biocompatibility, colloidal stability and versatility to changing surface chemistry. Moreover, validation of this SERS probe with a specific targeting ligand for carcinoma cells was studied through the targeting of a commonly overexpressed cancer receptor, epidermal growth factor receptor. Using this phospholipid design, optimizations with differing chemistries, targeting ligand or modifications for additional functionalities can be achieved for further development as a viable in vivo molecular imaging tool.

The indole and phenole rings comprise the main part of tryptophan and tyrosine side chains in proteins and play an important role in the stabilization of tertiary structure, interaction with active centers in biomolecules, and electron transfer phenomena. To get better insight into the interactions of these functional groups, the artificial monomolecular structures have been constructed from the synthesized bifuncional compounds with thiol and indole or phenole ring functional groups able to form self-assembled monolayers on gold, silver and copper electrodes. Properties of these monolayers were studied by Raman, infrared, and sum-frequency generation spectroscopies. The main tasks of this work were to assess the adsorption peculiarities of the bifunctional thiols at the initial stage of the monolayer formation, to determine the influence of the electrode nature on the monolayer structure, and to establish the potential influence on the properties of the terminal functional groups. It was demonstrated for the first time that at the initial stage of monolayer formation the methylene groups interact with the metal surface. Evidence for the metal-induced lowering of the CH stretching mode frequency down to 2820 cm-1 was provided. It was demonstrated that indole ring interacts with the Ag electrode surface at sufficiently negative potentials and this interaction can be recognized from the downshift of the W16 mode from ~ 1010 cm-1 to ~ 1001 cm-1. Investigations of indole... [to full text] / Triptofano ir tirozino aminorūgščių funkcinės grupės – indolo ir fenolio žiedai, stabilizuoja baltymų tretinę struktūrą, sąveikauja su aktyviais centrais biomolekulėse, dalyvauja elektronų pernašos procesuose. Siekiant giliau suprasti kaip šios grupės sąveikauja, buvo sukonstruotos dirbtinės monosluoksninės struktūros, sudarytos iš susintetintų bifunkcinių junginių, turinčių galines tiolio ir indolo žiedo arba fenolio žiedo grupes ir gebančių formuoti savitvarkius monosluoksnius ant aukso, sidabro ir vario elektrodų. Jų savybės ištirtos Ramano, infraraudonosios ir suminio dažnio generacijos spektroskopijų metodais. Pagrindiniai darbo tikslai buvo nustatyti bifunkcinių alkantiolių struktūrą ir adsorbcijos ypatumus pradinėje monosluoksnio formavimosi stadijoje, elektrodo prigimties įtaką monosluoksnių struktūrai ir potencialo įtaką galinių funkcinių grupių savybėms. Paviršiaus sustiprintos Ramano spektroskopijos metodu pirmą kartą parodyta, kad pradinėse monosluoksnių formavimo stadijose metileno grupės sąveikauja su metalo paviršiumi. Darbe įrodyta, kad dėl sąveikos su metalu spektruose atsiranda žemesnio dažnio („minkšta“) CH juosta ties 2820 cm-1. Pirmą kartą parodyta, kad indolo žiedas sąveikauja su Ag paviršiumi, esant pakankamai neigiamiems potencialams ir tą sąveiką galima spektriškai atpažinti pagal W16 modos ties ~1010 cm-1 dažnio sumažėjimu iki ~ 1001 cm-1. Tiriant indolo žiedu terminuotus ir mišrius monosluoksnius su įterptomis oktadekantiolio molekulėmis nustatytas... [toliau žr. visą tekstą]

Triptofano ir tirozino aminorūgščių funkcinės grupės – indolo ir fenolio žiedai, stabilizuoja baltymų tretinę struktūrą, sąveikauja su aktyviais centrais biomolekulėse, dalyvauja elektronų pernašos procesuose. Siekiant giliau suprasti kaip šios grupės sąveikauja, buvo sukonstruotos dirbtinės monosluoksninės struktūros, sudarytos iš susintetintų bifunkcinių junginių, turinčių galines tiolio ir indolo žiedo arba fenolio žiedo grupes ir gebančių formuoti savitvarkius monosluoksnius ant aukso, sidabro ir vario elektrodų. Jų savybės ištirtos Ramano, infraraudonosios ir suminio dažnio generacijos spektroskopijų metodais. Pagrindiniai darbo tikslai buvo nustatyti bifunkcinių alkantiolių struktūrą ir adsorbcijos ypatumus pradinėje monosluoksnio formavimosi stadijoje, elektrodo prigimties įtaką monosluoksnių struktūrai ir potencialo įtaką galinių funkcinių grupių savybėms. Paviršiaus sustiprintos Ramano spektroskopijos metodu pirmą kartą parodyta, kad pradinėse monosluoksnių formavimo stadijose metileno grupės sąveikauja su metalo paviršiumi. Darbe įrodyta, kad dėl sąveikos su metalu spektruose atsiranda žemesnio dažnio („minkšta“) CH juosta ties 2820 cm-1. Pirmą kartą parodyta, kad indolo žiedas sąveikauja su Ag paviršiumi, esant pakankamai neigiamiems potencialams ir tą sąveiką galima spektriškai atpažinti pagal W16 modos ties ~1010 cm-1 dažnio sumažėjimu iki ~ 1001 cm-1. Tiriant indolo žiedu terminuotus ir mišrius monosluoksnius su įterptomis oktadekantiolio molekulėmis nustatytas... [toliau žr. visą tekstą] / The indole and phenole rings comprise the main part of tryptophan and tyrosine side chains in proteins and play an important role in the stabilization of tertiary structure, interaction with active centers in biomolecules, and electron transfer phenomena. To get better insight into the interactions of these functional groups, the artificial monomolecular structures have been constructed from the synthesized bifuncional compounds with thiol and indole or phenole ring functional groups able to form self-assembled monolayers on gold, silver and copper electrodes. Properties of these monolayers were studied by Raman, infrared, and sum-frequency generation spectroscopies. The main tasks of this work were to assess the adsorption peculiarities of the bifunctional thiols at the initial stage of the monolayer formation, to determine the influence of the electrode nature on the monolayer structure, and to establish the potential influence on the properties of the terminal functional groups. It was demonstrated for the first time that at the initial stage of monolayer formation the methylene groups interact with the metal surface. Evidence for the metal-induced lowering of the C−H stretching mode frequency down to 2820 cm-1 was provided. It was demonstrated that indole ring interacts with the Ag electrode surface at sufficiently negative potentials and this interaction can be recognized from the downshift of the W16 mode from ~ 1010 cm-1 to ~ 1001 cm-1. Investigations of indole ring... [to full text]

This thesis work describes the fabrication and surface enhanced Raman spectroscopy (SERS) characterization of vertically aligned nitrogen (N) doped multi walled carbon nanotube (MWCNT) forests coated by silver (Ag) and gold (Au) nanoparticles. In the present work, the CNT forests were grown from a catalyst metal layer by the chemical vapor deposition (CVD) process at temperature of 800 oC and a physical vapor deposition (PVD) and annealing processes were applied subsequently for the evaporation and diffusion of noble metal nanoparticles on the forest. Transistor patterning of 20, 50 and 100 μm were made onto the silicon-oxide (SiO2) wafers through the photolithography process with and without depositing a thickness of 10 nm titanium (Ti) buffer layer on the Si-surfaces. Iron (Fe) and cobalt (Co) were used together to deposite a thickness of 5 nm catalyst layer onto the Single Side Polished (SSP) wafers. As carbon and nitrogen precursor for the CNT growth was used pyridine. Two different treatment times (20 and 60 minutes) in the CVD process determined the CNT forest height. Scanning Electron Microscopy (SEM) imaging was employed to characterize the CNT forest properties and Ag and Au nanoparticle distribution along the CNT walls. The existence of “hot spots” created by the Ag and Au nanoparticles through the surface roughness and plasmonic properties was demonstrated by the SERS measurements. Accordingly, the peak intensity at wave number of 1076 cm-1 was picked up from each SERS spectra to establish the Ag- and Au-trend curves with different concentrations of 4-ATP solution. The SERS mapping was also carried out to study the Ag- and Au-coated CNT surface homogeneity and “hot spots” distribution on the CNT surface. The SERS enhancement factors (EF) were calculated by applying an analyte solution of ethanolic 4-ATP on the CNT surface. The calculated values of EF from Ag- and Au-coated CNT forests were 9×106 and 2.7×105 respectively.

Gold nanoparticles were deposited onto a silicon substrate using electroless deposition. The process was optimized by adjusting the deposition time, the temperature of the plating solution, the amount of time that the silicon was exposed to hydrofluoric acid, and the concentration of the plating solution. The nanoparticles deposited on the silicon were characterized using scanning electron microscopy. The optimized electroless deposition process was then used to modify the surface of silicon solar cells with gold nanoparticles for enhanced power generation. Spectral response and I-V curve tests were performed on the modified solar cells to quantify the enhancements. The modified surfaces of the silicon solar cells were characterized by scanning electron microscopy and reflectance measurements. The electroless deposition process was also used to generate nanostructures for surface-enhanced Raman scattering (SERS). A template-nanohole array was fabricated on silicon by focused ion beam milling. Gold nanoparticles were deposited in the holes of the template, resulting in interesting gold-nanodoughnut structures. The gold nanodoughnuts were examined by scanning electron microscopy, and their potential as SERS substrates were tested using Rhodamine 6G as a molecular probe under 633 nm laser excitation. / Graduate / 0494 / 0485 / mmillard@uvic.ca

Gold nanoparticles were deposited onto a silicon substrate using electroless deposition. The process was optimized by adjusting the deposition time, the temperature of the plating solution, the amount of time that the silicon was exposed to hydrofluoric acid, and the concentration of the plating solution. The nanoparticles deposited on the silicon were characterized using scanning electron microscopy. The optimized electroless deposition process was then used to modify the surface of silicon solar cells with gold nanoparticles for enhanced power generation. Spectral response and I-V curve tests were performed on the modified solar cells to quantify the enhancements. The modified surfaces of the silicon solar cells were characterized by scanning electron microscopy and reflectance measurements. The electroless deposition process was also used to generate nanostructures for surface-enhanced Raman scattering (SERS). A template-nanohole array was fabricated on silicon by focused ion beam milling. Gold nanoparticles were deposited in the holes of the template, resulting in interesting gold-nanodoughnut structures. The gold nanodoughnuts were examined by scanning electron microscopy, and their potential as SERS substrates were tested using Rhodamine 6G as a molecular probe under 633 nm laser excitation. / Graduate / 0494 / 0485 / mmillard@uvic.ca

The clinical evaluation of people with possible myocardial infarction (MI) is often limited by atypical symptoms and inconclusive initial electrocardiograms. A recent consensus from the American College of Cardiology has redefined acute MI to include cardiac markers as central to diagnosis. To address this clinical need, a sensitive microfluidic surface-enhanced Raman spectroscopy (SERS) nanochannel-based optical device is being developed for ultimate use as a point-of-care device for the simultaneous measurement of MI blood biomarkers. The device can provide enhancements of the Raman signal of the analyte measured of up to 1013 using a mechanical aggregation technique at the interface of nanofluidic structures enabling repeatable SERS measurements. Specifically in this research iterations of a sensitive, low volume SERS platform technology were designed that provided quantitative information across a specific range. With the SERS platforms studied, not only were SERS enhancements of up to 1013 achieved but also imprecision values of less than 10% across the 10-50 pM range using a ratiometric approach and qualitative detection down to 100 aM was achieved. Beyond assessment of SERS substrates, assay designs were investigated and characterized including, label-free techniques and competitive immunoassay formats. Lastly, detecting the SERS signal of multiplexed reporter molecules was investigated. By identifying the analyte and assay constraints the design and optimization of future assays will be aided using this SERS platform technology.

Biological/biochemistry analyses traditionally require bulky instruments and a great amount of volume of biological/chemical agents, and many procedures have to be performed in certain locations such as medical centers or research institutions. These limitations usually include time delay in testing. The delays may be critical for some aspects such as disease prevention or patient treatment. One solution to this issue is the realization of point-of-care (POC) testings for patients, a domain in public health, meaning that health cares are provided near the sites of patients using well-designed and portable medical devices. Transportation of samples between local and central institutions can therefore be reduced, facilitating early and fast diagnosis. A closely related topic in engineering, lab-on-a-chip (LOC), has been discussed and practiced in recent years. LOC emphasizes integrating several functions of laboratory processes in a small portable device and performing analysis using only a very small amount of sample volume, to achieve low-cost and rapid analysis. From an engineer's point of view, LOC is the strategy to practice the idea of POC testing. This dissertation aimed at exploring the POC potentials of porous membrane-base LOC devices, which can be used to simplify traditional and standard laboratory procedures. In this study, three LOC prototypes are shown and discussed. First the protein sensor incorporating with silica nanofiber membrane, which has shown 32 times more improvement of sensitivity than a conventional technique and a much shorter detection time; secondly the bacteria filter chip that uses a sandwiched aluminum oxide membrane to stabilize the bacteria and monitor the efficacy of antibiotics, which has reduced the test time from 1 day of the traditional methods to 1 hour; the third is the sensor combining microfluidics and silica nanofiber membrane to realize Surface Enhanced Raman Spectroscopy on bio-molecules, which has enhancement factor 10^9 and detection limit down to nanomolar, but simple manufacturing procedures and reduced fabrication cost. These results show the porous-base membrane LOC devices may have potentials in improving and replacing traditional detection methods and eventually be used in POC applications.