Classification of migraineur and healthy subjects using statistical pattern classifiers on functional Near Infrared Spectroscopy (NIRS) data is the main purpose of this study. Also a statistical comparison between trials that have different type of classifiers, classifier settings and feature sets is done. Features are extracted from raw light measurement data acquired with NIRS device, namely Niroxcope, during two separate previous studies, using Modified Beer-Lambert Law. After feature extraction, Na&iuml / ve Bayes classifier and k Nearest Neighbor classifier are utilized with and with-out Principal Component Analysis in separate trials. Results obtained are compared within each other using statistical hypothesis tests namely Mc Nemar and Cochran Q.

Dissertation (Ph.D.)--University of Toledo, 2009. / Typescript. "Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Physics ." Bibliography: leaves 71-74.

The research and development of organic electron donors is essential in the discovery of photodynamic therapy photosensitizers and catalysts, as well as in the fabrication of organic-based electronic devices. Recently, [pi]-extended tetrathiafulvalenes (exTTFs) have emerged as important organic donors due to their superb electronic properties. However, in general, exTTFs lack significant absorption in the visible and near-infrared portions of the electromagnetic spectrum, thereby limiting their utility. This doctoral dissertation depicts the author's efforts to address this inherent drawback of exTTFs by extending the electronic conjugation of tetrathiafulvalene moieties through pyrrole-based chromophores. The reported findings describe the design, synthesis, properties and potential applications of exTTFs with greatly enhanced absorption profiles. The first Chapter provides a brief historical overview on the history and development of [pi]-extended tetrathiafulvalenes. The various conjugated linkers utilized in exTTF systems are reviewed. In the latter part of the Chapter, emphasis is given to the applications in which exTTFs find use. Chapter 2, as the major focus of the dissertation, details the synthesis and characteristics of a quinoidal porphyrin-bridged exTTF, termed MTTFP. Several metalated complexes, including the Zn, Co, Cu, and Ni derivatives of MTTFP are reported. Additionally, the electrochemical, photophysical, and structural properties of MTTFPs are discussed. We also detail our efforts to synthesize and characterize both the one- and two-electron oxidized forms of MTTFPs. Finally, we discuss our efforts to reversibly switch thermodynamic electron transfer from ZnTTFP to Li@C₆₀ through coordination of axial ligands. Chapter 3 describes the formation of a 2:1 supramolecular ionic porphyrin complex between the two-electron oxidized form of ZnTTFP and a tetranionic sulfonated porphyrin. The association constants and the X-ray crystal structure of the complex are reported. A brief discussion outlining the photophysical characteristics (performed in Prof. Shunichi Fukuzumi and Prof. Dongho Kim's group) of the porphyrin donor-acceptor complexes are included. Chapter 4 details the synthesis, photophysical properties, and spectroelectrochemistry of a difluoroboradiazaindacene (BODIPY) bridged exTTF. This compound is referred to as ex-BODIPY. A singlet oxygen generation study provides initial evidence that ex-BODIPY could potentially serve as a photosensitizer. All of the experimental procedures, characterization data, and X-ray crystallographic data tables are reported in Chapter 5. / text

MicroNIR is a portable near-infrared diffuse reflection spectroscope. Its suitability for identifying environmental plastic polymers was evaluated through a series of performance tests. The plastic samples were collected during a beach survey in the Caribbean. First a reference database was built by analysing a series of reference plastic polymers. Prediction models were constructed by using principal component analysis (PCA) and cluster analysis on 2D- and 3D-scatterplots. Measurements of samples with a surface area down to 1 mm2 were successfully identified with the prediction models. Blend spectra were created by measuring two polymers simultaneously, from which each polymer NIR-fingerprint were able to be individually extracted from the blend spectra by subtracting the NIR-fingerprint of the opposite polymer. Prediction models were used to identify the samples in the tests with household plastics and the environmental plastic samples, collected in the Caribbean. Out of the forty-eight samples collected forty (83%) were identified. Twenty-seven were identified as polyethylene (56%), eleven as polypropylene (23%), one as polystyrene (2%), and one as polyamide (2%).

This report is exploring the possibility of characterizing hot Jupiter atmospheres using ground-based high-resolution spectroscopy. The ESO CRIRES infrared spectrometer is selected as the observing tool. Simulated observations are computed for known transiting systems. The properties of observations (noise, spectral coverage, resolution) are estimated with the CRIRES Exposure Time Calculator. An inverse method is used for reconstructing the transmission spectra of exoplanetary atmospheres and identifying spectral features. The possibility of using this method for non-transiting systems is examined. Three exoplanets are deemed possible to reconstruct the spectrum of. / Den här rapporten studerar möjligheten att karaktärisera heta Jupiter atmosfärer genom att använda markbaserad högupplöst spektroskopi. ESO:s CRIRES infraröda spektrometer används som observeringsvektyg. Simulerade observationer beräknas för kända system där planeten genomgår en transit. Flera aspekter kring observationer (brus, våglängdstäckning, upplösning) uppskattas med CRIRES Exposure Time Calculator. En invers metod används för att rekonstruera exoplanetatmosfärers transmissionsspektrum och för att identifiera spektraldrag. Möjligheten att använda den här metoden för system utan transit utforskas. Tre exoplaneter antas vara möjliga att rekonstruera spektrat från.

The ability of sub 100 nm nanoparticles to target and modulate the biology of cells will enable major advancements in cellular imaging and therapy in cancer and atherosclerosis. A key challenge is to load an extremely high degree of targeting, imaging, and therapeutic functionality into small, yet stable particles. A general mechanism is presented for thin autocatalytic growth on nanoparticle substrates (TAGS), as demonstrated for a homologous series of < 5 nm textured Au coatings on < 42 nm iron oxide cluster cores. Very low Au supersaturation levels are utilized to prevent commonly encountered excessive autocatalytic growth that otherwise produce thick shells. The degree of separation of nucleation to form the seeds from growth is utilized to control the morphology and uniformity of the thin Au coatings. The thin and asymmetric Au shells produce strong near infrared (NIR) absorbance with a cross section of ~10⁻¹⁴ m², whereas the high magnetic content per particles provides strong r2 spin-spin magnetic relaxivity of 200 mM⁻¹s⁻¹. TAGS may be generalized to a wide variety of substrates and high energy coatings to form core-shell nanoparticles of interest in a variety of applications as diverse as catalysis and bionanotechnology. High uptake of the nanoclusters by macrophages is facilitated by the dextran coating, producing intense NIR contrast both in cell culture and an in vivo rabbit model of atherosclerosis. A novel conjugation technique further allows covalent binding of anti-epidermal growth factor receptor (EGFR) monoclonal antibody (Ab) to the nanoclusters for highly selective targeting to EGFR over expressing cancer cells. AlexaFluor 488 tagged Ab nanocluster conjugates were prepared to correlate the number of conjugated Abs with the hydrodynamic diameter. The high targeting efficacy was evaluated by dark field reflectance imaging and atomic absorbance spectrometry (AAS). Colocalization of the nanoparticles by dual mode in-vitro imaging with dark field and fluorescence microscopy demonstrates the Abs remained attached to the Au surfaces. The extremely high curvature of the Au shells with features below 5 nm influence the spacing and orientations of the Abs on the surface, which has the potential to have a marked effect on biological pathways within cells. These targeted small multifunctional nanoclusters may solve some key molecular imaging challenges for cancer and atherosclerosis. / text

Cereal grains are an important part of human diet; hence, there is a need to maintain high quality and these grains must be free of physical and biological contaminants. A procedure was developed to differentiate physical contaminants from wheat using NIR (1000-1600 nm) hyperspectral imaging. Three experiments were conducted to select the best combinations of spectral pre-processing technique and statistical classifier to classify physical contaminants: seven foreign material types (barley, canola, maize, flaxseed, oats, rye, and soybean); six dockage types (broken wheat kernels, buckwheat, chaff, wheat spikelets, stones, and wild oats); and two animal excreta types (deer and rabbit droppings) from Canada Western Red Spring (CWRS) wheat. These spectra were processed using five spectral pre-processing techniques (first derivative, second derivative, Savitzky-Golay (SG) smoothing and differentiation, multiplicative scatter correction (MSC), and standard normal variate (SNV)). The raw and pre-processed data were classified using Support Vector Machines (SVM), Naïve Bayes (NB), and k-nearest neighbors (k-NN) classifiers. In each experiment, two-way and multi-way classifications were conducted. Among all the contaminant types, stones, chaff, deer droppings and rabbit droppings were classified with 100% accuracy using the raw reflectance spectra and different statistical classifiers. The SNV technique with k-NN classifier gave the highest accuracy for the classification of foreign material types from wheat (98.3±0.2%) and dockage types from wheat (98.9±0.2%). The MSC and SNV techniques with SVM or k-NN classifier gave perfect classification (100.0±0.0%) for the classification of animal excreta types from wheat. Hence, the SNV technique with k-NN classifier was selected as the best model. Two separate model performance evaluation experiments were conducted to identify and quantify (by number) the amount of contaminant type present in wheat. The overall identification accuracy of the first degree of contamination (one contaminant type with wheat) and the highest degree of contamination (all the contaminant type with wheat) was 97.6±1.6% and 92.5±6.5%, for foreign material types; 98.0±1.8% and 94.3±6.2%r for dockage types; and 100.0±0.0% and 100.0±0.0%, respectively for animal excreta types. The canola, stones, deer, and rabbit droppings were perfectly quantified (100.0±0.0%) at all the levels of contaminations. / February 2016

The work reported in this dissertation describes the design and synthesis of different gold nanoshells with strong absorption coefficients at the near-infrared region (NIR) of the spectrum, and includes preliminary studies of their use for the photo-induced heating of pancreatic cancer cells and ex vivo tissues. As the emphasis was on gold nanoshells with maximum extinctions located at 800 nm, the methods explored for their synthesis led us to the preparation of silica-core and hollow gold nanoshells of improved stability, with maximum extinctions at or beyond the targeted within the near-infrared window. The synthesis of silica-core gold nanoshells was investigated first given its relevance as one of the pioneering methods to produce gold nanostructures with strong absorption and scattering coefficients in the visible and the near-infrared regions of the spectrum. By using a classical method of synthesis, we explored the aging of the precursor materials and the effect of using higher concentrations than the customary for the reduction of gold during the shell growth. We found that the aging for one week of the as-prepared or purified precursors, namely, the gold cluster suspensions, and the seeded silica particles, along with higher concentrations of gold in the plating solution, produced fully coated nanoshells of 120 nm in size with smooth surfaces and maximum extinctions around 800 nm. Additional work carried out to reduce the time and steps in the synthesis of silica-core gold nanoshells, led us to improve the seeding step by increasing the ionic strength of the cluster suspension, and also to explore the growth of gold on tin-seeded silica nanoparticles. The synthesis of hollow gold nanoshells (HGS) of with maximum extinctions at the NIR via the galvanic replacement of silver nanoparticles for gold in solution was explored next. A first method explored led us to obtain HGS with maximum extinctions between 650 and 800 nm and sizes between 30 and 80 nm from silver nanoparticles, which were grown by the addition of silver nitrate and a mild reducer. We developed a second method that led us to obtain HGS with maximum extinctions between 750 and 950 nm by adjusting the pH of the precursor solution of the silver particles without much effort or additional steps. The last part of this work consisted in demonstrating the photo-induced heating of two biological systems containing HGS. Photothermal therapy studies of immobilized PANC1 pancreas cancer cells in well-plates were carried out with functionalized HGS. We found that cells exposed to HGS remained viable after incubation. Moreover, the cells incubated with HGS modified with mercaptoundecanoic acid and folic acid turned non-viable after being irradiated with a laser at 800 nm. The other study consisted in the laser-induced heating between 750 and 1000 nm of ex vivo tissues of chicken and pork with nanoshells injected. In comparison with non-injected tissues, it was found that the temperature at the irradiated areas with HGS increased more than 10 °C. Moreover, the extent of the heated area was broader when the laser was used at wavelengths beyond 900 nm, suggesting that the heating was due to the radiation absorbed and transformed into heat primarily by the HGS and at a lesser extent by the water in the tissue.

Saving energy in buildings is of great importance because about 30 to 40 % of the energy in the world is used in buildings. An electrochromic window (ECW), which makes it possible to regulate the inflow of visible light and solar energy into buildings, is a promising technology providing a reduction in energy consumption in buildings along with indoor comfort. A polymer electrolyte is positioned at the center of multi-layer structure of an ECW and plays a significant role in the working of the ECW. In this study, polyethyleneimine: lithium (bis(trifluoromethane)sulfonimide (PEI:LiTFSI)-based polymer electrolytes were characterized by using dielectric/impedance spectroscopy, differential scanning calorimetry, viscosity recording, optical spectroscopy, and electrochromic measurements. In the first part of the study, PEI:LiTFSI electrolytes were characterized at various salt concentrations and temperatures. Temperature dependence of viscosity and ionic conductivity of the electrolytes followed Arrhenius behavior. The viscosity was modeled by the Bingham plastic equation. Molar conductivity, glass transition temperature, viscosity, Walden product, and iso-viscosity conductivity analysis showed effects of segmental flexibility, ion pairs, and mobility on the conductivity. A connection between ionic conductivity and ion-pair relaxation was seen by means of (i) the Barton-Nakajima-Namikawa relation, (ii) activation energies of the bulk relaxation, and ionic conduction and (iii) comparing two equivalent circuit models, containing different types of Havriliak-Negami elements, for the bulk response. In the second part, nanocomposite PEI:LiTFSI electrolytes with SiO2, In2O3, and In2O3:Sn (ITO) were examined. Adding SiO2 to the PEI:LiTFSI enhanced the ionic conductivity by an order of magnitude without any degradation of the optical properties. The effect of segmental flexibility and free ion concentration on the conduction in the presence of SiO2 is discussed. The PEI:LiTFSI:ITO electrolytes had high haze-free luminous transmittance and strong near-infrared absorption without diminished ionic conductivity. Ionic conductivity and optical clarity did not deteriorate for the PEI:LiTFSI:In2O3 and the PEI:LiTFSI:SiO2:ITO electrolytes. Finally, propylene carbonate (PC) and ethylene carbonate (EC) were added to PEI:LiTFSI in order to perform electrochromic measurements. ITO and SiO2 were added to the PEI:LiTFSI:PC:EC and to a proprietary electrolyte. The nanocomposite electrolytes were tested for ECWs with the configuration of the ECWs being plastic/ITO/WO3/polymer electrolyte/NiO (or IrO2)/ITO/plastic. It was seen that adding nanoparticles to polymer electrolytes can improve the coloring/bleaching dynamics of the ECWs. From this study, we show that nanocomposite polymer electrolytes can add new functionalities as well as enhancement in ECW applications.

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