The optical properties of metamaterials

This thesis studies the parametric investigation, polarisation dependence and characterization of fishnet structure at near infrared wavelengths. Detailed simulations are performed to understand the behaviour of the structure at near infrared and optical wavelengths. Simulations are performed to obtain negative refractive index of the fishnet structure formed from nanoimprint lithography (NIL) by taking into account the effect of substrate and polymethyl methacrylate (PMMA) beneath it. Two different structures have been designed and fabricated of varying dimensions using NIL and their resonant wavelength measured in the near infrared at 1.45 µm and 1.88 µm. Simulations suggest that a negative refractive index real part with the magnitude -0.24 is found at 1.53 µm and this decrease to a maximum magnitude of -0.57 at 1.9 µm. The PMMA and suppressed pillars are here responsible for the increasing material losses and limiting the value of negative refractive index. An analytical approach has been suggested to characterise fishnet structures at oblique incidence. The expressions for an absorbing medium are rewritten for an alternative definition of refractive index. The expressions are initially validated for a dielectric slab and a metal film. These results provide the possibility that this proposal may yield a general algorithm for obtaining the complex reflection and transmission coefficients for artificial structures. FDTD simulations have been extensively used in this thesis to understand the optical metamaterials and their characterization.

BODIPY-Porphyrazin-Hybride als panchromatische Lichtsammelsysteme für farbstoffsensibilisierte Solarzellen

In farbstoffsensibilisierten Solarzellen (DSSC) spielen Chromophore, die als Lichtsammel- und Energie-/Elektronentransfersysteme fungieren, eine zentrale Rolle. Phthalocyanine mit ihren intensiven Absorptionsbanden um 400 nm und 700 nm besitzen großes Potential für die effektive Sensibilisierung von Solarzellen. Trotz ihrer vielversprechenden physikochemischen Eigenschaften und intensiver Bemühungen erreichen Phthalocyanin-sensibilisierte Solarzellen nicht die Effizienzen, die bisher mit anderen Chromophorklassen erzielt werden konnten. In der vorliegenden Dissertation wurde die Entwicklung effizienter Lichtsammelsysteme für DSSC auf der Basis von Aza-substituierten Phthalocyaninen, sogenannten Pyrazinoporphyrazinen, verfolgt. Ein besonderer Fokus lag dabei auf einer Verbesserung der Absorptionseigenschaften der Chromophore im Bereich ihrer intrinsischen Absorptionslücke zwischen den Maxima um 400 nm und 700 nm. Um diese optische Lücke zu schließen wurden komplementär absorbierende BODIPY-Farbstoffe kovalent an synthetisch maßgeschneiderte Porphyrazine gebunden. Insgesamt wurden sechs neue Porphyrazin-Sensibilisatoren synthetisiert und photophysikalisch sowie elektrochemisch charakterisiert. Alle in dieser Arbeit untersuchten Porphyrazine tragen sterisch anspruchsvolle Tri(p-tolyl)propinyl-Gruppen um Agglomerationen zu vermeiden. Darüber hinaus wurden die Porphyrazine peripher entweder mit Hydroxy- oder Carboxygruppen als Bindungsstellen für oxidische Materialien ausgestattet sowie mit sechs BODIPY-Auxiliarfarbstoffen funktionalisiert, deren Substitutionsmuster variiert wurden. Zur Darstellung der komplexen Porphyrazine wurde eine Syntheseroute erarbeitet, die statistische Cyclisierungen unterschiedlicher Dinitril-Vorstufen beinhaltete und es ermöglichte, funktionelle Gruppen erst am vorgeformten Makrocyclus einzuführen. Die photophysikalische Untersuchung der hochfunktionalisierten Farbstoffe erfolgte über UV/Vis- und Fluoreszenzspektroskopie. Im Fall der BODIPY-Porphyrazin-Hybride schließt die zusätzliche Absorptionsbande der peripheren BODIPY-Einheiten die intrinsische Absorptionslücke der Porphyrazine. Die Hybride zeigen somit eine breite Absorption über den gesamten sichtbaren Spektralbereich mit hohen Extinktionskoeffizienten von ca. 4·10^5 M^−1cm^−1. Mittels Fluoreszenz- und Anregungsspektren wurde ein photoinduzierter Energie-transfer von den BODIPY-Einheiten auf den Porphyrazinkern nachgewiesen. Das elektrochemische Verhalten der BODIPY- und Porphyrazin-Verbindungen wurde mittels Cyclo- und Square-Wave-Voltammetrie untersucht. Die Effizienzen der Lichtenergieumwandlung wurden mit Hilfe von selbst-hergestellten und standardisierten farbstoffsensibilisierten Solarzellen bewertet. Alle Solarzellen zeigten eine messbare Photoaktivität unter Bestrahlung. Die Wirkungsgrade der Zellen lagen jedoch alle unter 1 %. Generell führten die Carboxyl-funktionalisierten Porphyrazine zu besseren Wirkungsgraden als die analogen, mit der tripodalen Ankergruppe ausgestatteten Derivate. Die mit Hilfe von Adsorptionsisothermen ermittelten Bindungskonstanten der Adsorption der Farbstoffe auf der TiO2-Oberfläche zeigten, dass beide Hafteinheiten eine feste Verankerung der Chromophore auf den TiO2-Elektroden ermöglichten. Insgesamt wirkte sich die Präsenz der peripheren BODIPY-Farbstoffe positiv auf die Wirkungsgrade der Solarzellen aus, jedoch nur in geringem Maß. Dieses Ergebnis wurde hauptsächlich auf die geringe Energiedifferenz zwischen der Leitungsbandkante des TiO2 und den LUMO-Energieniveaus der Chromophore zurückgeführt. Zusätzlich scheinen konkurrierende Prozesse wie die direkte Photoelektroneninjektion von den BODIPY-Einheiten in das TiO2 eine wichtige Rolle zu spielen. Neben der Anwendung in DSSC wurde die Wechselwirkung der Porphyrazine mit Graphen untersucht. Hierzu wurden A3B-Porphyrazine mit Pyrenyl-Seitenketten ausgestattet, die eine nicht-kovalente Verankerung des Chromophors auf Graphen ermöglichen. UV/Vis- und Fluoreszenzmessungen gaben u.a. erste Hinweise auf eine elektronische Kommunikation zwischen den beiden Hybridpartnern.

Infección por virus sincitial respiratorio y su relación con valores de IGG en niños críticos

Antecedente: La infección por el virus sincitial respiratorio (VSR) representa una elevada morbimortalidad, y en algunos casos necesidad de manejo en unidades de cuidado intensivo pediátrico (UCIP). La respuesta inmunológica influye de manera directa en la expresión de la severidad y pronóstico de los pacientes con infección respiratoria. Metodología: Estudio de una cohorte retrospectiva de pacientes con infección respiratoria grave secundaria a VSR, sin historia de inmunodeficiencia, atendidos en la UCIP del Hospital Universitario Clínica San Rafael. Se realizó análisis descriptivoglobaly de acuerdo a la categorización de las prueba de IgG. Resultados: De 188 pacientes que ingresaron a la UCIP, 13% presentaron infección por VSR (24), con una edad promedio de 7,3 (DE=3,6) meses. Pertenecían al sexo masculino79,83%. Se encontró que 12,5% tenían un valor de IgGbajo para su edad, 58,33% tenían valores en límite inferior y el 29,17% dentro de rangos normales para su edad. En los pacientes con IgG baja, fue mayor la presentación de choque séptico que no responde a líquidos (100 vs 92 vs 86%), la mediana de días de ventilación mecánica fue mayor (8 vs 6 vs 5 respectivamente), así como la mortalidad (67 vs 7,1 vs 0%). Conclusión: Nuestra serie encontró que aquellos pacientes con niveles bajos o valores en el límite inferior de IgG sérica tuvieron mayor compromiso sistémico, mayor duración de ventilación mecánica y mayor mortalidad. Se necesitan estudios prospectivos que relaciones niveles bajos de IgG con severidad y pronostico en estos pacientes con infección grave por VSR.

Efectos de una intervención educativa en los conocimientos y comportamientos relacionados con la fotoprotección durante la práctica de la actividad física en los estudiantes de un colegio público de Bogotá D.C., Colombia

Introducción: La incidencia del cáncer de piel melanoma y no melanoma es un problema de salud pública a nivel mundial. El incremento en la incidencia del cáncer de piel en los últimos años se debe a múltiples factores como: cambios en los estilos de vida, el envejecimiento de la población, cambios ambientales, el desconocimiento a la exposición a la radiación ultravioleta (RUV) durante la práctica de actividad física sin elementos de fotoprotección, siendo éste último reconocido como el principal factor de riesgo. Objetivo: Evaluar los efectos de una intervención educativa en los conocimientos y comportamientos relacionados con la fotoprotección durante la práctica de la actividad física en estudiantes de un colegio público de Bogotá D.C., Colombia. Métodos: Estudio de intervención, antes y después, no controlado en 281 estudiantes de los grados noveno, décimo y once de estratos 1-3 de un colegio público de Bogotá, con seguimiento a 1, 3 y 6 meses post-intervención. Se evaluaron los conocimientos y los hábitos de fotoprotección mediante un cuestionario Cancer Awareness Measure (CAM) y el modelo Transteórico de cambio comportamental de Prochaska y Di Clemente. El estudio se realizó durante el primer semestre de 2015 con 4 sesiones educativas de 60 minutos apoyadas con material audiovisual y pedagógico, acorde a la Guía para la Comunicación Educativa en el marco el control del cáncer publicada por el Instituto Nacional de Cancerología. Resultados: Del grupo de estudiantes que participaron del estudio, el 52,3% eran hombres, el promedio de edad fue de 15,46 ± 1,2 años. El tipo de piel predominante fue la trigueña con 65,8%. La intervención educativa produjo cambios significativos en los conocimientos de foto protección, finalizado el seguimiento al sexto mes. En cuanto a la prevención los estudiantes refirieron tener conocimiento de cómo examinar su piel en el momento basal (12,5% n=35), presentándose un aumento significativo de 62,6% (n=211) al sexto mes (p<0,05). Conclusión: El estudio demostró la efectividad de la intervención educativa, evidenciando cambios significativos en los conocimientos en fotoprotección y comportamientos preventivos del cáncer de piel durante la práctica de la actividad física en estudiantes de un colegio público de Bogotá D.C., Colombia.

Characterization of the volatile profile of Brazilian Merlot wines through comprehensive two dimensional gas chromatography time-of-flight mass spectrometric detection.

Wine aroma is an important characteristic and may be related to certain specific parameters, such as raw material and production process. The complexity of Merlot wine aroma was considered suitable for comprehensive two-dimensional gas chromatography (GCGC), as this technique offers superior performance when compared to one-dimensional gas chromatography (1D-GC). The profile of volatile compounds of Merlot wine was, for the first time, qualitatively analyzed by HS-SPME-GCxGC with a time-of-flight mass spectrometric detector (TOFMS), resulting in 179 compounds tentatively identified by comparison of experimental GCxGC retention indices and mass spectra with literature 1D-GC data and 155 compounds tentatively identified only by mass spectra comparison. A set of GCGC experimental retention indices was also, for the first time, presented for a specific inverse set of columns. Esters were present in higher number (94), followed by alcohols (80), ketones (29), acids (29), aldehydes (23), terpenes (23), lactones (16), furans (14), sulfur compounds (9), phenols (7), pyrroles (5), C13-norisoprenoids (3), and pyrans (2). GCxGC/TOFMS parameters were improved and optimal conditions were: a polar (polyethylene glycol)/medium polar (50% phenyl 50% dimethyl arylene siloxane) column set, oven temperature offset of 10ºC, 7 s as modulation period and 1.4 s of hot pulse duration. Co-elutions came up to 138 compounds in 1D and some of them were resolved in 2D. Among the coeluted compounds, thirty-three volatiles co-eluted in both 1D and 2D and their tentative identification was possible only due to spectral deconvolution. Some compounds that might have important contribution to aroma notes were included in these superimposed peaks. Structurally organized distribution of compounds in the 2D space was observed for esters, aldehydes and ketones, alcohols, thiols, lactones, acids and also inside subgroups, as occurred with esters and alcohols. The Fischer Ratio was useful for establishing the analytes responsible for the main differences between Merlot and non-Merlot wines. Differentiation among Merlot wines and wines of other grape varieties were mainly perceived through the following components: ethyl dodecanoate, 1-hexanol, ethyl nonanoate, ethyl hexanoate, ethyl decanoate, dehydro-2-methyl-3(2H)thiophenone, 3-methyl butanoic acid, ethyl tetradecanoate, methyl octanoate, 1,4 butanediol, and 6-methyloctan-1-ol.

Advanced fibre gratings fabricated in standard and infrared glass fibres by ultraviolet and near-infrared-femtosecond lasers

In this thesis, I describe studies on fabrication, spectral characteristics and applications of tilted fibre gratings (TFGs) with small, large and 45° tilted structures and novel developments in fabrication of fibre Bragg gratings (FBGs) and long period gratings (LPGs) in normal silica and mid-infrared (mid-IR) glass fibres using near-IR femtosecond laser. One of the major contributions presented in this thesis is the systematic investigation of structures, inscription methods and spectral, polarisation dependent loss (PDL) and thermal characteristics of TFGs with small (<45°), large (>45°) and 45° tilted structures. I have experimentally characterised TFGs, obtaining relationships between the radiation angle, central wavelength of the radiation profile, Bragg resonance and the tilt angle, which are consistent with theoretical simulation based on the mode-coupling theory. Furthermore, thermal responses have been measured for these three types of TFGs, showing the transmission spectra of large and 45° TFGs are insensitive to the temperature change, unlike the normal and small angle tilted FBGs. Based on the distinctive optical properties, TFGs have been developed into interrogation system and sensors, which form the other significant contributions of the work presented in this thesis. The 10°-TFG based 800nm WDM interrogation system can function not just as an in-fibre spectrum analyser but also possess refractive index sensing capability. By utilising the unique polarisation properties, the 81 °-TFG based sensors are capable of sensing the transverse loading and twisting with sensitivities of 2.04pW/(kg/m) and 145.90pW/rad, repectively. The final but the most important contribution from the research work presented in this thesis is the development of novel grating inscription techniques using near-IR femtosecond laser. A number of LPGs and FBGs were successfully fabricated in normal silica and mid-IR glass fibres using point-by-point and phase-mask techniques. LPGs and 1st and 2nd order FBGs have been fabricated in these mid-IR glass fibres showing resonances covering the wavelength range from 1200 to 1700nm with the strengths up to 13dB. In addition, the thermal and strain sensitivities of these gratings have been systematically investigated. All the results from these initial but systematic works will provide useful function characteristics information for future fibre grating based devices and applications in mid-IR range.

Spatial Modeling of a Soil Fertility Index using Visible-Near-Infrared Spectra and Terrain Attributes

Our objective was to develop a methodology to predict soil fertility using visible near-infrared (vis-NIR) diffuse reflectance spectra and terrain attributes derived from a digital elevation model (DEM). Specifically, our aims were to: (i) assemble a minimum data set to develop a soil fertility index for sugarcane (Sarcharum officinarum L.) (SFI-SC) for biofuel production in tropical soils; (ii) construct a model to predict the SFI-SC using soil vis-NIR spectra and terrain attributes; and (iii) produce a soil fertility map for our study area and assess it by comparing it with a green vegetation index (GVI). The study area was 185 ha located in sao Paulo State, Brazil. In total, 184 soil samples were collected and analyzed for a range of soil chemical and physical properties. Their vis-NIR spectra were collected from 400 to 2500 nm. The Shuttle Radar Topographic Mission 3-arcsec (90-m resolution) DEM of the area was used to derive 17 terrain attributes. A minimum data set of soil properties was selected to develop the SFI-SC. The SFI-SC consisted of three classes: Class 1, the highly fertile soils; Class 2, the fertile soils; and Class 3, the least fertile soils. It was derived heuristically with conditionals and using expert knowledge. The index was modeled with the spectra and terrain data using cross-validated decision trees. The cross-validation of the model correctly predicted Class 1 in 75% of cases, Class 2 in 61%, and Class 3 in 65%. A fertility map was derived for the study area and compared with a map of the GVI. Our approach offers a methodology that incorporates expert knowledge to derive the SFI-SC and uses a versatile spectro-spatial methodology that may be implemented for rapid and accurate determination of soil fertility and better exploration of areas suitable for production.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

Overtone Spectra of 1,2-Dichloro-And Dibromo-Ethanes in the Near Infrared Region

The vibrational overtone spectra 0f the liquid phase 1,2-dichloroethane and 1,2-dibromoethane in the spectral regions of CH stretching local mode overtones corresponding to delta v CH= = 2 to delta v CH=5 are reported. The observed spectral features are assigned using the local mode model. LocaI mode frequencies WCH and diagonal local mode anharmonicities XCH are obtained from an analysis of the spectra. The local-local combinations observed are interpreted on the basis of a coupled CH oscillator model hamiltonian. Local-normal combinations show complex structures and their possible assignments are given.

Overtone spectra of styrene and polystyrene in the visible and near infrared regions

Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

Fourier transform infrared spectra of H2CS and D2CS

Infrared spectra of thoformaldehyde, H2CS and D2CS, were observed in the gas phase at a resolution of better than 0.1 cm−1 from 4000 to 400 cm−1 using a Nicolet FTIR system. Vibrational band origins and rotational constants were determined for ν2, ν3, ν4, and ν6 of H2CS and for ν1, ν2, ν3, ν4, and ν6 of D2CS. The ν3, ν4, and ν6 bands of H2CS were analyzed as a set of three Coriolis interacting bands, and three Coriolis constants were determined; similarly the ν4 and ν6 bands of D2CS were analyzed as a pair of interacting bands and one Coriolis constant was determined. A general harmonic force field was determined, without constraints, to fit the vibrational wavenumbers, Coriolis constants, and centrifugal distortion constants. A zero-point (rz) structure was determined from the ground-state rotational constants, and the equilibrium (re) bond lengths were estimated.

Quantitative analysis of remote gas temperatures and concentrations from their infrared emission spectra

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments and on field trials. These emission spectra were obtained using an adapted FTIR spectrometer with 0.25 cm-1 spectral resolution. The CO2 and H2O vapour content in the plume from a 55 m smoke stack and the temperature of these gases were obtained by comparing the measured emission spectra with those modelled using the HITRAN atmospheric transmission database. The spatial distributions of CO2, CO and unburnt CH4 in a laboratory methane flame were reconstructed tomographically using a matrix inversion technique.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 mum (590-1666 cm-1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. (C) 2004 American Institute of Physics.