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Introduction: Currently, there are no objective techniques to assess burn depth. An early assessment of burn depth would enable accurate management decisions, which would improve patient outcomes. Near infrared (NIR) technology has shown promise as a non-invasive monitor of oxygenation and perfusion, and its potential to assess the depth of burn injuries has been investigated clinically over the past five years. The purpose of the thesis was to determine the capacity of NIR technology to differentiate acute thermal injuries. Methods: Burn sites (n=5) and control sites (n=5) were created on the dorsum of sixteen animals with brass rods held at constant pressure and heated to 100°C and 37.5°C respectively. NIR data was collected from the burns and control sites pre-burn, immediately post-burn, and 1, 12, 24, 36, 48 and 96 hours after the burn injury. Biopsies of the burn and control sites were acquired at each time point and used to confirm the depth of injury. NIR data was processed for the content of water, oxy-, deoxy- and methemoglobin. Results: Oxyhemoglobin and total hemoglobin decreased as burn depth increased. The proportion of oxy- and deoxyhemoglobin to total hemoglobin showed that the ratio of oxy- to deoxyhemoglobin decreased as burn injury increased. Methemoglobin levels as a ratio of total hemoglobin also showed that as the severity of injury increased the proportion of methemoglobin also increased. Finally, superficial partial thickness injuries (3 s and 12 s) showed early peak levels of water, which rapidly declined towards baseline. The deep partial thickness injuries (20 s and 30 s) do not experience peak levels and retain water over the course of the experiment. The full thickness injuries water levels remain close or below baseline levels throughout the experiment. Conclusion: NIR spectroscopy could distinguish burn depth using water, oxy-, met- and total hemoglobin as separate entities. The presence of methemoglobin in the burn wounds is a novel finding that has not been described previously in burn literature.

Diabetes Mellitus is a major health problem which affects about 200 million people worldwide. Diabetics require their blood glucose levels to be kept within the normal range in order to prevent diabetes-related complications from occurring. Blood glucose measurement is therefore of vital importance. The current glucose measurement techniques are, however, painful, inconvenient and episodic. This document provides an investigation into the use of near-infrared spectroscopy for continuous, non-invasive measurement of blood glucose. Artificial neural networks are used for the development of multivariate calibration models which predict glucose concentrations based on the near-infrared spectral data. Simulations have been performed which make use of simulated spectral data generated from the characteristic spectra of many of the major components of human blood. The simulations show that artificial neural networks are capable of predicting the glucose concentrations of complex aqueous solutions with clinically relevant accuracy. The effect of interference, such as temperature changes, pathlength variations, measurement noise and absorption due other analytes, has been investigated and modelled. The artificial neural network calibration models are capable of providing acceptably accurate predictions in the presence of multiple forms of interference. It was found that the performance of the measurement technique can be improved through careful selection of the optical pathlength and wavelength range for the spectroscopic measurements, and by using preprocessing techniques to reduce the effect of interference. Although the simulations suggest that near-infrared spectroscopy is a promising method of blood glucose measurement, which could greatly improve the quality of life of diabetics, many further issues must be resolved before the long-term goal of developing a continuous non-invasive home glucose monitor can be achieved.

Cell penetrating peptides (CPPs) have drawn the attention of researchers due to their ability to internalize large cargos into cells including cancer cells. The mechanism(s) with which the peptides enter the cell, however, is/are not clear and full of controversy. The peptide conformations and their microenvironment in live cells had been unknown until the development of a technique developed in our lab. As a first demonstration of principle, penetratin, a 16-residue CPP derived from the Antennapedia homeodomain protein of Drosophila, was measured in single, living melanoma cells. Carbon-13 labeling of the Phe residue of penetratin was used to shift the intense aromatic ring-breathing vibrational mode from 1003 to 967 cm-1, thereby enabling the peptide to be traced in cells. Difference spectroscopy and principal components analysis (PCA) were used independently to resolve the Raman spectrum of the peptide from the background cellular Raman signals. / On the basis of the position of the amide I vibrational band in the Raman spectra, the secondary structure of the peptide was found to be mainly random coil and b-strand in the cytoplasm, and possibly assembling as b-sheets in the nucleus. Next, label-free transportan was studied with the same methodology. The peptide, besides predominantly a-helix, adopted a significant portion of b-sheet conformation in the cytoplasm and nucleolus, which is different from the peptide in aqueous solution. The peptide microenvironment was also probed through H-bonding reported by the tyrosine Fermi doublet. Transportan displayed a tendency to accumulate in the cytoplasm over time which was unlike penetratin, which concentrated in the nucleus. The relative concentration of CPPs in various locations of live melanoma cells was directly estimated from the Raman spectra using average Phe concentration in the cell as an internal standard. / The rapid entry and almost uniform cellular distribution of both peptides, as well as the lack of correlation between peptide and lipid Raman signatures, indicated that the mechanism of CPP internalization under the conditions of study was probably non-endocytotic. Last, transportan and penetratin were studied using polarized Raman spectroscopy for more detailed vibrational spectroscopic information of the two peptides in water and TFE solutions. The majority of the bands in the Raman spectra of the peptides were highly polarized, consistent with the high symmetry of aromatic ring side chain vibrational bands dispersed throughout the spectra. This work has provided new insights into the structure of CPPs in live cells and in solutions. / by Jing Ye. / Thesis (Ph.D.)--Florida Atlantic University, 2011. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2011. Mode of access: World Wide Web.

Foram estudados através de espectroscopia vibracional, Raman e infravermelho, uma série de derivados do íon pentacianocobaltato(II), de fórmula geral [Co(CN)5-L-Co(CN)5]n-, onde L é H2C=CH2, H3COOC-C=C-COOCH3, C2H5COO-C=C-COOC2H5, SO2, O--2, O-2 ou NO2. Além desses Complexos, o íon dímero [Co2(CN)10]6- também foi objeto de estudo. No caso dos íons [Co(CN)5-L-Co(CN)5]n- os espectros vibracionais na região de estiramento CN são interpretados com base numa simetria C4v dos grupos Co(CN)5 isolados. A natureza das ligações C=N e das, ligações do ligante L para esses compostos é discutida com base nos resultados obtidos. / The vibrational spectra (Raman and infrared) of a series of compounds of general formula [Co(CN)5-L-Co(CN)5]n-, derived from the pentacianocobaltate(II) ion, where L is H2C=CH2, H3CCOO-C=C-COOCH3, C2H5COO-C=C-COOC2H5, NO2, SO2, O--2 or O-2, were studied. The dimer ion [Co2(CN)10]6- has also been subject of study. In the case of the [Co(CN)5-L-Co(CN)5]n- ions the vibrational spectra in the region of CN stretching vibrations were interpreted based on the C4v symmetry of the isolated Co(CN)5 groups. Characteristic frequencies of the ligand L and skeletal vibrations of Co(CN)5 group are tentatively assigned. The nature of C=N bonding and the structure of ligand L for these compounds are discussed on the basis of the obtained spectral results.

A presente tese trata da síntese e a análise conformacional de seis séries de compostos: 2-feniltioN;N-dietilacetamidas 4\'-substituídas (I); 2-fenilsulfinil-N,N-dietilacetamidas 4\'-substituídas (II); 2-fenilsulfonil-N,N-dietilacetamidas 4\'-substituídas (III); 2-feniltio-cicloexanonas 4\'-substituídas (IV); 2-fenilsulfonil-cicloexanonas 4\'-substituídas (V); 2-fenilsulfinil-cicloexanonas 4\'substituídas (IV). O estudo conformacional foi realizado por intermédio das espectroscopias no IV e RMN de hidrogênio, apoiados por cálculos teóricos. A análise de vCO no infravermelho para as séries I, II e III, de forma geral, se correlaciona bem com os cálculos em HF e B3LYP os quais demonstram a ocorrência de duas conformações estáveis para os compostos da série (I), tendo o confôrmero gauche mais estável em relação ao confôrmero cis. O efeito dos substituintes da série (I), observado experimentalmente, é mais concordante com os resultados calculados em B3LYP do que em HF. Com relação à série (II), há apenas uma conformação estável, ou seja, a cis, no gás e em solventes de diferentes polaridades. A série (III) apresentou a existência de três conformações estáveis, sendo duas conformações gauche de maior estabilidade que a terceira conformação cis (no gás e no solvente de baixa polaridade: CCl4). Nas séries das cicloexanonas (IV, V e VI) a análise de vCO no infravermelho e RMN de hidrogênio apresentou a conformação axial como preferencial em CCl4, sendo que esta preferência passou para equatorial em CH3CN (CD3CN). Os cálculos ab initio (HF) reproduziram o resultado experimental em CCl4, apenas para os derivados 2-fenilsulfonil-cicloexanonas 4\'-substituídas (V). Por outro lado, para estas cicloexanonas (IV - VI) os cálculos em B3LYP estão mais concordantes com os dados experimentais. O método NBO (Natural Bond Orbital) confirmou que as conformações gauche das séries (I, II e III) são estabilizadas por pelas interações: nN/π*C=O, πC=O/σ*C-S, σC-S/π*C=O, n(S)/π*C=O, π*C=O/σ*C-S, e as séries (IV, V e VI) pelas interações πC=O/σ*C-S, σC-S/π*C=O, n(S)/π*C=O, π*C=O/σ*C-S. Em contraste, estes resultados de NBO demonstraram também a importância das interações: nO(CO)/σC-S, nO(CO)/σ*S-O e nO(CO)/σ*C-H para a estabilização da conformação cis. Adicionalmente, a análise das cargas calculadas sugeriu a participação de interações Coulombicas na estabilização das conformações cis e gauche. Para todas as séries de compostos (I - VI), os cálculos incluindo o efeito do solvente (Onsager e PCM), para alguns compostos representativos, facilitaram a atribuição de cada conformação em solução. / This thesis reports the synthesis and conformational analysis of six sedes of compounds: N,N diethyl-2-[( 4-substituted)phenylthio] acetamides (I); N,N-diethyl-2-[(4-substituted)phenylsulfinyl] acetamides (II); N,N-diethyl-2-[(4-substituted)phenylsulfonyl] acetamides (III); [4 = OMe, Me, H, Cl, Br and N02]; 2-[(4-substituted)phenylthio] cyclohexanones (IV); 2-[(4-substituted)phenylsulfonyl] cyclohexanones (V) and 2-[(4-substituted)phenylsulfinyl] cyclohexanones (VI), [4 = OMe, H and N02]. The conformational study was performed through the IR and 1H NMR spectroscopies, supported by theoretical calculations. The vCO infrared analysis for the series I, II and III in general matches well with the HF and B3LYP calculations which showed the occurrence of two stable conformations for compounds of series (I), being the gauche the most stable and the cis the second one. As for the substituent effect of series (I), the agreement between the experimental results with B3LYP is better than with HF. calculations. Considering the serries (II), there is only one stable conformation, the cis one, in gas and in solvents of different polarity. The series (III) showed the existence of three stable conformations, being the two gauche the most stable and the cis the least stable (both in the gas and in the low polarity solvent, CCl4). In the cyclohexanones series (IV, V and VI) the vCO infrared and 1H NMR analyses showed a preference for the axial conformation, in CCl4, changing the preference to equatorial one in CH3CN (CD3CN). The ab initio (HF) calculations reproduced the experimental preference, in CCl4, for the 2-[(4-substituted)phenylsulfonyl] cyclohexanones only. On the other hand, for these cyclohexanones (IV-VI) the B3LYP calculations improved the agreement with the experimental data. The NBO (Natural Bond Orbital) method confirmed that the gauche conformations of the series (I, II and III) are stabilized by: nN/π*C=O, πC=O/&#963*C-S, σC-S/π*C=O, n(S)/π*C=O, π*C=O/σ*C-S, and for the series (IV, V and VI) by the interactions: πC=O/σ*C-S, σC-S/π*C=O, N(S)/π*C=O, π*C=O/σ*C-S. In contrast these NBO results also revealed the importance of the interactions nO(CO)/σ*C-S, nO(CO)/σ*S-O and nO(CO)/σ*C-H for the stabilization of the cis conformation. Additionally, the calculated charge analysis suggested the stabilization of both cis and gauche conformations due to Coulombic interactions. The inclusion of the solvent effect in the computations (Onsager and PCM methods) for some representative compounds of series (I-VI) facilitated the conformer attribution in solution.

Yeung Shun-hin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 52-54). / Abstracts in English and Chinese. / TITLE PAGE --- p.i / THESIS COMMITTEE --- p.ii / ABSTRACT (ENGLISH) --- p.iii / ABSTRACT (CHINESE) --- p.iv / ACKNOWLEDGEMENTS --- p.v / TABLES OF CONTENTS --- p.vi / LIST OF FIGURES --- p.viii / LIST OF TABLES --- p.x / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Computer-controlled Data Acquisition and Frequency Calibration System for a Ti: sapphire laser spectrometer --- p.3 / Chapter Section 2A --- Motivation and Overview --- p.3 / Chapter Section 2B --- The Hardware --- p.5 / Chapter Section 2C --- The Program --- p.12 / Chapter Section 2D --- Summary --- p.27 / Chapter Chapter 3 --- Cavity Enhanced Absorption Spectroscopy Using Phase-Sensitive Detection --- p.28 / Chapter Section 3A --- Motivation --- p.28 / Chapter Section 3B --- Cavity ring-down technique: the background --- p.29 / Chapter Section 3C --- Cavity enhanced absorption spectroscopy: a historical review --- p.34 / Chapter Section 3D --- Experimental Apparatus --- p.37 / Chapter Section 3E --- Results of Performance tests --- p.41 / Chapter Section 3F --- Applications --- p.45 / Chapter Section 3G --- Summary --- p.49 / Chapter Chapter 4 --- Concluding Remarks --- p.50 / REFERENCES --- p.52

Orientador: Gilbert Bannach / Coorientador: Luiz Carlos da Silva Filho / Banca: Egon Schnitzler / Banca: Aguinaldo Robinson de Souza / Resumo: O principal objetivo deste trabalho foi a síntese de um polímero com o uso de matérias primas renováveis e de origem vegetal e, além disso, seguir os princípios da Química Verde. Foi usado o óleo de macadâmia (extraído das castanhas de Macadamia integrifolia) em uma rota de síntese envolvendo condições brandas de temperatura e pressão. O polímero de macadâmia obtido foi caracterizado por diversas técnicas. A análise térmica foi utilizada na determinação da estabilidade térmica (140 °C), no entendimento do padrão de degradação térmica através de estudo cinético e na determinação da transição vítrea (Tg, 48 °C). Pela espectroscopia no infravermelho obteve-se uma ideia geral do mecanismo de polimerização do óleo de macadâmia com o pré-polímero (glicerol e anidrido maleico) e, possibilitou a identificação dos grupos funcionais presentes no polímero de macadâmia. Algumas propriedades interessantes do material sintetizado foram a sua fluorescência e a grande remoção de corantes orgânicos em solução, demonstrando a forte interação da superfície polimérica com o substrato orgânico. Esta primeira propriedade leva a potencial aplicação no desenvolvimento de sensores químicos. Já a segunda propriedade torna promissor o uso do polímero no encapsulamento de moléculas de interesse nutricional e/ou farmacológico, tendo-se em vista o fato de tanto o óleo de macadâmia quanto o glicerol serem comestíveis. / Abstract: The main objective of this work was the synthesis of a polymer using vegetable and renewable feedstock and following the green chemistry principles. The use of macadamia oil (extracted from Macadamia integrifolia nuts) in a synthesis route was achieved under mild temperature and pressure conditions. The produced material was submitted to a series of characterization techniques. Thermal analysis was used to determine its thermal stability (140 °C), its degradation pattern with the involved kinetic, and its glass transition (Tg 48 °C). Mid-infrared spectroscopy shows the general mechanism of polymerization of macadamia oil with pre-polymer (glycerol and maleic anhydride) and identified functional groups of the polymer. Some interesting characteristics of the macadamia polymer were its fluorescence and the great removal of organic dyes from aqueous solutions, which demonstrates the great interaction of its surface with organic molecules. The first characteristic indicates potential applications as chemical sensors. The other characteristic makes promising the use of the polymer as an encapsulation material for substances of nutritional and pharmacological interests, considering that macadamia oil and glycerol are edible substances. / Mestre

Lo, Yu Ching. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 79-82). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abbreviations --- p.ii / Abstract --- p.iii / Table of Contents --- p.v / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Basic Theory of FTIR --- p.1 / Chapter 1.1.1 --- Infrared Spectroscopy --- p.1 / Chapter 1.1.2 --- Dispersive Infrared Spectrometer --- p.2 / Chapter 1.1.3 --- Fourier Transform Infrared Spectrometer (FTIR) --- p.3 / Chapter 1.1.4 --- Advantages of FTIR --- p.5 / Chapter 1.1.4.1 --- Multiplex advantage --- p.5 / Chapter 1.1.4.2 --- Throughput advantage --- p.5 / Chapter 1.2 --- Traditional Chinese Medicine (TCM) --- p.6 / Chapter 1.3 --- Identification of Traditional Chinese Herbal Medicine --- p.8 / Chapter 1.3.1 --- Traditional method for the identification of TCM --- p.8 / Chapter 1.3.2 --- Instrumental method for the identification of TCM --- p.9 / Chapter 1.3.2.1 --- Identification of TCM using fingerprint method --- p.9 / Chapter 1.3.3 --- Identification of TCM using FTIR fingerprint method --- p.10 / Chapter 1.4 --- Objective --- p.11 / Chapter Chapter 2 --- Experimental / Chapter 2.1 --- Outline of the Method --- p.12 / Chapter 2.2 --- Reagents and Glassware --- p.13 / Chapter 2.3 --- Instrumentation --- p.13 / Chapter 2.4 --- Library Search Program --- p.13 / Chapter 2.5 --- Samples --- p.14 / Chapter 2.6 --- Sample Pretreatment --- p.16 / Chapter 2.7 --- Extraction of Ingredients --- p.16 / Chapter 2.8 --- Preparation of KBr Pellet --- p.17 / Chapter 2.9 --- IR Spectrum Measurement --- p.17 / Chapter 2.10 --- Data Processing --- p.18 / Chapter 2.11 --- IR Databases --- p.18 / Chapter 2.12 --- Reproducibility of Extraction --- p.29 / Chapter Chapter 3 --- Application of Library Search Techniques - Results and Disscussion / Chapter 3.1 --- Introduction --- p.31 / Chapter 3.2 --- Euclidean Search Method --- p.32 / Chapter 3.2.1 --- Similarly score of reference spectra --- p.32 / Chapter 3.2.2 --- Similarity score of known sample spectra --- p.37 / Chapter 3.3 --- Soft Independent Modeling of Class Analogy (SIMCA) --- p.45 / Chapter 3.3.1 --- Verification Diagnostic Report of the Reference flowers --- p.47 / Chapter 3.3.2 --- Classification of Flowers --- p.51 / Chapter 3.4 --- Performance Limitation --- p.75 / Chapter 3.4.1 --- Euclidean Search Method --- p.75 / Chapter 3.4.2 --- SIMCA --- p.75 / Chapter 3.5 --- Conclusion --- p.77 / References --- p.79

Foram estudados através de espectroscopia vibracional, Raman e infravermelho, uma série de derivados do íon pentacianocobaltato(II), de fórmula geral [Co(CN)5-L-Co(CN)5]n-, onde L é H2C=CH2, H3COOC-C=C-COOCH3, C2H5COO-C=C-COOC2H5, SO2, O--2, O-2 ou NO2. Além desses Complexos, o íon dímero [Co2(CN)10]6- também foi objeto de estudo. No caso dos íons [Co(CN)5-L-Co(CN)5]n- os espectros vibracionais na região de estiramento CN são interpretados com base numa simetria C4v dos grupos Co(CN)5 isolados. A natureza das ligações C=N e das, ligações do ligante L para esses compostos é discutida com base nos resultados obtidos. / The vibrational spectra (Raman and infrared) of a series of compounds of general formula [Co(CN)5-L-Co(CN)5]n-, derived from the pentacianocobaltate(II) ion, where L is H2C=CH2, H3CCOO-C=C-COOCH3, C2H5COO-C=C-COOC2H5, NO2, SO2, O--2 or O-2, were studied. The dimer ion [Co2(CN)10]6- has also been subject of study. In the case of the [Co(CN)5-L-Co(CN)5]n- ions the vibrational spectra in the region of CN stretching vibrations were interpreted based on the C4v symmetry of the isolated Co(CN)5 groups. Characteristic frequencies of the ligand L and skeletal vibrations of Co(CN)5 group are tentatively assigned. The nature of C=N bonding and the structure of ligand L for these compounds are discussed on the basis of the obtained spectral results.