Este trabalho investiga as interações entre o grupo carbonílico e enxofre, oxigênio ou dupla olefínica, através do estudo dos seguintes compostos: ciclopentanona (I), 3-tiaciclopentanona (II), 3-oxaciclopentanona (III), ciclohexanona (IV), 3-tiaciclohexanona (V), 3-oxaciclohexanona (VI), cicloheptanona (VII), 3-tiacicloheptanona (VIII), 4-tiaciclohexanona (IX), 4-tiacicloheptanona (X), ciclooctanona (XI), 5-tiaciclooctanona (XII) e 3-ciclohexenona (XIII). É fornecida uma revisão bibliográfica, na qual são apresentados os trabalhos sobre frequência de estiramento e basicidade relativa do grupo carbonílico de cetonas por espectroscopia no infravermelho, sendo destacados alguns aspectos mais intimamente ligados a este trabalho. Entre estes aspectos, podem ser enumerados: ressonância de Fermi na ciclopentanona, efeito de campo, efeito do tamanho do anel sobre a frequência e basicidade da carbonila, e impedimento estérico nas ciclanonas. São descritas as sínteses de algumas das cetonas da série estudada, a saber: 3-tiaciclopentanona (II), 3-tiaciclohexanona (V), 3-oxaciclohexanona (VI), 4-tiaciclohexanona (IX) e 4-tiacicloheptanona (X). São fornecidos os dados das medidas de deslocamentos das frequências de estiramento das hidroxilas de fenol e de p-clorofenol, em associação (1:1) com as treze cetonas cíclicas estudadas, à diluição infinita do doador em tetracloreto de carbono (ΔvoOH). São determinadas as constantes de associação (Kass) dos complexos formados entre p-clorofenol e cetonas (1:T), em tetracloreto de carbono, no infravermelho próximo, para as 3- e 4-tiaciclanonas (II), (V), (VIII), (IX) e (X), 3-oxaciclanonas (III) e (VI) e cetonas não substituidas correspondentes (I), (IV) e (VII). São apresentadas as frequências de estiramento do grupo carbonilico (vCO) das treze cetonas cíclicas estudadas, em tetracloreto de carbono. Os resultados de ΔvoOH e Kass para as ciclanonas substituídas em posições 3 e 4 por enxofre ou oxigênio, em comparação com as ciclanonas não substituídas correspondentes, indicam que: 1) 3-tiaciclanonas (II) , (V) e (VIII) apresentam uma diminuição de basicidade; 2) a ordem de diminuição de basicidade em 3-tiaciclanonas é: 3-tiaciclopentanona (II) > 3-tiaciclohexanona (V) = 3-tiacicloheptanona (VIII); 3) 4-tiaciclohexanona (IX) e 4-tiacicloheptanona (X) mostram uma diminuição de basicidade comparável à das 3-tiaciclanonas correspondentes; 4) 3-oxaciclopentanona (III) e 3-oxaciclohexanona (VI) apresentam uma diminuição de basicidade, que é da mesma ordem de grandeza em ambos os compostos; 5) a diminuição de basicidade em 3-oxaciclopentanona (III) é menor e em 3-oxaciclohexanona (VI) é maior do que nas tiaciclanonas correspondentes. As medidas de frequência de estiramento da carbonila (vCO) para as mesmas ciclanonas demonstram que: 1) não há diferenças significativas entre as frequências da carbonila de tiaciclanonas e ciclanonas não substituidas correspondentes; 2) há um aumento na frequência da carbonila, passando-se das ciclanonas não substituidas (I) e (IV) para as 3-oxaciclanonas correspondentes (III) e (VI). É apresentada uma discussão, em que a existência de possíveis interações é examinada pela interpretação dos dados experimentais, à luz dos efeitos indutivos e de campo, alterações no anel provenientes da introdução de um heteroátomo, e níveis de energia, proximidade e posição geométrica dos orbitais interagentes. É sugerida a ocorrência de uma interação no espaço significativa entre o heteroátomo e o grupo carbonílico em 3-tiaciclopentanona (II), 3-oxaciclopentanona (III) e 3-oxaciclohexanona (VI), e a ausência de uma tal interação Significativa em 3-tiaciclohexanona (V) e 3-tiacicloheptanona (VIII). Não se elimina, porém, a possibilidade da existência de uma fraca interação no espaço nos dois útimos compostos. O estudo de basicidade de 5-tiaciclooctanona (XII) e 3-ciclohexenona (XIII) indica: 1) um aumento na basicidade em relação às cetonas nao substituídas correspondentes; 2) um aumento de basicidade anormal com o aumento de concentração das cetonas em tetracloreto de carbono. Os dados de basicidade, em conjunto com os estudos efetuados paralelamente por Wladislaw e col. e com os resultados de outras medidas da literatura, permitem sugerir para a 5-tiaciclooctanona (XII) e 3-ciclohexenona (XIII): 1) a ocorrência de transferência de carga no estado fundamental; 2) a existência, em solução, de um equilíbrio entre duas conformações, uma em que há transferência de carga de enxofre ou dupla olefínica para a carbonila, e outra em que esta transferência é ausente. / This thesis investigates the interactions between the carbonyl group and sulphur, oxygen or ethylene double bond, in the following compounds: 3-thiacyclopentanone (I), 3-oxacyclopentanone (II), 3-thiacyclohexanone (III), 3-oxacyclohexanone (IV), 3-thiacycloheptanone (V), 4-thiacyclohexanone (VI), 4-thiacycloheptanone (VII), 5-thiacyclooctanone (VIII) and 3-cyclohexenone (IX), by comparison with the corresponding unsubstituted compounds. The thesis contains: A literature review on the stretching frequencies and relative basicities of the carbonyl group in ketones, in which some aspects connected with the present work, such as cyclopentanone Fermi ressonance, field effect, ring size influence and steric hindrance are emphasized. The syntheses of 3-thiacyclopentanone (I), 3-thiacyclohexanone (III), 3-oxacyclohexanone (IV), 4-thiacyclohexanone (VI) and 4-thiacycloheptanone (VII). The ΔvoOH data, as measured by i.r. shifts of OH stretching vibration of phenol and p-chlorophenol associated to the ketones studied (1:1), in carbon tetrachloride. The equilibrium constants (Kas.) for the association complexes (1:1) between p-chlorophenol and 3-and 4-thiacyclanones (I), (III), (V), (VI) and (VII) and 3-oxacyclanones (II) and (IV) and the corresponding unsubstituted ketones, in carbon tetrachloride, obtained from near infra-red measurements. The carbonyl stretching frequencies (vCO) for the ketones studied, in carbon tetrachloride. The basicities measurements data indicate that: 3-Thiacyclanones (I), (lII) and (V) are less basic than the corresponding unsubstituted ketones. The basicities decrease order in 3-thiacyclanones is: 3-thiacyclopentanone (I) > 3-thiacyclohexanone (III) = 3-thiacycloheptanone (V). The basicity decrease in the 4-thiacyclohexanone (VI) and 4-thiacycloheptanone (VII) is similar to that obtained for the corresponding 3-thiacyclanones. 3-Oxacyclopentanone (II) and 3-oxacyclohexanone (IV) show similar basicity decrease. The basicities of 3-oxacyclopentanone (II) and 3-oxacyclohexanone (IV) are, respectively lower and higher than those of the corresponding thia analogues. 5-Thiacyclooctanone (VIII) and 3-cyclohexenone (IX) are more basic than the corresponding unsubstituted ketones. An abnorml raise of basicity occurs in 5-thiacyclooctanone (VIII) and 3-cyclohexenone (IX) with the increase of concentration in carbon tetrachloride. The carbonyl stretching frequency measurements (vCO) show that: The vCO values for thiacyclanones do not differ significantly from those for the corresponding unsubstituted ketones. 3-Oxacyclanones exhibit higher vCO values than the corresponding unsubstituted ketones. A discussion is presented, in which: The possibility of through-space and through-bond interactions in the 3- and 4-substituted cyclanones is considered by examination of experimental data in the light of the possible effects described in the literature review, energy levels, proximity and geometry of the interacting orbitals. The possibility of a charge transfer from the sulphur atom or ethylene double bond to the carbonyl group in 5-thiacyclooctanone (VIII) and 3-cyclohexenone (IX) is examined by comparison of the experimental data of the present thesis with those reported in the 1iterature and those obtained by B.Wladislaw et al. The following conclusions are presented: A significant through-space interaction between sulphur or oxygen atoms and carbonyl group takes place in the 3-thiacyclopentanone (I), 3-oxacyclopentanone (II) and 3-oxacyclohexanone (IV). There is no evidence for a sicnificant through-space interaction between sulphur atom and carbonyl group in 3-thiacyclohexanone (III) and 3-thiacycloheptanone (V), though a weak interaction may be present. 5-Thiacyclooctanone (VIII) and 3-cyclohexenone (IX) exist in solution, as an equilibrium mixture of two conformations, one in which charge transfer occurs and another in which it is absent.

Abstract Internal rotation in symmetric top molecules offers an excellent opportunity to investigate large amplitude motion in a relatively simple intramolecular environment. Due to specific symmetry characteristics of a symmetric top molecular frame, the internal rotation degree of freedom is in the zeroth order approximation separable from the small amplitude vibrations and the overall rotation, thus enabling to characterize the vibrational-torsional-rotational energy structure with a relatively simple Hamiltonian. Lessons from symmetric internal rotor studies may be applied to more complex systems, such as asymmetric internal rotors and macromolecules. This thesis deals with internal rotation in CH3SiH3, CH3SiD3, CH3CF3 which have become a prototype of symmetric internal rotors. The thesis presents high resolution vibration-torsion-rotation spectra and detailed analysis of these molecules. Particular attention is focused on torsion-mediated interactions, such as Coriolis-type interactions and Fermi-type interactions, coupling the internal rotation and the small amplitude vibrational motion. The studies show that the expansion of the data to the small amplitude vibrations and inclusion of the torsion-mediated interactions play a crucial role in order to obtain an appropriate characterization of the vibrational-torsional-rotational energy level structure and physically meaningful molecular parameters.

Chronic changes in cardiac load can cause the vertebrate heart to remodel. For ectotherms, ambient temperature can directly alter cardiac load. Therefore, long-term ambient temperature change can initiate a dynamic cardiac remodelling response to preserve cardiac function. The aims of my PhD thesis were to study the effects of chronic temperature change on the ectothermic heart and cardiovascular system, using the cold-active rainbow trout and the cold-dormant freshwater turtle. In contrast to the majority of previous studies, my experiments focused on the passive, rather than active, properties of the heart. In results chapters 3, 4, 5 and 6, I studied the effects of thermal remodelling on the rainbow trout heart. Chronic cold caused a global increase in chamber stiffness, both at the whole chamber and micromechanical level, with an associated myocardial fibrosis. In the ventricle and atrium there was an up-regulation of collagen promoting genes. In the ventricle, I found cold-induced hypertrophy of the spongy myocardium with an up-regulation of hypertrophic growth factors, which was associated with an increase in tissue lipid suggesting an increase in fatty acid oxidation (FAO). In the atrium, there was no hypertrophy, but there was an increase in extra-bundular sinus, suggesting chronic dilation. Chronic warming initiated an opposite response, with increased cardiac compliance associated with an up-regulation of collagen degrading genes in the ventricle and atrium. In the outflow tract (OFT) and atrium, this increased activity of matrix metalloproteinase (MMPs) and in the OFT abundance of MMPs was increased. The warmed ventricle showed atrophy of the spongy myocardium with a decrease in lipid and an increase in glycogen suggesting a switch in cellular energetics from FAO to glycolytic pathways. In chapters 7, 8 and 9, I studied the effects of thermal remodelling on the freshwater turtle heart. I found an in vivo decrease in systemic resistance causing an increased right to left cardiac shunt flow, associated with an increased elastin content of the major outflow vessels. Cold acclimation increased cardiac sensitivity to preload as well as whole chamber passive stiffness and micromechanical stiffness of tissue sections, associated ventricular fibrosis and increased collagen coherency. In addition, chronic cold decreased the gelatinase activity of MMPs and increased mRNA expression of a tissue inhibitor of MMPs. Furthermore, chronic cold was associated with a decrease in tissue lipid and phosphates, but an increase in tissue protein, glycogen and lactate. These changes in tissue biochemistry suggest a switch in cellular energetics from FAO to glycolytic pathways, likely due to the decreased oxygen availability associated with winter inactivity. Overall, the chambers of the ectothermic heart show distinct remodelling phenotypes, which likely reflect their in cardiac function. Thermal remodelling of the fish ventricle serves both cardio-protection, from the haemodynamic strain of changes in cardiac preload and afterload, as well as compensation for the direct effects of temperature. In the turtle, changes in compliance and cellular energetics of the ventricle suggest a cardio-protective mechanism preparing the heart for increased haemodynamic stress and hypoxic or anoxic conditions during inactive winter hibernation.

The purpose of this study was to examine the consistency of near-infrared spectroscopy (NIRS) measures associated with a 10 minute vascular occlusion of the thigh during 5 consecutive days. A secondary purpose was to examine if the repeated daily occlusions modify the vascular response to such occlusions. The NIRS chromophores of oxygenated hemoglobin (HbO2), deoxygenated hemoglobin (HHb), total hemoglobin (tHb), hemoglobin difference (HbDiff), and total saturation index (TSI) were monitored at the vastus lateralis muscle during each testing session. Participants were female (age 18-30 yrs) and were randomly assigned to one of two groups. The Test Group (age 23 ± 2yrs) completed an occlusion test every day for 5 consecutive days while the Control Group (age 21 ±1.6yrs) was tested on days 1, 3 and 5. Each testing session involved 10 minutes rest in a supine position, 10 minutes of femoral artery occlusion (preset at 250mmHg), 10 minutes of recovery. At onset of occlusion, the rapid cuff inflation system inflated in 0.3 seconds to the preset 250mmHg. Following the 10 minutes of occlusion, the cuff was deflated in 0.3 seconds. Heart rate was monitored throughout all testing sessions and mean arterial pressure was calculated and compared between groups. There were no significant group or day main effects found, nor any significant interactions for the following hemoglobin chromophores measures: HbO2, HHb, HbDiff, and TSI. In all participants, the NIRS response pattern to rest, occlusion and recovery was consistent for all testing days regardless of group. The response pattern to the occlusion initiated by the rapid cuff inflation was as follows: HbO2, tHb, HbDiff, and TSI decreased then slowly plateaued over the 10 minutes while HHb increased initially and then plateaued. Following the rapid cuff deflation, HbO2, tHb, HbDiff and TSI increased to their maximum reperfusion levels and then plateaued over the remainder of the 10 minutes of recovery. During that same period, HHb decreased initially upon reperfusion and then plateaued. Unlike the other measures, TSI and tHb demonstrated inconsistencies in their response pattern regardless of group or day. The consistency of hemoglobin chromophores response pattern to daily 10 minute vascular leg occlusions over 5 consecutive days is an important finding of this study. This response indicates that there is no apparent change in vascular response to repeated occlusions and has implications for exercise studies that use occlusion in their methodology. The study also emphasizes the inconsistency of tHb and TSI as primary hemoglobin response measures to occlusion. Similarly, the results demonstrate the potential misinterpretation of results if only relying on one hemoglobin measure during occlusion. / Graduate

This dissertation focuses on the use of near-infrared spectroscopy (NIRS) to identify trends in regional cerebral oxygen saturation (rSO2) in both conscious and anaesthetised healthy horses. A cerebral/somatic oximeter sensor recorded rSO2 from the dorsal sagittal sinus of 6 healthy horses. Values for rSO2, arterial and venous oxygen and carbon dioxide tensions (PaO2, PvO2, PaCO2 and PvCO2 respectively), along with arteriovenous oxygen saturations (SavO2) were recorded in unsedated (recording period [RP] 1), sedated (RP2), and anaesthetised horses (RP3-5); and during recovery (RP6-8). During anaesthesia, horses were ventilated to achieve states of normo- (RP3), hyper- (RP4) and hypocapnoea (RP5). Overall mean ± s.d. values for rSO2, PaO2, PvO2, PaCO2, SavO2 and mean arterial pressure (MAP) varied significantly by RP. Significant decreases in rSO2 were identified between RP1 and the post-anaesthetic periods however no significant differences in rSO2 values were identified between RP1 and the intra-anaesthesia periods. Regional cerebral oxygen saturation was significantly correlated with PaO2, PvO2 and SavO2. No correlation was identified between rSO2 and lactate concentration. This is the first study to identify trends in rSO2 in horses using NIRS. A significant positive correlation was identified between rSO2 and PvO2, suggesting that alterations in cerebral oxygenation may be reflected in jugular PvO2. Results of this study demonstrate that NIRS can be used during general anaesthesia to monitor trends in rSO2 in healthy horses, and has the potential to alert clinicians to cerebral desaturation events when used in a clinical setting. / Dissertation (MMedVet)--University of Pretoria, 2013. / gm2014 / Companion Animal Clinical Studies / unrestricted

No description available.

In an attempt to reduce the costs and turn around times experienced with outsourcing starch analysis in finished feed products, the company decided to invest in a NIR instrument to carry out such analyses in house. The particular instrument purchased by the company comes with a build in calibration for specific finished feed products and the main objective of this investigation was to evaluate whether the instrumentation and build in calibration gives reliable analyses of a finished poultry feed. The results obtained showed that : - The NIR results obtained have a positive bias compared to the theoretical (formulation specified value) and also to the value obtained by enzymatic starch analysis. - Despite the positive bias, the starch values were well within the allowable limits - Repeatability measurements on the data generated by two different analysts showed that while the percentage relative standard deviations obtained (< 1.0 percent) were well within the company specifications of percentage RSD < 5.0 percent, the inter sample repeatability showed small, but significant variation. - The results for intermediate precision showed that there is no statistically significant difference between the results obtained by two different analysts, nor was there any difference in the results of the same samples analysed at different time periods. - Reproducibility could not be evaluated due to the lack of another instrument within the company that were similarly set up as the instrument used for the investigation. This investigation has shown that, given the restrictions enforced by the build incalibration of the NIR instrument, the use of NIR for the analyses of the finished feed product is valid, but will require that careful attention be paid to data collection procedures.

Infrared (IR) spectroscopy has shown potential to quickly and non-destructively measure the chemical signatures of biomedical samples such as single biological cells, and tissue from biopsy. The size of a single cell (diameter ~10-50 µm) are of a similar magnitude to the mid-IR wavelengths of light (~1-10 µm) giving rise to Mie-type scattering. The result of this scattering is that chemical information is significantly distorted in the IR spectrum.Distortions in biomedical IR spectra are often observed as a broad oscillating baseline on which the absorbance spectrum is superimposed. A spectral feature commonly observed is the sharp decrease in intensity at approximately 1700 cm-1, next to the Amide I band (~1655 cm-1), which pre-2009 was called the 'dispersion artefact'. The first contributing factor towards the 'dispersion artefact' investigated was the reflection signal arising from the air to sample interface entering the collection optics during transflection experiments. This was theoretically modelled, and then experimentally verified. It was shown that IR mapping could be done using reflection mode, yielding information from the optically dense nucleus which previously caused extinction of light in transmission mode.The most important contribution to the spectral distortions was due to resonant Mie scattering (RMieS) which occurs when the scattering particle is strongly absorbing such as biomedical samples. RMieS was shown to explain both the baselines in IR spectra, and the 'dispersion artefact' and was validated using a model system of poly(methyl methacrylate) (PMMA) of varying sizes from 5 to 15 µm. Theoretical simulations and experimental data had an excellent match thus proving the theory proposed. With an understanding of the physics/mathematics of the spectral distortions, a correction algorithm was written, the RMieS extended multiplicative signal correction (RMieS-EMSC). This algorithm modelled the measured spectrum as superposition of a first guess (the reference spectrum) which was of a similar biochemical composition to the pure absorbance spectrum of the sample, and a scattering curve. The scattering curve was estimated as the linear combination of a database of a large number of scattering curves covering a range of feasible physical parameters. Simulated and measured data verified that the RMieS-EMSC increased IR spectral quality.

M.Sc. (Chemistry) / The usefulness of vibrational spectroscopy in identifying surface species, determining adsorbate structures and studying surface reactions has been widely demonstrated. Most of the infrared work on surface species is currently performed using the transmission technique with very thin pressed discs of self supported catalysts. This technique has several disadvantages of which the limited transmission of many catalysts and the loss of available surface area during sample preparation, are but a few. Because of these limitations, information obtained from conventional transmission studies has limited application in terms of understanding and/or improving commercial catalysts. An alternative method which does not suffer from these limitations is Diffuse Reflectance Infrared Fourier Transform Spectroscopy or DRIFTS as it is commonly known. This spectroscopic technique has only recently been extended into the infrared region because of the progress in FTIR instrumentation. Because this is a reflectance technique, the sample is most appropriately a powder, so a high surface area catalyst in its normal powder form can be examined directly without altering its state. A spectroscopic facility which is capable of obtaining DRIFT spectra of adsorbed species at high sensitivity and in situ operating conditions has been established. This facility consists of an FTIR instrument fitted with a diffuse reflectance unit, a heatable high pressure cell and the necessary attachments for gas flow, pressure and temperature control. The project work consisted of an investigation into CO-adsorption on supported rhodium catalysts. By using different combinations of the three parameters: reduction temperature, metal loading and support material, several different species of surface bonded CO have been identified. The three rnein species being: geminal dicarbonyl, linear and bridging CO. As each of these species is associated with a specific Rh-site, conclusions concerning the oxidation state and dispersion of the Rh on the surface could be made. The thermal stability of the different CO-species was studied by increasing the catalyst temperature in a linear fashion. It was found that the geminal dicarbonyl species was the most stable in an oxidising atmosphere. The interconversion of chemisorbed . CO-species at higher temperatures has been spectroscopically verified. A mechanism for CO-dissociation on Rh-catalysts was proposed. In additional experiments the sensitivity of DRIFTS for adsorbed hydrocarbons has been demonstrated. It is concluded that this spectroscopic technique has been proven to be of great significance in the study of surface species on heterogeneous catalysts.

Near infrared spectroscopy (NIRS) is an emerging neuroimaging modality with high temporal and good spatial resolution. In this thesis, NIRS was applied to understand functionality of the fronto-temporal cortex in response to language-related tasks. A 32-channel NIRS system (Imagent ISS Inc.) was used to perform experimental studies on 15 right-handed normal adults. Block-design based Word Expression and Word Reception paradigms were independently presented to participants. Activation, functional connectivity and cortical lateralization analyses were performed. From word expression studies, results showed left anterior region (encompassing Broca) is majorly involved over right homologue and posterior regions. From the word reception studies, results showed that right posterior region (encompassing right homologue of Wernicke) is highly involved in language reception, with right anterior region (encompassing right homologue of Broca) also involved. The current study has potential future applications in surgical evaluation of language regions in populations with neurological disorders such as epilepsy, and schizophrenia.