published_or_final_version / Biological Sciences / Doctoral / Doctor of Philosophy

Theoretical and experimental aspects of high resolution spectroscopy are discussed. The theoretical work concentrates on the matrix elements of the rigid rotor and molecular hyperfine terms of the Hamiltonian of a rotating molecule. The experimental work consists of Stark cell and beam maser microwave spectroscopy on C1CN and HDO respectively. The theory of rotational spectroscopy is developed in a uniform manner based on the irreducible tensor method. It is shown how the effect of molecular symmetry may be incorporated into this method. The instrumentation required to observe the hyperfine splittings is discussed. This includes descriptions of the Stark cell and molecular beam maser microwave spectrometers. A new tunable C-band resonant cavity is described. The following molecular constants are reported for both common species of C1CN: rotational constant Bₒ, centrifugal distortion constant D(J), quadrupole coupling constant eqQ(k), and spin-rotation constant C(x). Values in MHz for C1CN are as follows: ³⁵C1CN; Bₒ = 5 907.820 ± 0.010, eqQ(C1) = -83.26 ± 0.06, eqQ(N) = -3.59 ± 0.08, C(C1) = -0.006 ± 0.006, C(N) = 0.013 ± 0.010; ³⁷C1CN; Bₒ = 5 847.246 ± 0.008, eqQ(C1) = -65.61 ± 0.06, eqQ(N) = -3.61 ± 0.08, C(C1) = -0.004 ± 0.006, C(N) = 0.010 ± 0.010. The following molecular constants for HDO are reported: quadrupole coupling tensor elements eqQ(D)(gg) and spin-rotation tensor elements C(x)(gg). The values in KHz are as follows: eqQ(D)(aa) = 276.45 ± .88, eqQ(D)(bb) = -110.97 ± 1.46, eqQ(D)(cc) = -165.77 ± 1.10, C(D)(aa) = 1.33 ± .20, C(D)(bb) = -4.38 ± .36, C(D)(cc) = -2.99 ± .24, C(H)(aa) = -58.42 ± .47, C(H)(bb) = -5.46 ± .83, C(H)(cc) = -23.28 ± .10. The values for the constants for C1CN agree with previous values but are more precise. Those for HDO do not agree with previous values but are thought to be more accurate since they are obtained for a larger data base.

Thesis (Ph. D.)--University of Chicago, 1932. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois." Bibliography: p. 6.

<p> In Part I of this thesis, the design, construction, and calibration of a twenty-one foot off-plane Eagle vacuum spectrograph, a Lyman source, and predispersion unit are described.</p> <p> In Part II, the results of an investigation of the electronic absorption spectra of the cyanogen halides, obtained with the apparatus described in Part I, are given. Several electronic absorption systems have been observed for each of the cyanogen halides. These have been correlated and assigned to electronic transitions. Vibrational analyses have been made and the excited state dimensions have been determined by a quantitative application of the Franck-Condon principle for two absorption systems of each of the cyanogen halides.</p> / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

The predictions of non-equilibrium radiation for a Titan aerocapture aeroshell vary significantly amongst Computational Fluid Dynamics (CFD) analyses and are limited by the physical models of the non-equilibrium flow. Of particular interest are the non-equilibrium processes associated with the cyanogen (CN) molecule which is known to be a strong radiator. It is therefore important to have experimental data for these radiating shock layers which will allow for validation of CFD models. Furthermore, a more detailed understanding of the chemical processes that lead to the formation of CN above equilibrium concentration is required. This thesis describes the modelling of the radiation behind a shock using a collisional-radiative (CR) model and presents measurements of radiation intensity behind a shock in simulated Titan and Martian atmospheres. The uncertainties in radiation is more significant at lower speeds (around 5-8 km/s) with these atmospheres when compared to Earth entry. This is due to the formation of CN and because of the highly non-equilibrium nature of the flow. The motivation for this work began with the successful landing of the Huygens probe on the surface of Titan which led to the renewed interest in inter-planetary missions. Thus radiative heating during atmospheric entry to Titan and Mars was the subject of several experimental campaigns and extensive computational analyses. In order to better understand the formation of CN, and the nonequilibrium radiation emitted under such atmospheric conditions, NASA Ames Research Center conducted a series of experiments on their Electric Arc Shock Tube facility, EAST. Furthermore, several research groups in Europe and the United States independently developed CR models to predict the measured levels of radiation. The results from these simulations showed some ma jor discrepancies and highlighted a lack of knowledge and understanding about the fundamental physics behind the formation and decay of the CN molecule and its associated excited states. Based on a comparison of the various simulations with the CR models and the EAST experimental data, it was concluded that the absolute level of peak radiation was well predicted, however, there was a significant discrepancy related to the decay rate of the radiation. Therefore, to add to the relatively small amount of experimental data for these highly non-equilibrium radiating flow conditions, experiments were performed on the X2 shock tube at The University of Queensland with the aim of producing a comprehensive set of benchmark data for Titan entry. The data obtained from these experiments have been used to validate the results from the NASA Ames testing, and due to the large parametric variation, as a source for code validation. In addition to the experimental component of this thesis, an investigation into the simulation of CN non-equilibrium radiation was conducted. It has been previously concluded that there was a significant discrepancy between the experimentally measured radiation decay rate and the predicted value from CR models. Therefore, the primary aim of the simulation work presented in this thesis is to explain the reason behind this discrepancy. Through a parametric study of important reactions combined with an analysis of the reaction set, it was concluded that the coupling between the dissociation of N2 and the formation of CN (through the reaction N2 + C ↔ CN + N) controlled the radiation decay rate. The reason for the super equilibrium concentrations was identified to be a result of the N2 + C ↔ CN + N reaction continuing to over-produce CN after nominal equilibrium values are reached. This is due to the slow build up of N to drive the reverse reaction. Thus it has been shown in this thesis that the behaviour of the CN concentration is controlled by the rate of N2 dissociation. This led to the implementation of a more thorough method for simulating the dissociation process of molecular nitrogen. Therefore, a mono-quantum vibration state specific model that includes excitation and de-excitation reactions for all the vibrational states of nitrogen was incorporated into the CR model developed by Magin et al. The nitrogen vibration state specific model that was implemented was developed by Pierott and is based on SSH theory. The model developed in this thesis is known as the ViSpeN CR model (Vibrationally Specific Nitrogen). The ViSpeN results show significantly better agreement with experimental data in terms of the decay rate, initial rise of the radiation and the overall trends in the data. However, the work in this thesis has shown there are still discrepancies in predicting the absolute level of radiation measured in shock tunnel experiments. This led to the development of a modification to the ViSpeN model (known as ViSpeN-L) which includes a proposed new value for the radiative lifetime of the CN violet transition. The agreement between the experimental data and the ViSpeN-L model is excellent for conditions relevant to Titan entry.

The synthesis and insecticidal activity of a series of 2,2-dicyano cyclopropane carboxylic acids, (3-phenoxyphenyl)- methyl esters were investigated. Synthesis of the compounds was accomplished by reaction of a dimethyl sulfonium carbethoxy ylide with propanedinitrile alkylidene compounds. Final products were formed in one step by use of the (3-phenoxyphenyl)-methyl ester of the ylide. Insecticidal activity was determined at 500 ppm application with Permethrin as the standard against houseflies, mexican bean beetles, and southern army worms.

by Ma Chin Kwan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 129-131). / Chapter Chapter 1. --- Introduction --- p.1 / Chapter Chapter 2. --- Theory --- p.4 / Chapter Chapter 3. --- The Retention Mechanism of Cyano-Bonded Stationary Phase for Some Basic Drugs in Polar Eluents / Chapter 3.1 --- Introduction --- p.18 / Chapter 3.2 --- Experimental / Chapter 3.2.1 --- Reagents --- p.20 / Chapter 3.2.2 --- Equipment --- p.21 / Chapter 3.2.3 --- Standard Preparation --- p.21 / Chapter 3.2.4 --- Procedures --- p.22 / Chapter 3.3 --- Results and Discussion / Chapter 3.3.1 --- Acetonitrile-Perchloric Acid Systems --- p.29 / Chapter 3.3.2 --- Acetonitrile-Perchlorate Salts Eluent Systems --- p.42 / Chapter 3.3.3 --- Retention and Acetonitrile Composition --- p.49 / Chapter 3.4 --- Conclusion --- p.54 / Chapter 3.5 --- References --- p.55 / Chapter Chapter 4. --- Detector Response / Chapter 4.1 --- Introduction --- p.56 / Chapter 4.2 --- Experimental / Chapter 4.2.1 --- Reagents and Equipment --- p.57 / Chapter 4.3 --- Results and Discussion / Chapter 4.3.1 --- "The Relationship between Peak Area, Peak Height, and Detector Response" --- p.58 / Chapter 4.3.2 --- Detector Response and Eluent Strength --- p.60 / Chapter 4.3.3 --- Detector Response and Flow Rate --- p.74 / Chapter 4.4 --- Conclusion --- p.77 / Chapter 4.5 --- References --- p.78 / Chapter Chapter 5. --- Determination of Benzhexol Hydrochloride and Ethambutol Hydrochloride tablets by HPLC / Chapter 5.1 --- Introduction --- p.79 / Chapter 5.2 --- Experimental / Chapter 5.2.1 --- Reagents --- p.84 / Chapter 5.2.2 --- Equipment --- p.85 / Chapter 5.2.3 --- Samples --- p.86 / Chapter 5.2.4 --- Preparation of Reagents and Standards --- p.88 / Chapter 5.2.5 --- Sample Preparation and Determination --- p.89 / Chapter 5.3 --- Results and Discussion / Chapter 5.3.1 --- Sample Treatment and Extraction of Active Ingredient(s) --- p.91 / Chapter 5.3.2 --- Explanation of Chromatograms --- p.92 / Chapter 5.3.3 --- Choice of Experimental Conditions --- p.96 / Chapter 5.3.4 --- Linear Dynamic Response --- p.102 / Chapter 5.3.5 --- Sensitivity --- p.102 / Chapter 5.3.6 --- Analysis Results --- p.103 / Chapter 5.3.7 --- Comparison of Results from the Methods --- p.106 / Chapter 5.3.8 --- Precision and Accuracy --- p.113 / Chapter 5.3.9 --- Effect of Methanol Content on the Chromatographic Behaviour in Analysing Benzhexol Hcl --- p.117 / Chapter 5.3.10 --- Discussion on the Pharmacopoeial Assay of Benzhexol HC1 Tablets --- p.120 / Chapter 5.3.11 --- Discussion on the Various Factors Influencing the Pharmacopoeial Assay of Ethambutol HC1 Tablets --- p.123 / Chapter 5.4 --- Conclusion --- p.128 / Chapter 5.5 --- References --- p.129 / Appendix --- p.132

Thesis (DTech (Environmental-health))--Cape Peninsula University of Technology, 2018. / The management of agricultural soil and its sustainable use, namely productivity, is paramount to the agricultural industry worldwide. Large-scale agricultural product producers and scientists emphasise using environmentally benign methods to increase agricultural production such as taking a green chemistry approach to agricultural activities and/or using cultivation techniques for the bio-augmentation of agricultural soil. Some of these agricultural products, such as cassava (Manihot esculenta), produce cyanogens which promote the infestation of a cyanogen-resistant microbial species known to produce mycotoxins during decomposition. Although cyanogens and mycotoxins are important components in the functioning of the earth system and agricultural soil, their cumulative effects can result in reduced soil productivity, hence degradation. Furthermore, the presence of mycotoxins in the environment and agricultural produce is hazardous to the environment, including the biotic communities in soil and humans. Therefore, an environmentally benign (green chemistry approach) method for the reduction of cyanogens and mycotoxins was proposed for this research study. The method investigated had to be applicable in-situ for the biodegradation of cyanogens and mycotoxins. Their reduction from decomposing cassava in cultivated soil, which can be used on a small and large scale, would mitigate deleterious effects of a less reported, unknown mycotoxins producer (fungal species), Cunninghamella bertholletiae (KT275316), found to be a free cyanide- (CN-) resistant isolate. The C. bertholletiae was isolated from decomposing cassava tubers and silt, subsequent to culturing on potato dextrose agar (PDA) and in an equivalent volume of nutrient broth (NB) containing KCN (4mg/40mL) at 30 °C for 120 hrs. The isolate demonstrated an ability to biodegrade CN- into NH3 and NO3. NH3 and NO3 are nitrogenous by-products produced when young cassava plants are cultivated in a controlled environment, with 80% of the initial CN- concentration being efficiently degraded to NH3/NO3 at a conversion rate of 77.5% and 72.5% (fungus from silt and cassava), respectively, within 120 hrs. From this research, it was observed that Sub-Saharan Africa is the largest contributor to the CN- load into the environment; from cassava cultivation as per FAO data. The quantity of CN- released was estimated at 0.025x10-3 to 6.71 ppq, with further increases of 60.5% being projected to be released into the environment by 2024. As such, it was hypothetically assumed that numerous species in cassava-cultivated soil become CN- resistant as they are exposed to CN- from decomposing cassava, becoming pathogenic thus antigonistic towards other biota in cassava-cultivated soil. Consequently, the pathogenicity of the isolate was investigated against organisms (n = 12) from cassava-cultivated soil. The isolate demonstrated inhibitory pathogenic activity against some soil bacterial communities such as Oligella ureolytica, Acinetobacter sp., Pseudomonas luteola and Sphingomonas paucimobilis. The isolate also demonstrated minor antagonistic effects against Myroides sp., Stenotrophomonas maltophilia, Candida lipolytica, Cryptococcus albidus and Rhodotorula sp.. Further research to identify extracellular metabolites produced by this organism, using a fermentation method was also carried out using a liquid state fermentation technique. 30 mL Erlenmeyer flasks containing 25 mL of NB/KCN (source of CN-) at 37 °C for 168 hrs, with a volume of (5 mL), extracts from the fermentation being filtered, centrifuged, mixed with chloroform for a liquid-liquid extraction procedure subsequent to a nitrogen-facilitated blow-down technique and reconstitution with 100% analytical grade methanol, for LC/MS-TOF 6230 analysis. The analysis revealed that the isolate was able to produce the mycotoxins/secondary metabolites, Fumonisin B1 (FB1) and Deoxynivalenol (DON). Though the isolate (KT275316) demonstrated the ability to biodegrade cyanide as well as produce mycotoxin, an environmentally benign strategy (green chemistry method) with a potential to biodegrade CN-/NH3/NO3/NO2 for the biodegradation of mycotoxins was evaluated, including the identification of biodegradation by-products post-biodegradation treatment. Thus, plant extracts from Nepenthes mirabilis were found to contain enzymes such as carboxylesterase, β-glucosidase, β-glucoronidase and phosphatidyl inositol phospholipase C (identified using both quantitative and qualitative methods). The plant extracts were used with treated samples from the fermentation and were subjected to biodegradation. Thus, resulting in biodegradation by-products such as Heptadecanone Octadecanamide, Octadecenal for FB1 and Tolmetin for DON, respectively. For future research, it is therefore recommended that plant extracts with similar properties to those observed for N. mirabilis extracts (juice) be sought for application of the proposed method.