Department of Chemistry and Polymer Science
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Browsing Department of Chemistry and Polymer Science by browse.metadata.advisor "Burger, B. V."
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- ItemChemical characterisation of the aroma of honeybush (Cyclopia) species(Stellenbosch : University of Stellenbosch, 2010-12) Cronje, Joan Christel; Le Roux, Maritha; Burger, B. V.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.ENGLISH ABSTRACT: Honeybush tea, also known as “South Africa’s sweetest tea”, is a herbal tea made from the leaves and twigs of Cyclopia spp., indigenous to the fynbos biome in the Western and Eastern Cape provinces of South Africa. The pleasant sweet aroma and taste of fermented honeybush, its low tannin content and the absence of caffeine have led to widespread interest in the commercial cultivation and processing of honeybush tea since the mid-1990s. Although more than 20 species of honeybush grow in the wild, only a few species are commercially exploited for the manufacture of tea. Currently the more prominent species are C. intermedia, C. subternata, C. genistoides, and C. sessiliflora. The present research contributes to a comprehensive honeybush research programme being conducted at the Agricultural Research Council (ARC) Infruitec-Nietvoorbij in South Africa. The first phase of the present study, using C. genistoides as representative species, was aimed at developing the necessary methodology for the analysis of extremely low concentrations of honeybush volatiles. A high-capacity headspace sample enrichment probe was applied successfully in conjunction with gas chromatography-mass spectrometry (GC-MS) to analyse the volatile organic compounds present in dry or infused unfermented and fermented honeybush. A total number of 255 volatile compounds were identified in unfermented and fermented honeybush, the majority of which are terpenoids (138; 54%) comprising mostly terpenes, terpene ketones, terpene alcohols and terpene ethers. Of the other compound classes, the aldehydes are the largest group, followed by esters, hydrocarbons and ketones. The stereochemistry of the identified compounds was determined whenever possible. This is the most comprehensive chemical characterisation of the volatile compounds in a South African herbal plant reported to date. A comparative study of green and fermented honeybush showed that the same compounds are, to a large extent, present in both, albeit in different relative concentrations. Not all of the identified honeybush volatiles are necessarily odour-active compounds contributing to the overall typical honeybush aroma. An important aspect of this research was thus the identification of the 46 odour-active compounds in fermented honeybush by means of gas chromatography-olfactometry (GC-O), using detection frequency and aroma extract dilution analysis methods. Fifteen of these compounds, mainly terpenoids, were singled out as the most intense individual contributors to the honeybush aroma based on consideration of all the relevant GC-O data. The odours of certain compounds, i.e. (6E,8Z)-megastigma-4,6,8-trien-3-one, (6E,8E)-megastigma- 4,6,8-trien-3-one, (7E)-megastigma-5,7,9-trien-4-one, 10-epi- -eudesmol, epi- -muurolol and epi- - cadinol, were perceived by GC-O assessors as typically honeybush-like. The quantitative GC-MS data of seven different Cyclopia samples (including four different species and variants thereof) were compared with respect to all the volatile components and particularly with respect to the odour-active compounds. Interesting variations were found in the concentrations of certain odour-active compounds in the various samples. The quantitative data obtained for the odour-active honeybush volatiles and data obtained from the sensory analysis of eight Cyclopia samples (including four different species and variants thereof) were subjected to statistical analysis and interesting associations between compounds with certain sensory aroma attributes were established. The present study has made a major contribution to the scientific knowledge regarding one of South Africa’s most popular indigenous herbal teas.
- ItemChemical characterisation of the uropygial secretion of Rhinopomastus cyanomelas(Stellenbosch : Stellenbosch University, 2004-03) Ghebrealfa Kahsai, Negassi; Le Roux, M.; Burger, B. V.; Stellenbosch University. Faculty of Science . Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: The uropygial gland of most birds produces a variety of hydrocarbons, lipids, waxes, fatty acids, alcohols and other organic compounds. These compounds have two widely recognized functions, viz. they are considered essential for the maintenance of a good plumage condition, and may be used for fungicidal, bactericidal or other hygienic purposes. Scimitar-billed woodhoopoes, Rhinopomastus cyanomelas, are groupterritorial birds that live in groups comprising between two and twelve individuals. Individuals enter the roost cavities shortly after sunset and exit the following morning soon after sunrise. During the period that the birds are inside the roost, they are vulnerable to a range of vertebrate predators, including snakes, genets and rats. When disturbed while roosting, woodhoopoes immediately face away from the threat hence presenting their uropygial glands in the direction of the threat. Typically, a drop of brown, highly pungent secretion is then formed at the tip of the papilla to the uropygial gland, and kept in place by a few tuft-like feathers. This response pattern has led some observers to believe that the secretion serves an anti-predatory role. It has been found that the synthetic volatile constituents of the uropygial secretion of the green woodhoopoe, P. purpureus, individually or as a mixture, have potent defensive properties against feline and reptilian predators. In addition, the compounds also showed activity against a range of bacteria. The aim of the present study was to determine the chemical composition of the uropygial secretion of the scimitar-billed woodhoopoe, Rhinopomastus cyanomelas, as a first step towards the evaluation of, inter alia, the semiochemical function of the secretion. Using gas chromatography-mass spectrometry, 179 constituents of the uropygial secretion of the scimitar-billed woodhoopoe have been identified. The majority of the constituents of the secretion are branched and unbranched aldehydes (aliphatic and aromatic), acids (aliphatic and aromatic), sulfides and ketones. This group of volatile compounds is responsible for the obnoxious odour of the secretion and possibly also for its defensive action against predators. The secretion also contains a large number of branched and unbranched alkanes and wax esters. The chemical composition of the secretion was compared with the secretion of P. purpureus as well as with that of the hoopoe, Upupa africana. The uropygial gland secretion of the scimitar-billed woodhoopoe is quite similar to that of the green woodhoopoe, although it is much more complex than that of the green woodhoopoe. In contrast to the uropygial secretions of the green and the scimitar-billed woodhoopoes, the secretion of Upupa africana does not have a strongly obnoxious odour and it also does not contain large quantities of alkanes and wax esters.
- ItemChemical communication : chemical characterization of volatile constituents of urine of the southern African cheetah, Acinonyx jubatus jubatus, using headspace sampling and GC-MS(Stellenbosch : Stellenbosch University, 2002-12) Visser, Runine (Runine Cecile); Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: The cheetah, Acinonyx jubatus, sometimes referred to as "the greyhound of the cats", is probably the most elegant member of the cat family. Formerly widespread in southern Africa it is now threatened with extinction. It occurs in open savanna and light woodland, but also hilly country on occasion. The cheetah is a predator that can reach speeds of more then 110 km/h in short bursts. With a mass of between only 40 to 60 kg, it is not very powerful and cannot defend itself very effectively against carnivores such as the lion and hyaena, for example. This might be the reason why, in order not to advertise its presence, the urine of this animal is practically odourless. In turn, this might explain why no research has so far been devoted to the urine of this animal. In contrast extensive work has been done on the chemical characterisation of the urine of many other carnivores, notably the lion. Extraction of the urine with dichloromethane gave too little material for GC-MS. SPME sampling of the urine itself gave insufficient sample enrichment. Better results were obtained when an SPME-type of headspace sampling, using a larger mass of polydimethylsiloxane, was employed although many of the constituents of the urine could still barely be detected. The compounds identified include a large number of ketones, aldehydes, cyclic and acyclic ethers, carboxylic acids, amides two sulphur compounds in barely detectable quantities, and elemental sulphur. Perhaps the most remarkable result of this thesis is that it was found that the urine of the cheetah, although it is a carnivore, does not contain several sulphur compounds in relatively high concentrations. However, it does contain elemental sulphur. Perhaps a mechanism exists by which the cheetah can convert strongly odorous sulphur containing compounds into the less strongly smelling sulphur.
- ItemChemiese karakterisering van die aroma van die heuningbosspesie Cyclopia Genistoides(Stellenbosch : University of Stellenbosch, 2006-03) Cronje, Christel; Le Roux, M.; Burger, B. V.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.Honeybush (Cyclopia spp.) is indigenous to South Africa and consists of more than 20 species of which only a few are used to make a herbal tea with a unique aroma and sweet taste. The aroma of unfermented and fermented honeybush tea differs considerably, indicating that changes take place in the chemical composition of the aroma during the fermentation process. Using a sample enrichment probe (SEP) and gas chromatography-mass spectrometry (GC-MS), the chemical composition of the aroma of unfermented and fermented C. genistoides, was analyzed and the resulting aroma profiles were compared. A total of 74 compounds were identified in the unfermented honeybush aroma, comprising, inter alia, a large number of saturated and unsaturated alcohols, aldehydes and methyl ketones that were found to be either absent, or present in lower relative concentrations, in the aroma of fermented honeybush. Most of these compounds, including 6-methyl-5-hepten-2-one, identified as one of the major constituents of unfermented honeybush, are probably responsible for its grassy, hay-like aroma. In the aroma of fermented honeybush 70 compounds were identified, of which 36 were found to be terpenoids. These compounds are probably responsible for the pleasant sweet aroma of the fermented honeybush. For instance, the major aroma constituent in the fermented honeybush, α-terpineol, is known to have a delicately floral and sweet odour. Other terpenoids occuring in significant quantities in the fermented honeybush, are linalool, cis and trans linalool oxide, nerol, geraniol, 2,6-dimethyl-1,7-octadien-3,6-diol, hexahydrofarnecyl acetone and phytol. These terpenoids are known to have sweet, sweet-woody en floral odours that probably contribute to the overall sweet aroma of the fermented honeybush. In the aroma of the unfermented honeybush a total of 25 terpenoids was identified, of which geranyl acetone, β-ionone, and dihydroactinidiolide are the most significant, since they are present in higher relative concentrations compared to the same terpenoids in the fermented honeybush. These three terpenoids have overall woody and even slightly green odours which contribute to the typical aroma of the unfermented honeybush. The terpenoids present in the aroma of unfermented and fermented honeybush belong to the following compound classes: • Terpenes • Terpene alcohols • Terpene aldehydes • Ketoterpenes • Terpene ethers • Terpene lactones Apart from the terpenoids present in the aroma of unfermented and fermented honeybush, the following classes of compounds are also present: • Aliphatic hydrocarbons (saturated) • Aliphatic alcohols (saturated and unsaturated) • Phenols • Aliphatic aldehydes (saturated and unsaturated) • Aliphatic ketones (saturated and unsaturated) • Aliphatic carboxylic acids (saturated) • Esters (methyl esters, ethyl and higher esters and aromatic esters) • Furane compounds • Lactones The present research was done to compare the chemical composition of the aroma of unfermented and fermented honeybush of one particular species, namely C. genistoides, to obtain an understanding of the evolution and/or disappearance of volatile compounds during fermentation that ultimately could help to identify compounds or compound types and their precursors responsible for its unique sweet aroma.
- ItemChemiese karakterisering van die preorbitale afskeiding van die suni-ooi, Neotragus moschatus(Stellenbosch : Stellenbosch University, 2001-03) Spies, Anena; Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: Please refer to fulltext for abstract
- ItemChemiese kommunikasie van die Suid-Afrikaanse gordelakkedisse(Stellenbosch : Stellenbosch University, 2003-12) Louw, Stefan; Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: The sungazer, Cordylus giganteus, is an endangered lizard species belonging to the family Cordylidae. It has been speculated that the function of semiochemical communication is performed by two types of skin glands, the femoral glands and the generation glands, which are also found in this family of lizards. Other skin glands and also the cloacal glands are further possible sources of semiochemicals. The investigation of these potential sources of chemical messages in C. giganteus, served as a starting point towards a better understanding of the chemical communication of lizard species belonging to the family Cordylidae. In continuation of this study the femoral gland secretion of the Cape girdled lizard, C. cordylus, was also investigated. Gas chromatography, low resolution GC-MS, GC-HR-MS, MO-TMS derivatisation and retention time comparison were used as analytical techniques in the chemical characterization of the femoral and generation gland secretions of C. giganteus and the femoral gland secretion of C. cordylus. Some compounds were not identified because of their low concentration in the secretions and/or mass spectra could not be obtained for pure compounds because of co-elution with other compounds. Compounds identified in the femoral gland secretion include the following: Carboxylic acids - saturated and unsaturated Alcohols Ketones Aldehydes - saturated and unsaturated Esters - saturated and unsaturated Hydrocarbons - saturated and unsaturated Nitriles Amides - saturated and unsaturated y-Lactones Squalene u-Tocopherol Steroids Quantitative analysis of the femoral and generation gland secretions of a number of sungazers indicated distinct differences between the secretions of males and females (in the case of the femoral gland secretions), but no apparent trend could be found in the differences between the femoral and generation gland secretions of individual lizards of the same gender. Qualitative seasonal differences were however observed in the femoral gland secretions of all individuals of C giganteus.
- ItemElektrofiele addisiereaksies in die sintese van hormone en feromone(Stellenbosch: University of Stellenbosch, 1977-03) Visagie, Hester E.; Gerbers, C. F.; Burger, B. V.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.Please refer to full text.
- ItemIdentification of the putative urinary intraspecific recognition pheromone of the caracal caracal caracal(Stellenbosch : Stellenbosch University, 2017-03) Hailemichael Goitom, Aron; Burger, B. V.; De Villiers, Andre J.; Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science.ENGLISH ABSTRACT: Sheep husbandry makes a considerable contribution to the economy of South Africa. However, it has been pressure during the last few decades due to the rapidly growing numbers of predators such as the caracal, Caracal caracal, and the red jackal, Canis mesomelas. Currently, sheep farming is hardly viable in the arid southern parts of the country. When experimenting with various methods of controlling caracal numbers, sheep farmers found that this problem animal could be effectively lured into traps using the urine of another male or female caracal. The main disadvantage here is that a sheep farmer could incur serious stock losses before he is able to obtain a starting sample of urine from another source (e.g., another farmer). It was hypothesised that caracal urine contains a volatile organic substance, or substances (VOCs), that are involved in the semiochemical communication between members of this species. The objective of this investigation was to identify these putative attractants in the urine, for the subsequent formulation of a caracal lure composed of synthetic analogues of the natural VOCs. As sheep farmers reported that male and female urine were equally effective attractants, it was considered unlikely that the attracting agent could be a sex pheromone; rather, it could have an intraspecific signalling function. Efforts were made to identify all the VOCs present in caracal urine samples donated by farmers from different sheep farming areas of the country. A total of 191 VOCs, including five steroid hormones, were identified. The identification of 86% of these VOCs was corroborated by gas chromatographic-mass spectrometric (GC-MS) comparison of the natural substances with authentic synthetic analogues. Obligate proteinuria is known in certain animals, in which it is not an indicator of renal abnormality. In the house mouse, Mus domesticus, for example, so-called major urinary proteins (MUPs) bind dehydro-exo-brevicomin and 2-(sec-butyl)-4,5-dihydrothiazole elicit male aggression. The carboxylesterase-like urinary excreted pheromone-binding protein, also known as cauxin, has been identified in the urine of several felids, but was not found in caracal urine. However, the pheromone-binding proteins ‘Transgelin fragment (M3WJ37)’ and ‘Uncharacterized protein (M3XEJ0)’, both previously identified in Felis catus and Felis silvestris catus, were identified in caracal urine. The macrocyclic C15 ketone, cyclopentadecanone, was identified as one of the VOCs present in the headspace gas of caracal urine. The headspace concentration of this ketone increased when the urine was heated at 95 ºC for 10 min. A similar, but more pronounced increase in cyclopentadecanone concentration was observed when urinary protein present in caracal urine was denatured by subjecting it to similar treatment. This was interpreted as an indication that this ketone is a ligand of caracal urinary protein. The C13, C14, C16, and C17 macrocyclic ketones were subsequently also identified as urinary protein ligands. In bioassays, a mixture of synthetic analogues of a large number of the other ketones identified in caracal urine, including cyclopentadecanone, elicited typical feline behaviour in two male caracal in captivity. Similar behavioural patterns were observed when a mixture of the C13, C14, C15, and C16 macrocyclic ketones were tested. It was concluded that these ketones, that are ligands of the caracal’s urinary protein, could play an essential role in the intraspecific communication of the caracal.
- ItemInvestigation into the semiochemical communication involved in neonatal offspring recognition in sheep(Stellenbosch : University of Stellenbosch, 2010-03) Viviers, Marlize Zaretha; Burger, B. V.; Le Roux, M.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.ENGLISH ABSTRACT: Sheep husbandry substantially contributes to South Africa’s economy. Lamb mortality is regarded as a major constraint to sustainable sheep production, and an important factor in lamb survival is the strong ewe–lamb bonding. This is a well-known phenomenon in all sheep races and strong evidence exists that the selective ewe–lamb bond formation has a pheromonal basis, in that the ewe can distinguish her lamb by its unique, familiar smell. Sheep farmers and scientists have examined various methods of making alien lambs acceptable to foster ewes. The survival rate of offspring could be substantially increased if a reliable method could be devised to prevent ewes from rejecting their own lambs or if ewes could be induced to accept alien lambs. A better understanding of the semiochemicals involved in this communication between ewe and offspring could facilitate the development of a method by which ewes can be coaxed into adopting foster lambs. This would positively contribute to efficient sheep production in South Africa. The objective of this study was to characterise the volatile constituents present in the wool and the amniotic fluid collected from the Döhne Merino lambs to achieve a better understanding of the ewe–lamb semiochemical communication. The volatile organic constituents associated with the wool and amniotic fluid were characterised and a total of 133 volatile organic compounds were identified. Several compound classes are represented in these samples and the majority of these compounds have previously been identified in the excretions and secretions of numerous mammalian species. A number of different aspects of ewe–lamb kin recognition were investigated. First, the odour profiles of twin lambs were compared to those of other twins. The results of these analyses revealed that the wool volatiles of twin lambs are qualitatively as well as quantitatively practically identical, but different from those of other lambs in the flock. Second, the change in the odour profiles of lambs was studied over a seven-day period. It was found that the odour profiles of lambs are not fixed, and for as long as a ewe makes use of olfactory recognition as the main mode of identification of her lamb she has to continue learning the odour of her lamb. Third, the amniotic fluid was investigated as a possible source of maternal labels, i.e. as chemical codes consisting of mixtures of compounds in specific quantitative ratios that are imprinted on lambs by their mothers at birth. It was found that the amniotic fluids of first- and second-born lambs are qualitatively and quantitatively different. It is possible that the duration of the lambing birth process could contribute to this change in amniotic fluid composition. Fourth, the role of residual proteins in the dissemination of the semiochemicals involved in ewe– lamb communication was investigated and six proteins were identified as amniotic fluid and wool-associated proteins. Bioassays carried out during the lambing season of 2009 confirmed the role of the odour of the lamb in ewe-lamb recognition, but bioassays carried out with synthetic pheromone formulations gave inconclusive results.
- ItemDie isolering en identifisering van die hondafwerende faktor in die kutikulêre afskeiding van die geelhondebosluis, Haemaphysalis leachi(Stellenbosch : Stellenbosch University, 2004-12) Marx, Brenda; Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: When in close contact with the Yellow Dog Tick, Haemaphysalis leachi, dogs show clear signs of disgust or even nausea. It is accepted that the secretion is produced by the tick in order to prevent the dog from removing the tick from its body with its teeth, thereby increasing the chances for the tick's survival. The composition of this secretion was studied in order to identify the chemical compounds responsible for the repellent action of the secretion. Because of the dog's keen sense of smell, the tick only needs to produce minute quantities of this repellant, which significantly complicated the detection of the different components by conventional GC-methods. Several sampling and sample enrichment methods were explored, including solvent extraction, SPME sample enrichment, adsorption on active charcoal, cryoprecipitation, sorption in a phasecoated open tubular trap, as well as solventless sampling, in order to determine which method would ensure an appropriate amount of sample for gas chromatographic detection. Two of these sampling methods yielded acceptable results: The first method consisted of rinsing irritated female ticks with dichloromethane and, after concentrating the sample by evaporation, GC-MS analysis using normal splitless injection. The second method entailed collecting secretions by wiping irritated ticks with glass micro fibre filter paper after which the paper was inserted directly into the inlet liner of the GCMS system, where thermal desorption of the volatile constituents of the secretion preceded gas chromatographic separation and mass spectral detection. Live dogs were needed for the evaluation of the isolated material to determine whether the samples had an aversive effect on them. The extract was separated into different fractions, which were further separated into subfractions. After each separation process, all the fractions were tested for efficacy in order to determine which fraction contained the active components, narrowing down the number of candidate target compounds. It was concluded that a combination of aldehydes, namely hexanal, heptanal, octanal, nonanal, decanal, undecanal and dodecanal, is responsible for the dog repelling action of the secretion. In most cases the semiochemicals of insects and mammals are secreted in a more complex matrix to ensure prolonged activity. For this reason some of the other compounds in the complex cuticular secretion of this tick species were also identified during the course of this study.
- ItemDie karakterisering van die reukmerkvloeistof van die Bengaalse tier, Panthera Tigris Tigris(Stellenbosch : University of Stellenbosch, 2006-03) Viviers, Marlize Z.; Burger, B. V.; Le Roux, M.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.Although the Bengal tiger, Panthera tigris tigris, appears on the IUCN Red Data List for endangered animals, very little information is available in the literature on the components of this animal's marking fluid. Scent marking is the main form of communication in all cat species. In some species, including the Bengal tiger, the liquid used for spraying is not pure urine, but is mixed with scent gland secretions. The objective of this study was to characterise the volatile components in the marking fluid of the Bengal tiger to achieve a better understanding of the semiochemical communication of this animal. The marking fluid of the tiger was characterised through the use of analytical techniques, such as gaschromatography, low resolution gas chromatography - mass spectrometry and retention time comparison. Homologous series of alkanes, alcohols, aldehydes, methyl ketones, carboxylic acids, γ- and δ-lactones, amides and lactams, as well as esters and nitrogen containing compounds, were identified. Of these identified compounds the unbranched alkanes, saturated alcohols, aldehydes, branched methyl ketones, saturated carboxylic acids and γ- and δ- lactones are commonly found in mammalian secretions. Compounds that aren't as common in their secretions are the methyl ketones, branched carboxylic acids, dimethyl esters of dicarboxylic acids and amides. The marking fluid contains a phthalic acid ester. Phthalic acid esters are used in the polymer industry and are nowadays found almost everywhere in nature. It is known that these pollutants have endocrine disrupting properties. The heat, humidity and wet conditions that are characteristic of the Bengal tiger's natural habitat makes it necessary for the tiger to make use of a fixative to prolong the life of the semiochemical message. The compounds and the concentrations in which these compounds are present in the urine and the lipid fraction of the marking fluid of the tiger was determined and compared to assess the fixative role of the lipids. This study has provided evidence that the lipid material has a greater affinity for the volatile organic constituents of the marking fluid and that it can therefore extend the lifetime of a semiochemical message left by the tiger.
- ItemOlfactory communicatiaon : chemical characterization of the interdigital secretion of the black wildebeest, Connochaetes gnou(Stellenbosch : Stellenbosch University, 2000-12) Slade, Desmond; Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science . Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: The black wildebeest, Connochaetes gnou, is a terriorial animal and although it is not generally accepted, it is believed that it defines its territory by scent marking, using interdigital and preorbital secretions, faeces, and urine. The aim of this study was to characterize the chemical constituents of the interdigital secretion. Due to the complexity of the secretion, only one hundred and ten of the approximately 350 compounds could be determined with known techniques. Gas chromatography, low resolution GC-MS and retention-time comparison were the main analytical techniques used. Classes of compounds identified in the interdigital secretion include the following: • Hydrocarbons - Aliphatic (saturated and unsaturated) and aromatic • Alcohols - Aliphatic (saturated, unsaturated, cyclic and diols) • Phenols and Phenylalkanols • Aldehydes - Aliphatic (saturated and unsaturated) and aromatic • Ketones - Aliphatic (saturated, unsaturated, cyclic and diketones) and aromatic • Hydroxy ketones - Aliphatic and cyclic • Carboxylic acids - Aliphatic (saturated, unsaturated and cyclic) and aromatic • An anhydride • Esters - Methyl esters, ethyl and higher esters, unsaturated esters and aromatic esters • Lactams • A steroid Only small qualitative and quantitative differences were found between the male and female interdigital secretions.
- ItemOntwikkeling van instrumentasie vir omvattende tweedimensionele gaschromatografie(Stellenbosch : Stellenbosch University, 2001-12) Snyman, Tertia; Burger, B. V.; Le Roux, M.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: Even capillary gas chromatography does not always give complete separation of the components of complex mixtures. During the last few decades several two-dimensional gas chromatographic techniques were developed to circumvent this problem and towards the end of the previous century, a technique that became known as comprehensive twodimensional gas chromatography, was introduced with which the peak capacity of capillary gas chromatography could be increased by at least two orders of magnitude. This technique is based on utilizing different separation mechanisms of two coupled chromatographic columns to get a better separation of complex mixtures than would be possible with the individual columns. To be classified as comprehensive twodimensional gas chromatography, the analytes eluted from the first or primary column must al be transferred to the second column as sharp sample pulses by, for example, focusing of analytes. Focusing of the analytes can be achieved by trapping or immobilizing the analytes in a short capillary tube that serves as a connection between the two columns, after which the trapped material is released as a sharp pulse into the secondary column by rapidly, i.e. within a fraction of a second, heating this capillary which therefore serves to modulate the effluent from the primary column. This ensures optimum separation on the secondary column and the independence of retention times of the analytes on the two columns. A modulator consisting of a capillary (modulator capillary) coated with a thick film of an apolar stationary phase was used in the present project to immobilize or trap the analytes. This capillary was housed in a stainless-steel tube (heater) which was subdivided into a number of segments of equal lengths (maximum of 10). These segments were heated sequentially to desorb the analytes from the inlet end of the modulator to its outlet end at such a rate as to generate and transfer a sharply focused analyte pulse into the secondary column. In a typical analysis each of the 10 segments of a lO-segment heater would, for example, be heated to a temperature 50°C higher than that of the gas chromatograph's oven (50°C temperature increment) within 200 milliseconds, after which each segment would be allowed to immediately cool down to the temperature of the oven. After the last segment had been heated, a pause of, for example, two seconds followed to allow analytes to be trapped in the modulator capillary after which the cycle was repeated until the analysis had been completed. For several reasons, heating the segments resistively by using a current of between 1 and 20 Ampere was preferred to the application of high voltages. A computer controlled power supply was developed with which any combination of duration of the energizing pulses of the segments from 10 to 2500 milliseconds, pause times from 100 milliseconds to 100 seconds and temperature increments of 100°C or higher could be used with acceptable precision and high reproducibility in comprehensive two-dimensional gas chromatographic analyses. The effectivity of the focusing that can be achieved with heaters having different numbers of segments, modulator capillaries with different inside diameters, different heating increments, as well as different rates at which the modulators are heated, were investigated. The best results were obtained with heaters having 8 and 10 segments, a modulator capillary with an inside diameter of 0.2 mm, a heating increment between 50°C and 10Goe, and a heating cycle composed of a total heating time of two seconds followed by a pause time of two to three seconds before the next cycle is started. A light petroleum oil fraction was used in a preliminary evaluation of the comprehensive two-dimensional system that was developed. At this stage of the project the influence of various parameters such as the average carrier gas velocity, the temperature program and the length of the secondary column was investigated. It was found that changing one parameter required the re-optimization of the other parameters. The concentrations of the sample also had a marked influence on the parameters that had to be used to achieve optimum results. A low sample concentration appeared to require a higher carrier gas velocity, a higher temperature-programming rate or considerably longer pause times to achieve satisfactory focusing of analytes, whereas too high a concentration resulted in breakthrough of the analytes from the modulator capillary. The two-dimensional gas chromatographic device was also interfaced to a quadrupole mass spectrometer. A GC-MS analysis of a petroleum oil sample gave mass spectra of surprisingly good quality in spite of the high scanning speed that was required by the sharp constituent peaks produced by the gas chromatographic component of the system. The two-dimensional system that was developed therefore appears to offer a costeffective alternative to other systems that have been developed elsewhere in which other modulation mechanisms are used. One remaining problem that still has to be solved is the unsatisfactory synchronization of the timing device of the power supply with that of the computer on which data are accumulated. Although the difference in timing may seem negligible, the result is that certain software packages cannot be used for the two-dimensional visualization of the data Of several possible solutions to the problem, redesigning the control circuitry of the power supply will be the first option to be explored. An important consideration in the development of the system was to avoid having moving parts so that the modulator could be installed in any gas chromatograph without requiring structural alterations to the instrument. No provision was therefore made to install the two columns and the modulator in separate temperature-programmable compartments in the oven of the gas chromatograph. During the evaluation of the present system it was, however, found that the parameters which gave acceptable results were confined to rather narrow limits. Not being able to cool the modulator to temperatures below that of the oven was found to be the most important limiting factor. A simple solution to this problem is to cool the modulator to a selected suitable temperature below the oven temperature with compressed air, the flow of which is regulated by a computer controlled mass flow regulator to maintain the same increment below the oven temperature right through an analysis. As this development was considered to be outside the scope of the present project, this idea was not implemented and evaluated. However, successful exploratory experiments were done in which the flow was mechanically regulated. A prototype of the component in which the modulator can be cooled was built and the mass flow regulator, control unit and software will be commissioned shortly.
- ItemThe role of micro-organisms in the production of semiochemicals in the interdigital secretion of the bontebok, Damaliscus pygargus pygargus(Stellenbosch : Stellenbosch University, 2004-03) Scott, Gary Terri; Le Roux, M.; Burger, B. V.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: Bontebok, Damaliscus pygargus pygargus, formerly classified as D. dorcas dorcas, are territorial animals with interdigital glands between the toes of the forelegs. Males regularly defecate on dung heaps, on which they often lie, to communicate with other members of their species. They also communicate by means of visual displays, scent marking and occasionally with scraping or pawing of dung heaps. It is assumed that scent marking with the interdigital secretion serves to define territories frequented by these antelope. These glands secrete a complex mixture of volatile and non-volatile compounds and the volatile compounds in the secretion serve as a chemical signal for other bontebok. It has been suggested that the interdigital secretion is not produced in its final composition by the interdigital gland alone, but that microbial activity is responsible for many of the compounds present in the secretion. In general, many compounds can be attributed to the by-products of microbial hydrolysis of triglycerides, a common characteristic of sebum. It is well documented that micro-organisms inhabit the deep recesses of sebaceous glands and the presence of micro-organisms has been found to be consistent in all antelope exocrine glandular areas. This study involved the chemical characterisation of the volatile metabolites produced in vitro by micro-organisms from the interdigital cavity of the bontebok. Various comparative studies were made, one of which was comparison of the metabolites produced by the individual microbial species as well as the total community of bacteria incubated in different media. A comparison of the compounds identified in the interdigital secretion and the metabolites produced by the micro-organisms in the different media was also made. The volatile metabolite extracts of the individual bacterial species and of the total community were chemically characterised by low-resolution gas chromatography-mass spectroscopy. Classes of compounds identified from the volatile metabolite extracts include: • Acids - Aliphatic (saturated and unsaturated) • Alcohols - Aliphatic (saturated and unsaturated) • Aldehydes - Aliphatic (saturated and unsaturated) • Aromatic compounds • Ketones - Aliphatic (saturated and unsaturated) • Pyrazines • Dimethyldisulphide • Squalene and cholesterol Several qualitative differences were found between the compounds identified in the volatile metabolite extracts of the micro-organisms when incubated in tryptic soy broth (TSB) and minimal salt medium (MSM). In particular, when the microbes were incubated in TSB medium a number of pyrazines were found that were not present when utilising MSM as a medium. Additional qualitative differences were found between the compounds identified in the metabolite extracts of the individual bacterial species and the total community of bacteria, when incubated in both TSB and MSM media. A comparison of the interdigital secretion and the metabolite extracts of the microbial communities incubated in TSB and MSM revealed that many compounds produced in MSM corresponded to the compounds identified in the interdigital secretion. These corresponding compounds were found to be saturated and unsaturated acids, aldehydes and squalene. Furthermore, there was only one corresponding compound in the case of TSB as medium.
- ItemStir bar sorptive extraction and gas chromatography : mass spectrometry for the analysis of biological matrices(Stellenbosch : University of Stellenbosch, 2007-12) Stopforth, A.; Sandra, P. J. F.; Crouch, A. M.; Burger, B. V.; University of Stellenbosch. Faculty of Science. Dept. of Chemistry and Polymer Science.This study describes the development of simplified analytical methods for the analysis of trace quantities of selected naturally occurring target compounds in complex biological matrices by stir bar sorptive extraction (SBSE) and gas chromatography/mass spectrometry (GC/MS). SBSE facilitates the direct extraction of organic compounds from aqueous samples by allowing the solutes to partition between the aqueous phase and a glass stir bar that is coated with a layer of polydimethylsiloxane (PDMS). The partitioning of polar compounds into the PDMS coating was enhanced by using different derivatization techniques in combination with SBSE. The derivatization of polar functional groups was performed with ethyl chloroformate, acetic acid anhydride, and O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine directly in the aqueous samples. Headspace derivatization of compounds containing a secondary alcohol group was performed directly on the stir bar coating in the presence of acetic acid anhydride vapors. The derivatized compounds were thermally desorbed (TD) and analyzed on-line by GC/MS. A number of experimental parameters, including salt addition, temperature and time were optimized to improve the recovery of the derivatized compounds by SBSE. The optimized methods were validated in terms of linearity, precision, and detection and quantitation limits prior to performing the quantification. Trace levels of tuberculostearic acid, a marker of tuberculosis, was detected in sputum samples that were decontaminated and concentrated before being analyzed by SBSE-TD-GC/MS. The method is sufficiently sensitive to detect the marker without the need to culture the organisms, namely M. Tuberculosis. The analysis of 4-hydroxynonenal has also been demonstrated by detecting trace levels of this oxidative stress marker in urine samples obtained from healthy volunteers. Furthermore, abnormally low testosterone/epitestosterone ratios were detected in a group of HIV positive patients by means of SBSE-TD-GC/MS. Further research is required to determine the clinical significance of this finding in the context of HIV infection. Finally, the excessive urinary excretion of estrone and 17β-estradiol following the administration of a high dose of the conjugated equine estrogens to a female volunteer has also been demonstrated.
- ItemSynthesis and radiochemical stability evaluation of radiopharmaceutical compounds containing radioiodinated prosthetic groups(Stellenbosch : Stellenbosch University, 2004-12) Rossouw, Daniel Du Toit; Burger, B. V.; Stellenbosch University. Faculty of Science. Dept. of Chemistry & Polymer Science.ENGLISH ABSTRACT: A study was undertaken to investigate the radiochemical stability of the βiodoethoxyl moiety, a relatively novel prosthetic group employed in radiopharmaceutical chemistry, in which an oxygen atom in a β-position relative to the radioiodine atom has a stabilising effect on the aliphatic carbon-iodine bond. The investigation was started as a pilot study by synthesising various model compounds containing a β-radioiodoethoxyl moiety, as well as two reference compounds lacking such a moiety. The purpose was to determine the influence of various groups in the vicinity of the β-oxygen atom on the stability of the abovementioned moiety. Radiochemical stability tests were carried out in vitro at 37°C in human blood serum. The results confirmed the superior stability of such a moiety compared to that of the reference compounds and also showed that the branching of such an aliphatic unit resulted in a considerable improvement in its stability, especially over a longer period. The investigation was extended to the synthesis of other compounds containing a few selected β-iodoethoxyl moieties that showed improved stability in the pilot study work. Reference compounds containing the classical iodovinyl unit, as well as those lacking a stabilising β- oxygen atom, were also prepared. The carrier molecules used in this part of the work was a benzamide containing a phenolic oxygen atom which acted as the β-oxygen atom, as well as two heterocyclic amines, benzotriazole and 2-methyl-5-nitroimidazole, in which the β- iodoethoxyl moiety was linked to a secondary nitrogen atom. Various suitable alkylating agents were prepared, chemically linked to the carrier molecules, the resulting intermediate compounds converted into tosylate or triflate iodination precursors and labelled with radioiodine by means of iodide-for-tosylate/triflate exchange. In vitro stability tests of these compounds showed similar trends to those obtained with the model compounds. Moreover, the stability of the stabilised β-iodoethoxyl moiety compared favourably with that of the iodovinyl unit, especially when incorporated into a heterocyclic amine. The results of this study have shown that some of the radioiodinated compounds synthesized in this work, especially the nitroimidazole derivatives, have the potential to be considered as novel radiopharmaceuticals.