Thesis(B.Sc.(Hons.))--University of Adelaide, Dept. of Botany. / Typescript.

Selected species of two South African rutaceous genera, Agathosma Willd. and Zanthoxylum L., were phytochemically studied. Two species of the former genus, A. puberula (Steud.) Fourc . and A. elavisepala R. A. Dyer, yielded a novel O-prenylcoumarin, puberul in, the structure of which was fully elucidated as 6,8- dimethoxy-7-prenyloxycoumarin. This represents the first report of a coumarin from that endemic genus. In another study the alkaloids in three species of Zanthoxylum, Z. davyi (Verdoorn) Waterm., Z. thorneroftii (Verdoorn) Waterm. and Z. humile (E .A. Bruce) Waterm . , were investigated. Chelerythrine, nitidine, (-) -α-N-methylcanadine, (+)-laurifoline and (+)-magnoflorine were isolated and characterized in the stem and root bark of Z. davyi, while the root bark of Z. thorneroftii contained skimmianine and decarine in addition to the alkaloids present in Z. davyi. Skimmianine, decarine, N-norchelerythrine, chelerythrine, (-)-α-N-methylcanadinc, candicine and tembetarine were identified in the root bark of Z. humile. The chemotaxonomic significance of these alkaloids occurring in the South African taxa in relation to other African Zanthoxylum taxa, is discussed. Several non-alkaloids (lupeol, β-sitosterol and (-)-sesamin) were also isolated and characterized in Z. davyi and Z. humile. Horizontal cellulose column chromatography and low pressure liquid chromatography have been applied to the separation of quaternary alkaloids

From Introduction: Buchu leaf is a very widely used household medicine in South Africa, and is usually administered in the form of a brandy tincture or a vinegar, known as "buchu brandy" and "buchu vinegar" respectively. These preparations have a great reputation in curing diseases of the kidney and urinary tract, and in addition are employed as local applications to bruises, and for the relief of rheumatic pains. We owe its introduction into medicine to the Hottentot, who gave the name "buchu" or "bookoo" to any aromatic herb or shrub which they found suitable for use as a dusting powder.

No description available.

Chan Lai-Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 83-84). / Abstracts in English and Chinese. / Abstract --- p.i / Acknowledgements --- p.iii / Table of Contents --- p.iv / List of Abbreviations and symbols --- p.viii / List of Appendices --- p.x / List of Figures --- p.xi / List of Tables --- p.xii / Chapter Chapter 1: --- General Introduction --- p.1 / Chapter 1.1 --- Studies of Plant Constituents --- p.1 / Chapter 1.2 --- Extraction of Chemical Ingredients --- p.2 / Chapter 1.3 --- Separation and Purification of Chemical Ingredients --- p.2 / Chapter 1.3.1 --- Thin Layer Chromatography (TLC) --- p.3 / Chapter 1.3.2 --- Open Column Chromatography (OCC) --- p.4 / Chapter 1.4 --- Methods of Structural Identification --- p.4 / Chapter 1.4.1 --- Nuclear Magnetic Resonance (NMR) --- p.5 / Chapter 1.4.1.1 --- Proton NMR Spectroscopy (1H-NMR) --- p.5 / Chapter 1.4.1.2 --- Carbon-13 NMR Spectroscopy (13C NMR) --- p.5 / Chapter 1.4.1.3 --- Distortionless Enhancement by Polarization Transfer (DEPT) Experiment --- p.6 / Chapter 1.4.1.4 --- Two-dimensional Homonuclear Correlation Experiment --- p.6 / Chapter 1.4.1.5 --- Two-dimensional Heternuclear Chemical shift Correlation Experiment --- p.7 / Chapter 1.4.2 --- Mass Spectroscopy --- p.7 / Chapter 1.5 --- Literature Review --- p.8 / Chapter 1.5.1 --- Medical information on the genus Zanthoxylum --- p.8 / Chapter 1.5.2 --- Compounds found in the genus Zanthoxylum --- p.8 / Chapter 1.5.3 --- Compounds found in the Zanthoxylum acanthopodium --- p.9 / Chapter 1.5.4 --- Biological activities of the genus Zanthoxylum --- p.9 / Chapter 1.6 --- Research plan and Objectives of the present study --- p.16 / Chapter 1.7 --- References --- p.17 / Chapter Chapter 2: --- Materials and Methods --- p.20 / Chapter 2.1 --- General experimental procedures --- p.20 / Chapter 2.1.1 --- Solvents --- p.20 / Chapter 2.1.2 --- Chromatographic methods --- p.20 / Chapter 2.1.2.1 --- Normal phase chromatography --- p.20 / Chapter 2.1.2.2 --- Macro-reticular resinous adsorption chromatography --- p.20 / Chapter 2.1.3.3 --- Normal phase preparative thin layer chromatography --- p.21 / Chapter 2.1.3.4 --- Thin layer chromatography --- p.21 / Chapter 2.1.3 --- Determination of physical data --- p.21 / Chapter 2.1.3.1 --- Melting point determination --- p.21 / Chapter 2.1.3.2 --- Optical Rotation (OR) --- p.21 / Chapter 2.1.3.3 --- Ultraviolet (UV) absorption spectra --- p.22 / Chapter 2.1.3.4 --- Infra-red (IR) absorption spectra --- p.22 / Chapter 2.1.3.5 --- Nuclear Magnetic Resonance spectra (NMR) --- p.22 / Chapter 2.1.3.6 --- Mass Spectra (MS) --- p.22 / Chapter Chapter 3: --- Results / Chapter 3.1 --- "Procurement, extraction and initial fractionation of dried leaves and stem bark of Zahthoxylum acanthopodium" --- p.23 / Chapter 3.2 --- Chromatographic separation of the hexane and ethyl acetate extract --- p.24 / Chapter 3.2.1 --- Column chromatographic separation of fraction HEA-E --- p.24 / Chapter 3.2.1.1 --- Characterization of β -sitosterol --- p.24 / Chapter 3.2.2 --- Column chromatographic separation of fraction HEA-F --- p.25 / Chapter 3.2.2.1 --- Characterization of β -amyrin --- p.25 / Chapter 3.2.2.2 --- Characterization of 1 - octacosanol --- p.26 / Chapter 3.2.2.3 --- Characterization of (-)-sesamin --- p.26 / Chapter 3.2.3 --- Column chromatographic separation of fraction HEA-G --- p.27 / Chapter 3.2.3.1 --- Characterization of methyl hexacosanoate --- p.27 / Chapter 3.2.3.2 --- Characterization of methyl pluviatilol --- p.28 / Chapter 3.2.4 --- Column chromatographic separation of fraction HEA-H --- p.28 / Chapter 3.2.4.1 --- Characterization of (+)-methyl piperitol --- p.29 / Chapter 3.2.4.2 --- Characterization of (-)-epieudesmin --- p.29 / Chapter 3.2.5 --- Column chromatographic separation of fraction HEA-K --- p.29 / Chapter 3.2.5.1 --- Characterization of (+)-syringaresinol --- p.30 / Chapter 3.2.6 --- Column chromatographic separation of fraction HEA-M --- p.30 / Chapter 3.2.6.1 --- Characterization of daucosterol 6'-stearate --- p.31 / Chapter 3.2.7 --- Column chromatographic separation of fraction HEA-P --- p.31 / Chapter 3.2.7.1 --- Characterization of β -sitosterol- β -D-glucoside --- p.31 / Chapter 3.3 --- Chromatographic separation of the n-butanol extract --- p.32 / Chapter 3.3.1 --- Column chromatographic separation of fraction Bu-I --- p.32 / Chapter 3.3.1.1 --- Characterization of collettiside III --- p.32 / Chapter 3.3.1.2 --- Characterization of gracilline --- p.33 / Chapter Chapter 4: --- Discussion --- p.35 / Chapter 4.1 --- Isolated compounds --- p.35 / Chapter 4.1.1 --- Sterols --- p.35 / Chapter 4.1.1.1 --- Identification of -sitosterol --- p.36 / Chapter 4.1.1.2 --- Identification of β -sitosterol- β -D-glucoside --- p.41 / Chapter 4.1.1.3 --- Identification of daucosterol 6'-stearate --- p.45 / Chapter 4.1.2 --- Saponins --- p.50 / Chapter 4.1.2.1 --- Steroid glycosides --- p.51 / Chapter 4.1.2.1.1 --- Identification of collettiside III --- p.51 / Chapter 4.1.2.1.2 --- Identification of gracilline --- p.55 / Chapter 4.1.3 --- Terpenoid --- p.60 / Chapter 4.1.3.1 --- Identification of β -amyrin --- p.61 / Chapter 4.1.4 --- Lignans --- p.66 / Chapter 4.1.4.1 --- Identification of (-)-sesamin --- p.68 / Chapter 4.1.4.2 --- Identification of (-)-epieudesmin --- p.69 / Chapter 4.1.4.3 --- Identification of (+)-methyl piperitol --- p.70 / Chapter 4.1.4.4 --- Identification of methyl pluviatilol --- p.71 / Chapter 4.1.4.5 --- Identification of (+)-syringaresinol --- p.72 / Chapter 4.1.5 --- Alkanol --- p.78 / Chapter 4.1.5.1 --- Identification of 1 -octacosanol --- p.78 / Chapter 4.1.5.2 --- Identification of methyl hexacosanoate --- p.79 / Chapter 4.2 --- Conclusion --- p.81 / Chapter 4.3 --- References --- p.83

Thesis (M. Sc.)--University of Hong Kong, 1961. / Accompanied by The triterpenoid constituents of the Hong Kong Ericaceae ([4] p. 24 1/2 cm) by H.R. Arthur [and] S.W. Tam. Melbourne, Commonwealth Scientific & Industrial Research Organization. 1960. In pocket. Reprinted from the Australian Journal of Chemistry. v.13, no. 4. pp. 506-509. Accompanied by Matteucinin (a new flavanoid glycoside) and other constituents of the Ericaceae of Hong Kong ([4] p. 25 1/2 cm.) by H.R. Arthur and S.W. Tam. London, Chemical Society, 1960. Reprinted from the Journal of the Chemical Society, August, 1960. pp. 3197-3200. Typewritten copy. Includes bibliographical references (leaves 90-102).

This thesis concerns a general approach to the total synthesis of yuehchukene 2 and its analogues. Yuehchukene has a potent anti-implantation activity. It also lacks the estrogenic side effect of most compounds with similar biological activity. However, it is somewhat unstable and this could bring some problems when administered to humans. Development of a versatile synthesis of yuehchukene capable of producing a variety of analogous structures in order to fully exploit the pharmacological properties of this novel molecular system and/or to make a more stable product without losing its biological properties was the central objective of this project. Specifically, the total synthesis of yuehchukene 2 and its analogue 6a-ep/-yuehchukene 25 are described. After some preliminary studies, it was found that a kinetic carboxylation (lithium 2,6-di-tert-butyl-4-methylphenoxide, CO₂) of isophorone 26 followed by a reduction (NaBH₄) produced stereoselectively cis-hydroxyacid 46 in good yield. The latter was transformed into indoleacid 48 by dibenzoylation (PhCOCI, DMAP) and treatment with indolylmagnesium iodide. The key intermediate trans-ketone 60 was obtained by treatment of 48 with oxalyl chloride followed by indolylmagnesium iodide. Epimerization of 60 to the more stable cis-ketone 24 was accomplished quantitatively under basic conditions (MeONa/MeOH, reflux). Reduction (LiAlH₄) and dibenzoylation (PhCOCI, DMAP, Et₃N) of 24 furnished the benzoate 68 which was subjected to a nucleophilic substitution with indolylmagnesium iodide to give N-benzoylyuehchukene 69. The latter transformation also gave the interesting compound 75 which was submitted to an X-Ray diffraction analysis. The total synthesis of yuehchukene 2 was then achieved by methanolysis (NaOMe/MeOH) of 69. As far as the synthesis of 6a-epi-yuehchukene 25 is concerned, it was found that, after a thorough study, it was best to transform trans-ketone 60 into its SEM-derivative 85 (SEM-CI,NaH). The latter was reduced (DIBAL) and acetylated (Ac₂O, DMAP, Et₃N) to produce stereoselectively the acetate 87 which, by treatment with indolylmagnesium iodide, furnished SEM-trans-yuehchukene 88. The newly incorporated indole group bears a 1,3-diaxial-like interaction with the β-methyl group at C-7. Unlike 88, tosylacetate 82 gave the compound 84. Finally, the total synthesis of 6a-epi-yuehchukene was accomplished by deprotection of the indole system. Various compounds from this study are now under investigation at WHO and in Hong Kong but, unfortunately, biological results are unavailable at present. [Formula Omitted] / Science, Faculty of / Chemistry, Department of / Graduate

Galipeinae (Galipeeae, Rutoideae) é a subtribo mais diversificada de Rutaceae na região Neotropical. Evidências moleculares recentes sustentam a monofilia do grupo. Embora a delimitação dos gêneros e espécies da subtribo seja baseada principalmente em características florais, existem poucos estudos detalhados sobre a estrutura floral de representantes da subtribo, o que dificulta o uso acurado dos caracteres florais em estudos sobre sistemática e evolução do grupo. Além disso, pouco se sabe sobre as implicações funcionais dessas características na biologia das espécies, sendo necessários mais estudos ecológicos, ainda escassos sobre o grupo. Neste contexto, analisamos comparativamente a estrutura floral de diversos gêneros de Galipeinae e de gêneros americanos proximamente relacionados, apresentando descrições detalhadas e discutindo a implicação dos resultados na sistemática e evolução do grupo. Adicionalmente, investigamos as implicações funcionais de algumas características florais de Galipeinae, por meio do estudo da biologia floral e polinização de três táxons do grupo (Almeidea rubra, Conchocarpus macrophyllus e Angostura bracteata), e com base em dados da literatura e de observações pontuais feitas sobre outras espécies. Como principais resultados das análises estruturais, encontramos diversas características florais que sustentam a monofilia de Galipeinae, excluindo-se uma espécie, Adiscanthus, como a prefloração coclear ascendente ou oblíqua da corola, filetes achatados dorsiventralmente, carpelos com região sincárpica basal curta alcançando menos da metade do comprimento do ovário. Encontramos ainda características florais sustentando o par de gêneros-irmãos Adiscanthus e Hortia, como a conexão posgenital das pétalas apenas na fase de botão, por meio da conexão de células epidérmicas curtas com projeções cuticulares, antera com feixe vascular ramificado no ápice bem como na base, ápice das pétalas inflexo no centro do botão. Outras feições florais reportadas no presente trabalho auxiliam na sustentação de relações filogenéticas recentes no nível genérico ou infragenérico. Em relação ao papel funcional das feições florais de Galipeinae, a sinorganização das peças de diferentes verticilos revelou padrões variados nas espécies aqui estudadas e a arquitetura floral resultante parece refletir diretamente no acesso ao néctar e na polinização. Discutimos essas questões ecológicas ao nível familiar, notadamente em relação a polinizadores nectarívoros de língua e/ou bico relativamente longo, como lepidópteros e aves. Destaca-se ainda a evidência de que a hercogamia seja amplamente distribuída nas Galipeinae, e alguns aspectos funcionais da monossimetria do androceu de algumas espécies são apresentados. Finalmente, os atributos florais analisados em algumas espécies indicam maior especialização floral voltada aos principais grupos de polinizadores, os lepidópteros, notadamente características ligadas ao tubo floral, ao volume e concentração do néctar, ao odor floral e à presença de delicadas plataformas de pouso na flor. Este estudo permitiu identificar diversas hipóteses a serem exploradas em futuros estudos integrativos sobre a estrutura floral, biologia, polinização e evolução em Rutaceae / Galipeinae (Galipeeae, Rutoideae) is the most diversified subtribe of Rutaceae in the Neotropical region. Recent molecular phylogenies support the monophyly of the group. Even though the circumscription of taxa in the subtribe is based mainly on floral traits, there are few detailed studies on the floral structure of the group, preventing an accurate use of floral features in systematic and evolutionary studies. Furthermore, the functional implications of the floral features to the biology of the species in the group still need support from ecological studies, since these are scarce. In this context, we analyzed comparatively the floral structure of several genera of Galipeinae and closely related american genera, presenting detailed descriptions and discussing the relevance of the findings to the systematics and evolution of the group. Additionally we investigated the functional implications of some floral features on an ecological approach, through floral biology and pollination studies of three species of the group (Almeidea rubra, Conchocarpus macrophyllus e Angostura bracteata), as well as based on literature data and field observations on other species. Here we found that floral features strongly support the Galipeinae clade without Adiscanthus, such as cochlear aestivation of petals (either ascending or oblique), filaments dorsiventrally flattened, and a short basal syncarpous zone of carpels, with usually less than half-length of the ovary. The close relationship of Adiscanthus and Hortia, indicated by current molecular phylogenies, is supported by structural features, such as the postgenital connection of petals formed through the interlocking of short epidermal cells and cuticle projections only in bud stage; anthers with the vascular bundle forked towards its apex and base; and petal tips inwardly bent in the centre of the bud. Floral features further support other phylogenetic relationships recently found at the generic or infrageneric levels. Regarding the functional role of floral features, the synorganization of organs of different floral whorls shows several patterns among the studied species, and the resulting floral architecture seems to influence on the nectar access to pollinators. These ecological issues are discussed at the familiar level, notably their relation to long-tongued and/or long-beaked nectarivorous pollinators, such as lepidopterans and birds. Also, we found evidence that herkogamy is a widespread feature in Galipeinae, and the functional role of the androecium monosymmetry is now reported for some species. Finally, floral features indicate in some species floral specialization toward the main groups of pollinators found (lepidopterans), such as nectar volume and concentration, floral tube features, scent and delicate landing platforms. In this study we have also identified a series of hypotheses to be explored in future integrative studies with floral structure, biology, pollination and evolution in Rutaceae

published_or_final_version / Chemistry / Master / Master of Science

Coleonema album is a South African green treasure, endemic to the Cape region and hard to find in other parts of the country. It is ranked among the most highly utilized medicinal plants at present. The plant extracts exhibit a wide range of pharmacological activities due to its bioactive compounds. Immunat, a tincture from this plant is marketed commercially. Medicinal plant gatherers are on the lookout for this plant due to its high demand and market price. Several natural product companies in South Africa are now exporting Coleonema album oil. Its showy beautiful white flowers make it a valuable ornamental plant. There is no accredited germination protocol available for this medicinal and ornamental plant till date. In this study, the chemical and environmental conditions required for optimum seed germination and seedling growth were studied. The effect of light, temperature shifts, cold and warm stratifications, smoke-water, butenolide, pH levels, plant growth regulators (kinetin, 6-benzyladenine, indole acetic acid and α-Naphthalene acetic acid), salt solutions (sodium chloride and ammonium nitrate) on seed germination were investigated. Seeds showed favourable response of germination at low temperatures (10 and 15 ºC). Seeds exposed to continuous darkness at low temperatures showed highest germination at 15 ºC. Temperature shift (from 20 ºC to 15 ºC) favoured seed germination. pH 6 is the most conducive pH level for Coleonema album seed germination (52.5%). Sodium chloride and ammonium nitrate solutions (pretreatment for 2 weeks) significantly improved germination at a 10-2 M concentration with 62.5 and 75% germination respectively. Coleonema album seeds exhibit a temperature-dependent physiological dormancy. Seed germination of this plant is quite erratic as seed germination started 21 days after incubation and lasted for over 90 days. Germination rate of the seeds is too slow to meet the local and international demand for this plant. Plant tissue culture techniques have been used as an alternative for mass cultivation of plants that are difficult to propagate from seeds. Therefore, an effective micropropagation protocol was developed as a measure to conserve this highly utilized medicinal plant. The effects of the cytokinins: BA, kinetin, TDZ and topolins on in vitro shoot formation of Coleonema album were investigated. Of all the cytokinins tested, 5 μM mT gave the highest number of shoots (14.50) per explant. Combination of 5 μM mT with various concentrations of IBA and NAA significantly increased shoot production. Shoots cultured on IBA supplemented medium produced roots. Root production from NAA cultures is unfavourable as most of the shoots developed callus at the base of the stem. The result of this study has shown that mT has potential as a highly active alternative to BA and other cytokinins for Coleonema album in vitro shoot production. Over 1,000,000 plantlets could be produced annually using the in vitro propagation protocol developed in this study. The results of this study will be useful as a guide for mass cultivation of this ornamental and medicinal plant. It will also provide an opportunity for propagation of Coleonema album in other parts of the country. By virtue of this, the pressure on the wild population of this species could be greatly reduced. / Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2012.