Orientador: Rosangela da Silva de Laurentiz / Banca: Jean Richard Dasnoy Marinho / Banca: Lizandra Guidi Magalhães / Resumo: Devido à importância do bioma cerrado, inclusive para a manutenção de outros biomas interligados, nas últimas décadas pesquisadores das mais variadas áreas vêm propondo alternativas de uso das espécies do cerrado como forma de preservar a fauna e flora local. Uma das formas para auxiliar na preservação dessas espécies esta o estudo sobre constituintes fitoquímicos e propriedades medicinais de plantas desse bioma usadas na medicina tradicional. O objetivo desse estudo é a confirmação do potencial terapêutico bem como da toxicidade dessas plantas usadas na medicina tradicional local, bem como estudar o potencial medicinal de plantas ainda não investigadas. A espécie Dipteryx alata Vogel (baru) é uma das espécies nativas do cerrado que apresenta grande potencial nutricional e farmacológico a ser investigado, pois segundo a medicina tradicional ela é utilizada no combate à bronquite, diarreia, disenteria, dor, dor de garganta, gripe, picada de cobra, tosse e como cicatrizante, entretanto, apenas a atividade contra picada de cobra foi cientificamente comprovada. Desta forma, na tentativa de aliar o valor nutricional da polpa dos frutos do baru a um possível efeito terapêutico, foram realizados estudos sobre os fitoconstituintes presentes nesta parte da planta, a fim de guiar estudos sobre as possíveis propriedades biológicas valorizando o fruto como um alimento nutracêutico, em áreas de ocorrência da planta que apresentam elevados índices de doenças negligenciadas. Os resultados dos estudos fitoquímicos mostraram a presença de alcaloides, taninos, flavonoides, glicosídeos cardiotônicos e saponinas em consideráveis concentrações e antraquinonas em baixa concentração. A presença desses fitoconstituintes forneceu suporte para a realização de ensaios para a determinação do potencial antiparasitário. A atividade antimicrobiana também foi avaliada devido ao uso medicinal da planta para infecções do trato ... / Abstract: Due to the importance of the cerrado biome, including the maintenance of other interconnected biomes in recent decade's researchers from different fields have proposed alternative use of the cerrado species as a way to preserve the local fauna and flora. One way to help the preservation of species is the study of the medicinal properties of plants of this biome used in traditional medicine. The objective of these studies is to confirm the therapeutic potential and the toxicity of these plants used in traditional local medicine as well as studying the medicinal potential of plants yet to be investigated. The specie Dipteryx alata Vogel (baru) is a native species of the cerrado with great nutritional and pharmacological potential to be investigated, because according to traditional medicine it is used to combat bronchitis, diarrhea, dysentery, pain, sore throat, flu, snakebite, cough and as cicatrizant, however, only the activity against snakebite has been scientifically proven. Therefore, trying to combine the nutritional value of baru fruits pulp to the potential therapeutic effect, studies on the determination of phytochemicals present were performed to guide studies on possible biological properties valuing the fruit as a nutraceutical food in areas of occurrence of the plant that show high negligible diseases indices. The results of the phytochemical studies showed the presence of alkaloids, tannins, flavonoids, saponins and cardiotonic glycosides in considerable amounts and anthraquinones at low concentration. The presence of these phytochemicals has given support for conducting tests to determine the antiparasitic potential. Antimicrobial activity was also evaluated due to the medicinal use of the plant for the urinary tract infections. In addition, the cytotoxicity of the pulp was also evaluated on LLC- MK 2 cells to support the safe use of the fruit. Antimicrobial assays were performed using the bacterial strains Proteus sp., E. ... / Mestre

Orientador: Wagner Vilegas / Coorientador: Marcelo Aparecido da Silva / Banca: Marcos José Salvador / Banca: Claudia Quintino da Rocha / Banca: Camilo Dias Seabra Pereira / Banca: Douglas Gatte-Picchi / Resumo: Mimosa é um dos maiores gêneros da família Fabaceae e subfamília Mimosaceae, são fontes de alcaloides, ácidos fenólicos, terpenoides, carotenoides e principalmente flavonoides. Apesar da maioria das espécies serem encontradas na Caatinga e Cerrado, principalmente na região nordeste do Brasil, ainda são poucos os estudos químicos e biológicos sobre essas plantas. Por isso, neste trabalho contribuímos no conhecimento a respeito dessa família, investigando as folhas de Mimosa caesalpiniifolia, indicada contra doenças inflamatórias, antimicrobianas e infecções. O extrato foi preparado por percolação com etanol 70% com rendimento em massa de 25%. Em seguida, foi fracionado usando técnicas cromatográficas convencionais. As estruturas foram identificadas por análises espectroscópicas (UPLC-MS; ESI-IT-MSn e RMN de 1H e de 13C). A investigação química levou à identificação de vinte e sete substâncias sendo três flavonoides descritos pela primeira vez na literatura. Na quantificação dos marcadores químicos, em 100,0 mg do extrato hidroalcoólico de Mimosa (EHM), há 0,82 mg de galato de etila (1) e 0,44 mg de cassiaoccidentalina A (21). No ensaio de genotoxicidade, o EHM nas doses de 62,5 e 125 mg/Kg e na fração acetato de etila (Fr-EtOAc) na dose de 62,5 mg/Kg não apresentaram efeitos tóxicos. Os resultados demonstraram que o EHM foi capaz de prevenir lesões oxidativas do DNA nas células do fígado induzidas pelo peróxido de hidrogénio in vitro e diminuição de danos genômicos foi detectada em células de fígado após a exposição à Fr-EtOAc. No ensaio de colite o EHM na dose de 125 mg/Kg apresentou efeito preventivo e a Fr-EtOAc na dose de 50 mg/Kg efeito terapêutico com redução na intensidade das lesões. No ensaio de edema de orelha... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Mimosa is family Fabaceae and subfamily Mimosaceae, are sources of alkaloids, phenolic acids, terpenoids, carotenoids and flavonoids mainly. Although most species are found in Caatinga and Cerrado, especially in northeastern Brazil, there are few chemical and biological studies on these plants. Therefore, this work contribute knowledge about this family, investigating the leaves of Mimosa caesalpiniifolia indicated against inflammatory, antimicrobial and infections. The extracts were prepared by percolation with 70% ethanol to yield 25% mass. Then they were fractionated using conventional chromatographic techniques. The structures were identified by spectroscopic analysis (UPLC-MS, ESI-IT-MSn and 1H NMR and 13C). The chemical research led to the identification of twenty-seven substances with three flavonoids first described in the literature. In quantification of chemical markers in 100.0 mg of the hydroalcoholic extract of Mimosa (EHM), there are 0.82 mg of ethyl gallate (1) and 0.44 mg cassiaoccidentalina A (21). In the genotoxicity test, the EHM at doses of 62.5 and 125 mg/kg and the ethyl acetate fraction (Fr-EtOAc) at a dose of 62.5 mg/kg showed no toxic effects. The results showed that the EHM was able to prevent oxidative DNA damage in liver cells induced by hydrogen peroxide in vitro and decreased DNA damage was detected in liver cells following exposure to Fr-EtOAc. In the EHM colitis test in a dose of 125 mg/kg showed a preventive effect and Fr-EtOAc 50 mg / kg therapeutic effect with a reduction in the intensity of the lesions. In the test ear edema induced by the EHM xylene (125 and 250 mg/kg) significantly inhibited 52% and 64%, respectively, and exhibited 82% antidiarrheal activity induced by castor oil. In the antifungal assay FR-EtOAc showed... (Complete abstract click electronic access below) / Doutor

Studies were undertaken to identify the basis of differences in seed coat pigmentation between selected yellow- and brown-seeded Brassicaceae, and near-isogenic yellow- and brown-seeded lines of </i>Brassica carinata</i> (PGRC/E 21164). Histochemical analyses of dissected seed coats from six genera of the Brassicaceae revealed condensed tannin (proanthocyanidin) and phlobaphene pigments in dark-seeded species and in scattered spots in most yellow-seeded species. Anthoeyanins were not detected in any seed coat tissue of these species. In leaf tissue, anthocyanin content was lower in yellow-seeded 'B. carinata' at the three- to four-leaf stage grown at 20 to 25°C, compared to similarly grown brown-seeded plants. At 15 to 18°C, both yellow- and brown-seeded lines produced similar amounts of anthocyanin in the seedling leaves. In TLC and HPLC analyses, 't'-cinnamic acid, dihydromyricetin [trace amounts], dihydroquercetin, dihydrokaempferol and flavonols (quercetin, kaempferol) were more abundant in extracts from seed coats of yellow-seeded ' B. carinata' than in extracts from seed coats of brown-seeded ' B. carinata'. Myricetin was not detected in any seed coat extracts. Mass spectra were determined for phenylpropanoid and flavonoid aglycones from the seed coat extracts and for authentic standards. Dihydroflavanol reductase ('DFR') transcripts from developing seed were absent or less abundant at 5, 10, 20 and 30 days after pollination in the yellow-seeded line compared to the brown-seeded line of 'B. carinata'. 'DFR' transcripts in seedling leaves from the yellow-seeded line grown in warm, bright conditions were less abundant compared to similarly grown brown-seeded material. Seedlings grown at 15 to 18°C produced greater amounts of 'DFR' transcript in both yellow- and brown-seeded lines of 'B. carinata' compared to warm-grown plants. Data from these experiments suggest that seed coat pigmentation in the Brassicaceae is due to condensed tannin and phlobaphene accumulation, not anthocyanins, and that seed coat pigment biosynthesis is down-regulated at dihydroflavonol reductase. The regulatory factor controlling 'DFR' expression in developing seed may be temperature sensitive and also affect anthocyanin biosynthesis in seedlings and in related metabolic pathways: thioglycolic lignin concentration was significantly lower in the yellow-seeded Brassicaccae and in the seed coat tissue of yellow-seeded 'B. carinata' compared to dark-seeded samples.

published_or_final_version / Medical Sciences / Master / Master of Medical Sciences

The Hyacinthaceae family is richly represented in southern Africa. Of the five subfamilies, three are found in southern Africa. These are the Urgineoideae (URG), Ornithogaloideae (ORN) and the Hyacinthoideae (HYA). The overview of Pfosser and Speta (1999), revealed chemotaxonomic trends at a subfamily level for the Hyacinthaceae family of the Flora of southern Africa region. Homoisoflavanones were found to define the Hyacinthoideae subfamily whilst the Ornithogaloideae subfamily and the Urgineoideae subfamily are defined by steroidal compounds namely, cholestane glycosides and bufadienolide glycosides respectively. Representatives of all three subfamilies were investigated phytochemically. From Eucomis comosa (HYA), five homoisoflavanones were isolated. Omithogalum tenuifolium (ORN) contained a spirostanol saponin of which the crystals were amenable to X-ray analysis. Evidence of a novel stereoisomer was obtained. Extraction of the bulbs of Galtonia princeps (ORN) led to the isolation of two cholestane glycosides, one known and one novel, and a homoisoflavanone. Two novel bufadienolides were isolated from Urginea Iydenburgensis (URG). Structures were elucidated on the basis of spectroscopic data and chemical evidences. Homoisoflavanones and related compounds were then screened for antibacterial and anti-inflammatory activity. Several compounds showed antibacterial activity against Staphylococcus aureus, a gram-positive bacteria. Inhibition of the inflammatory process in microsomal cells was first evaluated, followed by screening of specific inhibition of cyclooxygenase enzymes. These are membrane-associated enzymes occurring in different isoforms. High levels of anti-inflammatory activity were detected especially in microsomal cells. This biological information made it possible to rationalize the ethnomedicinal use of some of the plants from which the compounds were isolated. 15 Biological screening was followed by a computer-based quantitative structureactivity relationship (QSAR) study. This study produced five equations with significant prediction value of anti-inflammatory and antibacterial activity for homoisoflavanones and related compounds. The derived models also provided valuable parameter guidelines of those properties influencing the antiinflammatory and antimicrobial activity of the studied compounds. / Thesis (Ph.D.)-University of KwaZulu-Natal, Durban, 2004.

This work describes the isolation and structural elucidation of extractives from four species of the Meliaceae and one of the Simaroubaceae families. All five species examined are endemic to the island of Madagascar. One novel seco-ring A protolimonoid with a bourjotinolone A-type side-chain was isolated from Turraea sericea, while Malleastrum antsingyense yielded one known and one novel limonoid of the vilasinin group. Neobeguea leandreana was found to contain three novel limonoids of the phragmalin class, including a relatively rare 17-keto seco-ring D compound and one containing a oxidized C-19 methyl group. Quivisia papinae has afforded eight novel and five known protolimonoids and limonoids of the azadiradione, evodulone, and mexicanolide classes. Included among these are a mexicanolide group limonoid with a 17-keto seco-ring D, and two further mexicanolide limonoids containing a hitherto unreported 9a,11a-epoxide ring and a Δ 9(11)-double bond. One C19 and four C20 quassinoids, of which one is novel, together with a known but rare triterpenoid, were isolated from the Madagascan Simaroubaceae Samadera madagascariensis. These findings support the suggestion that this species is closely related to, if not synonymous with, the companion species Samadera indica and Quassia indica. A literature survey on the effect of structural variations in ring B on coupling constants in 11,12-disubstituted havanensin-group limonoids was also undertaken, resulting in the observation of a remarkable correlation between ring structure and coupling constant values for a wide range of compounds isolated from different sources. An explanation for these observations is advanced. / Thesis (Ph.D.)-University of Natal, Durban, 2001.

This work is an account of investigations into the chemistry of members of the Amaryllidaceae and Hyacinthaceae families. The plants of the family Amaryllidaceae are a large group comprising over sixty genera and more than a thousand species. They are widely distributed, but are found more richly in the tropics, with a particularly high density in South Africa, with smaller centers of diversity in Andean South America and the Mediterranean. Amaryllidaceae plants have been extensively used by local traditional healers and have been reported to have numerous pharmacological uses. The alkaloids isolated from this family are a group of isoquinoline alkaloids found exclusively in this family. Plants belonging to two Amaryllidaceae genera were investigated phytochemically, one from each of the sub-tribes Crinineae and Amaryllidineae were investigated phytochemically. Brunsvigia natalensis is used in local traditional medicine to "straighten bones of children", treat barrenness in women and ease childbirth. This is the first phytochemical investigation of Brunsvigia natalensis, and yielded two new alkaloids, a new ceramide type compound and a known flavanoid. A comparative phytochemical investigation was carried out on the bulbs and seeds of Crinum stuhlmanni, which resulted in a number of different alkaloids being isolated from the seeds and bulbs of this plant. The southern African Hyacinthaceae is a large and chemically morphologically diverse group of plants. This family comprises approximately sixty-seven genera and nine hundred species worldwide, of which twenty-seven genera and three hundred and sixty - eight species are found locally. There are five sub-families of which three occur in southern Africa. The chemical constituents of this family can be divided into four classes, namely homoisoflavanones, steroidal compounds, bufadienolides and miscellaneous compounds. These plants are used in local traditional medicine for treating ailments such as hangovers, rheumatic fever, sprains and even cancer. The phytochemistry of three Hyacinthaceae plants was studied. The phytochemical investigation of Drimia macrocentra and Urginea riparia yielded a novel bufadienolide glycoside. These glycosides are quite unusual with the glycone attached to the aglycone at C-2 and C-3 and this has only been reported only once before in this family. The phytochemical investigation of Ledebouria revoluta yielded a number of homoisoflavanones. These homoisoflavanones have been shown to have anti-inflammatory activity and all of the compounds isolated in this work have been screened for this activity. Structural elucidation was carried out using spectroscopic methods such as NMR, MS, UV and IR. / Thesis (Ph.D.)-University of KwaZulu-Natal, Durban, 2004.

The relationship between extractable invertase activities and sucrose accumulation in the sugarcane (Saccharum spp. hybrids) culm and in vivo invertase mediated sucrose hydrolysis was investigated to determine the significance of invertases in sucrose utilisation and turnover. In vitro activities were determined by assaying the soluble acid invertase (SAI), cell wall bound acid invertase (CWA) and neutral invertase (NI) from internodes three to ten in mature sugarcane plants of cultivar NCo376. Extractable activities were verified by immunoblotting. In vivo invertase mediated sucrose hydrolysis was investigated in tissue discs prepared from mature culm tissue of the same cultivar. Sugarcane NI had a higher specific activity than SAI (apoplastic and vacuolar) in the sucrose accumulating region of the sugarcane culm. CWA was also present in significant quantities in both immature and mature tissue. Sugarcane NI was partially purified from mature sugarcane culm tissue to remove any potential competing activity. The enzyme is non-glycosylated and exhibits catalytic activity as a monomer, dimer and tetramer. Most of the activity elutes as a monomer of native Mr ca 60 kDa. The enzyme displays typical hyperbolic saturation kinetics for sucrose hydrolysis. It has a Km of 9.8 mM for sucrose and a pH optimum of 7.2. An Arrhenius plot shows the energy of activation of the enzyme for sucrose to be 62.5 kJ.mol-1 below 30°C and -11.6 kJ.mol-1 above 30°C. Sugarcane NI is inhibited by its products, with fructose being a more effective inhibitor than glucose. Sugarcane NI is significantly inhibited by HgCI2, AgNO-3, ZnCI2, CuSO4 and CoCI2 but not by CaCI2, MgCI2 or MnCI2. Sugarcane NI showed no significant hydrolysis of cellobiose or trehalose. When radiolabelled fructose was fed to sugarcane internodal tissue, label appeared in glucose which demonstrates that invertase mediated hydrolysis of sucrose occurs. A combination of continuous feeding and pulse chase experiments was used to investigate the in vivo contribution of the invertases and the compartmentation of sugars. Sucrose is synthesised at a rate greater than the rate of breakdown at all stages of maturity in sugarcane culm tissue. The turnover time of the total cytosolic label pool is longer for internode three than internode six. A higher vacuolar:cytosolic sugar molar ratio than previously assumed is indicated. Developmentally, the greatest change in carbon allocation occurs from internodes three to six. The main competing pools are the insoluble and neutral fractions. As the tissue matures, less carbon is allocated to the insoluble and more to the neutral fraction. The neutral fraction consists mainly of sucrose, glucose and fructose. The compartmented nature of sugarcane storage parenchyma carbohydrate metabolism results in a system that is complex and difficult to investigate. A computer based metabolic flux model was developed to aid in the interpretation of timecourse labelling studies. A significant obstacle was the global optimization of the model, while maintaining physiologically meaningful flux parameters. Once the vacuolar:cytosolic molar ratio was increased, the model was able to describe the internode three and six labelling profiles. The model results were in agreement with experimental observation. An increase in the rate of sucrose accumulation was observed with tissue maturation. Only the internode three glucokinase activity was greater than the experimentally determined limit. The rate was however physiologically feasible and may reflect the underestimation of the in vivo rate. SAI and NI contributed to sucrose hydrolysis in internode three but not in internode six. The rates in internode six were set to fixed low values to enable the model to fit the experimental data. This does not however preclude low levels of in vivo SAI and NI activity, which would prove significant over a longer time period. The flow of label through the individual pools, which comprise the experimentally measured composite pools could be observed. This provides insight into the sucrose moiety label ratio, SPS:SuSy sucrose synthesis ratio, and the rate of 14CO2 release. The model provides a framework for the investigation and interpretation of timecourse labelling studies of sugarcane storage parenchyma. / Thesis (Ph.D.)-University of Natal, Durban, 2000.

Part A of this thesis is an account of the extractives isolated from one member of the Melianthaceae and two members of the Meliaceae. Plants belonging to these families are known to produce compounds with medicinal applications. Crude extracts from these plants are known to be widely used in traditional medicine. Structural elucidation was facilitated by the use of infrared, mass and nuclear magnetic resonance spectroscopic techniques. Three 20(29)-lupene type compounds (two known and one knew) were isolated from the bark of Bersama swinnyi (Melianthaceae); oleanolic acid was isolated from the leaves. The Meliaceae family is only represented b~ one species, Dysoxylum spectabile, in New Zealand. Two diterpenoids and two limonoids were isolated from the bark. The extracts of the rootbark and stembark of the hitherto uninvestigated species Turraea holstii (Gurke), supplied by Professor H. S. Rajab, Moi University, Kenya, were examined. Eight limonoids and a protolimonoid were isolated from the rootbark. A limonoid and a protolimonoid were isolated from the stembark. Some of the compounds isolated were found in both extracts. Four of the eight limonoids isolated were of the neotrichilenone type. The spectra for the compounds discussed in this text are presented in a separate book. / Thesis (Ph.D.)-University of Natal, 1997.

<p>Since Helichrysum is known by the indigenous people of Africa for therapeutic properties, such as against colds, flu and wounds, the aim of this study was to focus on the patulum species found predominantly in the Western Cape region of South Africa and by means of isolation and identification of the plant constituents, be able to relate the therapeutic activity on the basis of literature precedents, to the compounds extracted.</p>