Bioassay Directed Chemical Study of Antimalarial Substances from Clerodendrum myricoides and Dodonaea angustifolia and Comparative Chemical Studies of Moringa stenopetala and Moringa oleifera

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2015-06

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Addis Ababa Universty

Abstract

Human beings have since time immemorial used plants for different purposes including as food, for flavor, cosmetic, dying clothes, and above all as medicine for treating a wide spectrum of diseases. The main aim of this dissertation work is to find rationale for the use of selected plants in combating one of the most challenging diseases in the world, namely, malaria. The selection of the plant materials for the study was based on ethnomedicinal uses. This led to the need for systematic investigation of two plants, Clerodendrum myricoides (Lamiaceae) and Dodonaea angustifolia (Sapindaceae), which are indigenous medicinal plants traditionally used as remedies against malaria in some parts of Ethiopia. In the course of this study, bioassay guided investigation on the antiplasmodial activities of the leaves of C. myricoides resulted in the isolation of two active compounds, namely, α-spinasterol (63) and sitosterol-3-O-β-D-glucoside (64), which significantly suppress parasitaemia by 51% and 44% at 40 mg/kg, respectively. Furthermore, the acetone extract of the leaves of C. myricoides afforded verbascoside (12), ixoroside (73), and compound 71. To our knowledge there is no report in the literature for compound 71. Tetracosanoic, behenic, icosanoic, stearic, and palmitic acid were also identified from the leaves of this plant. Investigation of the radical scavenging activities of the above constituents resulted in verbascoside as the most active compound comparable to ascorbic acid. Bioassay guided fractionation of the ethyl acetate soluble portion of the 80% aqueous MeOH extract of the leaves of D. angustifolia afforded three compounds, namely, pinocembrin (86), santin (81) and 15,16-epoxy-2-hydroxy-3,13(16),14-clerodtriene-18-oic acid (128) which exhibited high percent suppression of parasitaemia by 81% at 40 mg/kg, 80% at 50 mg/kg and 70% at 40 mg/kg, respectively. Under similar conditions chloroquine suppressed parasitaemia by 100% at 25 mg/kg. Column chromatographic fractionation of the ethyl acetate soluble portion of the ethanol extract of D. angustifolia leaves gave three other compounds in addition to 81, 86 and 128, identified as 5,7,4’-trihydroxy-3,6-dimethoxyflavone (80), ent-16-hydroxy-labdan-3α,8β- dihydroxy,13(14)-en-15,16-olide (114), and 5,6,7-trihydroxy-3,4’-dimethoxyflavone (125). To our knowledge compound 125 has not been reported before as a natural product. The extracts and the four flavonoids isolated from the leaves of D. angustifolia were tested for their antiradical properties, which led to 5,7,4’-trihydroxy-3,6-dimethoxyflavone (80) as the most active compound. The leaves of two Moringa species, M. stenopetala which is confined to the horn of Africa namely Ethiopia, Somalia and Kenya and M. oleifera originally from the Indian subcontinent but now cultivated in different parts of the world including Africa, were compared with respect to their main chemical constituents. Different techniques including TLC, HPLC-MS, and UV-Vis spectrophotometry were employed. Our results unambiguously showed significant differences in the chemical profiles of the leaves of the two species. Rutin (163) is the only principal flavonoid glycoside of the leaves of M. stenopetala, which however is not detected in the leaves of M. oleifera. On the other hand M. oleifera contains significant amounts of two other glycosides, namely, quercetin-3-O-β-D-glucoside (159) and kaempferol-3-O-β-D-glucoside (161). These results are significant in distinguishing the two Moringa species. Furthermore, a simple high performance thin layer chromatographic method was developed and validated for quantitative analysis of rutin in the leaves of M. stenopetala. The level of rutin in the leaves of M. stenopetala was found to be 1.9±0.08%. These fingerprinting results can be used not only to differentiate the two species but also to establish presence or absence of adulterants, an issue that is significant in the use and marketing of crude and derived products from Moringa leaves Further chemical investigation on the leaves of M. stenopetala afforded three compounds identified as heptacosanol (185), sitosterol-3-O-β-D-glucoside (64), and inositol dimer (186). The seed kernel and husk of M. stenopetala was also investigated in this study for the first time. This resulted in the isolation and characterization of stearic acid (77), 4-(α-L-rhamnopyranosyloxy) benzyl glucosinolate (164) and sucrose (187) from the seed kernel while the husk furnished allantoin (191) and compound 190. To our knowledge compound 190 was not reported before as natural product. GC-MS analysis of the fatty acids of the oil of M. stenopetala afforded oleic acid (52%), stearic acid (9%), palmitic acid (9%), behenic acid (5%), archidic acid (5%), palmitoleic acid (1%) and myristic acid (0.2%). The above flavonoid glycosides displayed pronounced radical scavenging and anti-lipid peroxidation activities. Key words: Bioassay, Clerodendrum myricoides, Dodonaea angustifolia, Sapindaceae, Lamiaceae, Antiplasmodial, radical scavenging, pinocembrin, santin, verbascoside, Moringaceae, Fingerprint, HPLC-MS, TLC, UV, Moringa stenopetala, Moringa oleifera, quality control, radical scavenging

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Keywords

Bioassay, Clerodendrum myricoides, Dodonaea angustifolia, Sapindaceae, Lamiaceae, Antiplasmodial, Radical scavenging, Pinocembrin, Santin, verbascoside, Moringaceae

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