thành phần hóa học của cây lá xuân hoa mạng pseuderanthemum reticulatum radlk họ ô rô (acanthaceae)

ĐẠI HỌC QUỐC GIA THÀNH PHỐ HỒ CHÍ MINH ĐẠI HỌC KHOA HỌC TỰ NHIÊN  NGUYỄN PHI LINH THÀNH PHẦN HÓA HỌC CỦA LÁ CÂY XUÂN HOA MẠNG Pseuderanthemum reticulatum Radlk. HỌ Ô RÔ (Acanthaceae) LUẬN VĂN THẠC SĨ KHOA HỌC HÓA HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC GS. TS. NGUYỄN KIM PHI PHỤNG Tp. Hồ Chí Minh, 2011 iv TABLE OF CONTENTS ABSTRACT i ACKNOWLEDGEMENTS iii TABLE OF CONTENTS iv LIST OF ABBREVIATIONS vi LIST OF TABLES viii LIST OF FIGURES AND SCHEMES ix Chapter 1: LITERATURE REVIEW & AIM OF STUDY 1 1.1. General information of Pseuderanthemum 1 1.1.1. Generic description 1 1.1.1.1. P. acuminatissimum (Miq.) Kuntze. 1 1.1.1.2. P. bracteatum Imlay. 4 1.1.1.3. P. carruthersii 4 1.1.1.3.1. P. carruthersii (Seem.) Guill. var. atropurpureum (Bull.) Fosb. 4 1.1.1.3.2. P. carruthersii var. ovatifolium (Brem.) Brem. 4 1.1.1.4. P. palatiferum (Nees) Radlk. 4 1.1.1.5. P. reticulatum Radlk. 5 1.1.2. Pharmaceutical studies of Pseuderanthemum 5 1.1.2.1. In vitro assays 5 1.1.2.2. In vivo assays 6 1.1.3. Chemical studies of Pseuderanthemum 7 1.1.3.1. Eranthemum pulchellum 7 1.1.3.2. P. carruthersii atropurpureum 7 1.1.3.3. P. latifolim 8 1.1.3.4. P. palatiferum 8 1.2. Aim of study 11 v Chapter 2: EXPERIMENTAL 12 2.1. Materials 12 2.2. Plant material 12 2.3. Extraction and isolation procedures 12 2.4. Analysis of fatty acid of two glycoglycerolipids 13 Chapter 3: RESULTS & DISCUSSION 16 3.1. Structure elucidation of compound RE-EA1 16 3.2. Structure elucidation of compound RE-EA3 16 3.3. Structure elucidation of compound RE-EA4 17 3.4. Structure elucidation of compound RE-EA6 18 3.5. Structure elucidation of two diastereomers RE-EA7 and RE-EA8, which were isolated from RE-EA2 20 3.5.1. Structure elucidation of compound RE-EA7 21 3.5.2. Structure elucidation of compound RE-EA8 23 3.6. Structure elucidation of compound RE-Bu2 24 3.7. Structure elucidation of compound RE-Bu3 28 3.8. Structure elucidation of compound RE-Bu4 30 3.9. Structure elucidation of compound RE-PE1 34 3.10. Structure elucidation of compound RE-PE2 35 Chapter 4: CONCLUSION 40 LIST OF PUBLICATIONS 42 REFERENCES 43 APPENDICES vi LIST OF ABBREVIATIONS 1D/2D-NMR : One/Two Dimensional – Nuclear Magnetic Resonance AchE : Acetylcholinesterase ALT : Alanine aminotransferase AST : Aspartate aminotransferase brd : Broad doublet brs : Broad singlet brt : Broad triplet Bu : n-Butanol COSY : Correlated spectroscopy d : Doublet dd : Doublet of doublet DMSO : Dimethyl sulfoxide DEPT : Distortionless Enhancement by Polarization Transfer. EA : Ethyl acetate HIV : Human Immunodeficiency Virus HSQC : Heteronuclear Single Quantum Correlation. HMBC : Heteronuclear Multiple Bond Coherence. HPLC : High Performance Liquid Chromatography HR-ESI-MS : High Resolution - Electrospray Ionization - Mass Spectrometry J : Coupling constant GC-MS : Gas Chromatography - Mass Spectrometry LC : Liquid Chromatography m : Multiplet vii m/z : Mass to charge ratio MDA : Malondialdehyde Me : Methyl NMR : Nuclear Magnetic Resonance PE : Petroleum ether ppm : Part per million R f : Retardation factors s : Singlet TLC : Thin-Layer Chromatography t : Triplet UV : Ultraviolet [α] D : Specific rotation o C : Degree Celcius viii LIST OF TABLES Table 1: The content of some major and trace minerals in the leaves of P. palatiferum 8 Table 2: The NMR data of RE-EA1 and comparison of its ones with those of tyrosol 17 Table 3: The NMR data of RE-EA3 and comparison of its ones with those of uracil 18 Table 4: The NMR data of RE-EA4 and comparison of its ones with those of stigmasterol, β -sitosterol and β-D-glucopyranose 20 Table 5: The NMR data of RE-EA6 22 Table 6: The NMR data of RE-EA8 and RE-EA7 and comparison of their ones with those of (6S,9S)-vomifoliol 24 Table 7: The comparison of 13 C-NMR data of RE-EA7, RE-EA8 and the aglycon of RE-EA6 with those of the aglycons of four roseoside diastereomers 26 Table 8: The NMR data of RE-Bu2 and comparison of its ones with those of salidroside 28 Table 9: The NMR data of RE-Bu3 and comparison of its ones with those of uridine 29 Table 10: The NMR data of RE-Bu4 and comparison of its ones with those of apigenin 7-O-β-D-rutinoside 33 Table 11: The NMR data of RE-PE1 and comparison of its ones with those of 1-linolenoyl-2-palmitoyl-3-galactosylglycerol 36 Table 12: The NMR data of RE-PE2 39 ix LIST OF FIGURES AND SCHEMES Figure 1: Xuân Hoa Nhọn, P. acuminatissimum (Miq.) Kuntze 2 Figure 2: Xuân hoa lá-hoa, P. bracteatum Imlay. 2 Figure 3: Xuân hoa đỏ, P. carruthersii (Seem.) Guill. var. atropurpureum (Bull.) Fosb. 2 Figure 4: Nấp vũm, P. carruthersii var. ovatifolium (Brem) Brem. 2 Figure 5: P. crenulatum (Lindl.) R. Ben. 2 Figure 6: P. eberhardtii R. Ben. 2 Figure 7: Xuân hoa, P. palatiferum (Nees) Radlk. 2 Figure 8: P. poilanei R. Ben.Z 2 Figure 9: Xuân hoa mạng, P. reticulatum Radlk. 3 Figure 10: P. tonkinense R. Ben. 3 Figure 11: Eranthemum pulchellum 3 Figure 12: P. alatum 3 Figure 13: P. laxiflorum 3 Figure 14: P. sinuatum. 3 Figure 15: P. tuberculatum (Hook. f.) Radlk 3 Figure 16: P. variabile 3 Figure 17: The HMBC correlations of RE-EA6 19 Figure 18: The HMBC correlations of Re-Bu3 27 Figure 19: The HMBC correlations of RE-Bu4 30 Figure 20: The HMBC correlations of RE-PE1 35 Figure 21: The HMBC correlations of RE-PE2 37 Scheme 1: Extraction procedure of Pseuderanthemum reticulatum Radlk. leaves 14 Scheme 2: Isolation procedure of compounds from the PE residue of scheme 1 14 x Scheme 3: Isolation procedure of compounds from the EA residue of scheme 1 15 Scheme 4: Isolation procedure of compounds from the Bu residue of scheme 1 15 Pseuderanthemum reticulatum Radlk. Literature review & Aim of study 1 Chapter 1 LITERATURE REVIEW & AIM OF STUDY 1.1. General information of Pseuderanthemum Pseuderanthemum or Eranthemum [1] is a member of Acanthaceae. The genus contains about 196 species, including perennial shurbs or herbs. The characteristics of the genus are beautiful flowers and foliage, high humidity need, flowering in spring and summer. In Vietnam, Pseuderanthemum has nine species and two varieties [1] including P. acuminatissimum (Miq.) Kuntze. (figure 1), P. bracteatum Imlay. (figure 2), P. carruthersii (Seem.) Guill. var. atropurpureum (Bull.) Fosb. (figure 3), P. carruthersii var. ovatifolium (Brem.) (figure 4), P. crenulatum (Lindl.) R. Ben (figure 5), P. eberhardtii R. Ben (figure 6), P. palatiferum (Nees) Radlk (figure 7), P. poilanei R. Ben.Z (figure 8), P. reticulatum Radlk (figure 9) and P. tonkinense R. Ben (figure 10). In addition, we collected pictures of some species of Pseuderanthemum from internet such as Eranthemum pulchellum (figure 11) [32] , P. alatum (figure 12) [33] , P. laxiflorum (figure 13) [34] , P. sinuatum (figure 14) [35] , P. tuberculatum (Hook. f.) Radlk (hình 15) [36] and P. variabile (figure 16). [37] 1.1.1. Generic description In this section, the botanic morphology of some Vietnamese Pseuderanthemum species was described. 1.1.1.1. P. acuminatissimum (Miq.) Kuntze. [1],[2] Vietnamese name: Xuân hoa nhọn (figure 1). Perennial shrub. Stems terete in older positions, glabrous and tetragonal in younger positions. Leaves 10-20 cm long, 5-9 cm wide; costa and lateral veins 6 pairs, petioles 4-5 cm long; peduncle 20 cm long. Flowers in cymes, bisexual, often zygomorphic; calyx 3.5 cm long, glabrous; corolla tube 3.5 cm long. Capsule 3.5 cm long, glabrous. The herb, a species of Java Island (Indonesia), has been planted in Singapore and Vietnam (Bảo Lộc, Sài Gòn). Pseuderanthemum reticulatum Radlk. Literature review & Aim of study 2 Figure 1: Xuân hoa nhọn, P. acuminatissimum (Miq.) Kuntze. Figure 2: Xuân hoa lá-hoa, P. bracteatum Imlay. Figure 3: Xuân hoa đỏ, P. carruthersii (Seem.) Guill. var. atropurpureum (Bull.) Fosb. Figure 4: Nấp vũm, P. carruthersii var. ovatifolium (Brem) Brem. Figure 5: P. crenulatum (Lindl.) R. Ben. Figure 6: P. eberhardtii R. Ben. Figure 7: Xuân hoa, P. palatiferum (Nees) Radlk. Figure 8: P. poilanei R. Ben.Z [...].. .Pseuderanthemum reticulatum Radlk Literature review & Aim of study Figure 9: Xuân hoa mạng, P reticulatum Radlk Figure 10: P tonkinense R Ben Figure 11: Eranthemum pulchellum Figure 12: P alatum Figure13: P laxiflorum Figure 14: P sinuatum Figure 15: P tuberculatum (Hook f.) Radlk Figure 16: P variabile 3 Pseuderanthemum reticulatum Radlk Literature review & Aim of... 5-lobed but often 2-lipped with lower lip 3-lobed and upper lip; stamens 2, attached to corolla Capsule woody, clavate with long, glabrous 4 Pseuderanthemum reticulatum Radlk Literature review & Aim of study 1.1.1.5 P reticulatum Radlk. [1] Vietnamese name: Xuân hoa mạng (figure 9) Perennial shrub, 0.5-2.5 m tall Stems quadrangular and ciliate in younger positions Leaves opposite and decussate, 8-15 cm... (4) and asperglaucide (36) were isolated from the roots of P palatiferum by Trần Công Khánh et al.[7] (2007) 9 Pseuderanthemum reticulatum Radlk Literature review & Aim of study HO R HO COOH HO R R COOH: Oleanolic acid (14) CH3: b-Amyrin (17) COOH HO Ursolic acid (15) Pomolic acid (16) 10 Pseuderanthemum reticulatum Radlk Literature review & Aim of study R3' R4' R8 R7 O R6 R3 R5 R3 R5 OCH3 OH OH OH... some Pseuderanthemum species have been used as medicinal herb for treating digestive disorder, liver disease, restoring health, ect However, there have been a few studies about the phytochemistry and bioactivity of Pseuderanthemum and, above all, no studies on P reticulatum Radlk Therefore, the thesis on contribution to the chemical study of leaves of P reticulatum Radlk has been carried out 11 Pseuderanthemum. .. layer were applied to GC-MS on HP-5 MS capillary column, programmed from 45 °C to 300 °C (10 13 Pseuderanthemum reticulatum Radlk Experimental °C/min), then held constant for 4 mins in order to determine the fatty acid moities of two glycoglycerolipids Scheme 1: Extraction procedure of Pseuderanthemum reticulatum Radlk Ground material (3.2 kg) - Macerate with ethanol at ambient temperature - Concentrate... 127.1 201.2 50.7 130.0 201.3 50.8 42.4 201.2 50.8 42.4 Aglycon of RE-EA6 C (CD3OD) Pseuderanthemum reticulatum Radlk Results & Discussion Table 7: The comparison of 13C-NMR data of RE-EA7, RE-EA8 and the aglycon of RE-EA6 with those of the aglycons of four roseoside diastereomers[24] 26 Pseuderanthemum reticulatum Radlk Results & Discussion 3.6 Structure elucidation of compound RE-Bu2  Compound RE-Bu2... (Seem.) Guill var atropurpureum (Bull.) Fosb and P carruthersii var ovatifolium (Brem.) Brem 1.1.1.3.1 P carruthersii (Seem.) Guill var atropurpureum (Bull.) Fosb.[1],[2],[4] Vietnamese name: Xuân hoa đỏ, Ô rô đỏ, Nhớt tím (figure 3) Shrub, 1-2 m tall Leaves, elliptic-ovate, smooth, violet-red, mottled yellowgreen, short petioles Flowers in cymes, bisexual; corolla tube rosy-purple, 1.3 cm long; stamens... (Seem.) Guill var atropurpureum (Bull.) Fosb due to leaves oval, 8.5 cm long, 4.5 cm wide, costa and lateral veins 7-8 pairs The herb has wildly growed in Sông Bé provine and Sài Gòn 1.1.1.4 P palatiferum (Nees) Radlk. [1],[2],[5] Vietnamese name: Xuân hoa (figure 7) Perennial shrub, 1-2 m tall Leaves 12-17 cm long, 3.5-5 cm wide, opposite, decussate, lanceolate, petioles 1.5-2.5 cm long Flowers in cymes,... 14: P sinuatum Figure 15: P tuberculatum (Hook f.) Radlk Figure 16: P variabile 3 Pseuderanthemum reticulatum Radlk Literature review & Aim of study 1.1.1.2 P bracteatum Imlay.[1] Vietnamese name: Xuân hoa lá- hoa, Hoàn ngọc đỏ, Hồng ngọc (figure 2) Herb, 50-60 cm tall Stems quadrangular and ciliate in younger positions Leaves 5-9 cm long, 3-5 cm wide; costa and lateral veins 5-6 pairs; petioles 2-3 cm... growed in Bà Nà mountain, Đà Nẵng province 1.1.2 Pharmaceutical studies of Pseuderanthemum Until now, there has only been the pharmaceutical information on three species of Pseuderanthemum including P carruthersii (Seem.) Guill var atropurpureum (Bull.) Fosb., P latifolim and P palatiferum (Nees) Radlk However, P palatiferum (Nees) Radlk has merely been studied on pharmaceutical by modern methods P carruthersii . HỌC QUỐC GIA THÀNH PHỐ HỒ CHÍ MINH ĐẠI HỌC KHOA HỌC TỰ NHIÊN  NGUYỄN PHI LINH THÀNH PHẦN HÓA HỌC CỦA LÁ CÂY XUÂN HOA MẠNG Pseuderanthemum reticulatum Radlk. HỌ Ô RÔ. XUÂN HOA MẠNG Pseuderanthemum reticulatum Radlk. HỌ Ô RÔ (Acanthaceae) LUẬN VĂN THẠC SĨ KHOA HỌC HÓA HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC GS. TS. NGUYỄN KIM PHI PHỤNG Tp Sài Gòn). Pseuderanthemum reticulatum Radlk. Literature review & Aim of study 2 Figure 1: Xuân hoa nhọn, P. acuminatissimum (Miq.) Kuntze. Figure 2: Xuân hoa lá- hoa, P. bracteatum