Juan Hua

Defensive Sesterterpenoids with Unusual Antipodal Cyclopentenones from the Leaves of Leucosceptrum canum

Two novel sesterterpenoids, leucosceptroids C (1) and D (2), possessing unusual antipodal cyclopentenones while maintaining the stereochemistry and functionality of the tricyclic cores, were discovered from the leaves of Leucosceptrum canum (Labiatae). Their structures including absolute stereochemistries were determined by comprehensive NMR, MS, and single-crystal X-ray diffraction analyses. The potent antifeedant activity of 1 against the generalist plant-feeding insect Helicoverpa armigera (EC(50) = 0.017 μmol/cm(2)) suggested them to be new defensive sesterterpenoids of L. canum.

Peltate glandular trichomes of Colquhounia coccinea var. mollis Harbor a new class of defensive sesterterpenoids

A new class of unique sesterterpenoids, colquhounoids A-C (1-3), were identified from the peltate glandular trichomes of Colquhounia coccinea var. mollis (Lamiaceae) through precise laser-microdissection coupled with UPLC/MS/MS and spectroscopic analyses and X-ray diffraction. Very interestingly, their structural features and defensive function are closely related to leucosceptroid-class sesterterpenoids harbored by the glandular trichomes of another Lamiaceae taxon, Leucosceptrum canum, even though this is morphologically distinct and taxonomically distant.

Defense sesterterpenoid lactones from Leucosceptrum canum

Ten sesterterpenoids, leucosceptroids E-N (1-10), possessing an α,β-unsaturated γ-lactone moiety, were isolated from the leaves and flowers of a woody Labiatae, Leucosceptrum canum. Their structures including relative stereochemistry were determined by comprehensive 1D and 2D NMR, MS, and in the case of 1 and 10, by single crystal X-ray diffraction analyses. This class of unique plant terpenoids was designated as leucosceptrane sesterterpenoids (=leucosceptroids). The potent antifeedant activity of the most abundant compound, leucosceptroid G (3), and a representative compound, leucosceptroid N (10), against the generalist plant-feeding insect Helicoverpa armigera suggested that they might also be defense compounds of L. canum against insects.

New Antifeedant C20 Terpenoids from Leucosceptrum canum

Three novel C(20) terpenoids, norleucosceptroids A-C (1-3), were isolated from the leaves and flowers of Leucosceptrum canum (Labiatae) and were identified by comprehensive spectroscopic analysis and, in the case of 1, single-crystal X-ray diffraction. Structurally, compounds 1-3 should be categorized as pentanor-sesterterpenoids rather than diterpenoids. Moderate antifeedant activity of 1-3 against the generalist plant-feeding insect Helicoverpa armigera was detected, suggesting that they might also be involved in the plant defense against insect herbivores.

Secondary Metabolites from Glycine soja and Their Growth Inhibitory Effect against Spodoptera litura

The wild soybean (Glycine soja Sieb. et Zucc) has been reported to be relatively resistant to insect and pathogenic pests. However, the responsible secondary metabolites in the aerial part of this important plant are largely unknown. From the aerial part of G. soja, 13 compounds were isolated and identified, including seven isoflavonoids (1-7), a cyclitol (8), two sterol derivatives (9 and 10), and three triterpenoids (11-13). Compound 7 is a new isoflavonoid, and compounds 9 and 10 are reported as natural products for the first time. The growth inhibitory activity of 1, 3, 4, and 8 against the larvae of Spodoptera litura was investigated. The most abundant isoflavonoid in the aerial part of G. soja, daidzein (1), which could not be metabolized by S. litura, was found to inhibit the insect larvae growth significantly in 3 days after feeding diets containing the compound. Compounds 3, 4, and 8, which could be partially or completely metabolized, were inactive. Our results suggested that the isoflavonoid daidzein (1) might function as a constitutive defense component in G. soja against insect pests.

Unraveling the Metabolic Pathway in Leucosceptrum canum by Isolation of New Defensive Leucosceptroid Degradation Products and Biomimetic Model Synthesis

Seven new leucosceptroid degradation products possessing a C20, C21, or C25 framework, norleucosceptroids D-H (1-5), leucosceptroids P (6), and Q (7), have been isolated from Leucosceptrum canum. Their structures were determined by comprehensive NMR, MS, and single-crystal X-ray diffraction analyses. Discovery of these key intermediates, together with the biomimetic oxidation of a model system, supports the hypothesis that two biosynthetic pathways are operative. Antifeedant activity was observed for compounds 1-3.

Limonoids from Aphanamixis polystachya and Their Antifeedant Activity

Eight new aphanamixoid-type aphanamixoids (C-J, 1-8) and six new prieurianin-type limonoids, aphanamixoids K-P (9-14), along with 10 known terpenoids were isolated from Aphanamixis polystachya, and their structures were established by spectroscopic data analysis. Among the new limonoids, 13 compounds exhibited antifeedant activity against the generalist Helicoverpa armigera, a plant-feeding insect, at various concentration levels. In particular, compounds 1, 4, and 5 showed potent activities with EC50 values of 0.017, 0.008, and 0.012 μmol/cm(2), respectively. On the basis of a preliminary structure-activity relationship analysis, some potential active sites in the aphanamixoid-type limonoid molecules are proposed.

Peltate glandular trichomes of Colquhounia seguinii harbor new defensive clerodane diterpenoids

Glandular trichomes produce a wide variety of secondary metabolites that are considered as major defensive chemicals against herbivore attack. The morphology and secondary metabolites of the peltate glandular trichomes of a lianoid Labiatae, Colquhounia seguinii Vaniot, were investigated. Three new clerodane diterpenoids, seguiniilactones A-C (1-3), were identified through precise trichome collection with laser microdissection, metabolic analysis with ultra performance liquid chromatography-tandem mass spectrometer, target compound isolation with classical phytochemical techniques, structure elucidation with spectroscopic methods. All compounds showed significant antifeedant activity against a generalist plant-feeding insect Spodoptera exigua. Seguiniilactone A (1) was approximately 17-fold more potent than the commercial neem oil. α-Substituted α,β-unsaturated γ-lactone functionality was found to be crucial for strong antifeedant activity of this class of compounds. Quantitative results indicated that the levels of these compounds in the peltate glandular trichomes and leaves were sufficiently high to deter the feeding by generalist insects. Moderate antifungal activity was observed for seguiniilactone C (3) against six predominant fungal species isolated from the diseased leaves of C. seguinii, while seguiniilactones A and B were generally inactive. These findings suggested that seguiniilactones A-C might be specialized secondary metabolites in peltate glandular trichomes for the plant defense against insect herbivores and pathogens.

Capitate glandular trichomes of Paragutzlaffia henryi harbor new phytotoxic labdane diterpenoids.

The morphology and chemical profile of the capitate glandular trichomes (CGTs) of Paragutzlaffia henryi (Acanthaceae) were investigated. Four new labdane diterpenoids named paraguhenryisins A-D (1-4), together with the known physacoztomatin (5), were localized to the CGTs using laser microdissection coupled with cryogenic (1)H NMR and HPLC analyses and were traced and isolated from the CGT extract of inflorescences. Their structures were determined by spectroscopic methods and single-crystal X-ray diffraction. Bioassays indicated significant inhibitory effect for these diterpenoids on Arabidopsis thaliana seed germination and seedling root elongation. The most potent inhibitor, paraguhenryisin C (3), was interestingly detected in both the rhizosphere soil and water rinsed inflorescences extract of P. henryi but not the roots, with average contents in the rhizosphere soil relevant to its phytotoxic EC50 values. These results suggested that phytotoxic labdane diterpenoids in the CGTs might be released into the environment as a defensive measure for P. henryi against other competitive plants.

Localisation of Two Bioactive Labdane Diterpenoids in the Peltate Glandular Trichomes of Leonurus japonicus by Laser Microdissection Coupled with UPLC-MS/MS

INTRODUCTION Glandular trichomes of plants are biochemical factories that could produce, store and secrete copious pharmaceutically important natural products. The Labiatae plant Leonurus japonicus is an important traditional Chinese medicine used to treat gynecological diseases, and has abundant peltate glandular trichomes (PGTs), in which the secondary metabolites accumulated are still unknown. OBJECTIVE To study the secondary metabolites specifically accumulated in the PGTs of L. japonicus and their biological activities, and provide a new way to pinpoint bioactive natural products from plants. METHODOLOGY Morphology of the trichomes on L. japonicus were observed under a scanning electron microscope. The PGTs of L. japonicus were precisely collected using laser microdissection (LMD) and analysed for their secondary metabolites with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Targeted compounds were isolated with classical phytochemical methods, and their structures were elucidated by spectroscopic analysis. Biological activities were evaluated by in vitro assays. RESULTS Two labdane diterpenoids, leoheterin (1) and galeopsin (2), were localised in the PGTs of L. japonicus. Antithrombotic activity of 1 in anti-platelet aggregation assay induced by arachidonic acid was observed. Both compounds showed potential anti-inflammatory activity by inhibiting proinflammatory cytokine TNF-α. In addition, anti-proliferative effect of both compounds on several cancer cell lines was also detected. CONCLUSION Two bioactive labdane diterpenoids were localised in the PGTs of L. japonicus. The findings suggested that it might be an efficient approach to explore bioactive natural products from the glandular trichomes of medicinal plants with LMD-UPLC/MS/MS. Copyright