Reproductive and Pollination Biology of Magnolia and its Allied Genera (Magnoliaceae). I. Floral Volatiles of Several Magnolia and Michelia Species and their Roles in Attracting Insects

Abstract Volatile substances emitted from the flowers of eight Magnolia taxa ( M. sieboldii ssp. japonica, M. praecocissima var. praecocissima and var. borealis, M. tomentosa, M. salicifolia, M. obovata, M. denudata, and M. grandiflora ) and one Michelia species ( M. compressa ) (Magnoliaceae) were examined and identified using GC-MS. Volatile substances of these Magnolia and Michelia species consist primarily of monoterpenoids and sesquiterpenoids produced by the mevalonate pathway, acetogenins by the acetate-malonate pathway, and phenyl-propanoids by the shikimate pathway. These Magnolia and Michelia species all possessed various combinations of volatile monoterpenoids, acetogenins, and phenylpropanoids, except for Magnolia obovata , which emitted primarily sesquiterpenoids. Free amino acids in pollen of 12 Magnolia and one Liriodendron species were also analyzed, and their value as food sources for pollinators evaluated.
Pollinators visiting the flowers of five Magnolia species were collected in their native sites and identified. Their behaviors and roles as pollinating agents were assessed.     

The biosynthesis of trichothecin from acetate- [1,2- 13C2]

The coupling pattern of trichothecin biosynthesized from acetate-[1,2-¹³C₂] is in accord with previous enrichment studies. Multiple labelling was observed. Exogenous acetate has been shown to inhibit the utilization of glucose and the incorporation of radioactivity from pyruvate-[2-¹⁴C] and citrate-[1,5-¹⁴C] into the metabolites. Two pairs of ¹³C NMR assignments are interchanged.     

The configuration of the sesquiterpenoid 4-hydroxy-myoporone (athanagrandione)

The conversion of eremoacetal to (?)-1-(furan-3-yl)-4-hydroxy-4,8-dimethylnonane-1,6-dione establishes the configuration of (?)-4-hydroxymyoporone (athanagrandione) as R.     

Two New Sesquiterpenoid Glucosides from the Aerial Parts of Saussurea involucrate

Two new sesqulterpenoid glucosides, namely α-hydroxycostic acid 6-β-D-glucopyranoside （compound 1） and 11 βH-11,13-dlhydrodehydrocostuslactone 8α-O-（6＇-acetyl）-β-D-glucopyranoside （compound 2）, along with 11 known sesqulterpenoids （compounds 3-13） were isolated from the aerial parts of Saussurea involucrate （Kar. et Kir.） Sch.- BIp. The structures of the new sesquiterpenoid glucosides were established by one- and two-dimensional nuclear magnetic resonance and mass spectrometry analysis.     

Nitric oxide inhibitory constituents from Siegesbeckia pubescens

Two new sesquiterpenoids (1 and 2) and a new ent-pimarane type diterpenoid (3), together with eighteen known compounds (4–21), were isolated from the whole plants of Siegesbeckia pubescens. The structures of the new compounds were determined on the basis of 1D-, 2D NMR and HRESIMS data. All compounds were evaluated for their inhibitory effects on LPS-induced nitric oxide production in RAW 264.7 macrophages. Of these, highly oxygenated germacrane type sesquiterpenoids (1–2 and 13–14) showed significant inhibitory effects with IC₅₀ values ranging from 3.9 to 16.8 μM.     

Cadinane-type sesquiterpenoids from Schisandra bicolor

The phytochemical investigation on the stems of Schisandra bicolor led to the isolation of seven cadinane-type sesquiterpenoids, 2-hydroxy-11,12-dehydrocalamenene (1), ent-T-muurolol (2), (+)-ent-epicubenol (3), (1S,4S)-7,8-dihydroxy-11,12-dehydrocalamenene (4), cadinane-T-cadinol (5), (−)-cadin-4,10(15)-dien-11-oic acid (6), and cadina-4,10(15)-dien-3-one (7). Their structures were determined by extensive analysis of their spectroscopic data. All the isolates were isolated from this species for the first time. The chemotaxonomic significance of these compounds was also summarized.     

Chemical races in the red alga Laurencia nipponica (Rhodomelaceae, Ceramiales)

Genetic variation in the synthesis of halogenated secondary metabolites in the Japanese marine red alga Laurencia nipponica Yamada (Rhodomelaceae, Ceramiales) has been investigated in laboratory crossing experiments and chemical analyses, F₁ tetrasporophytes and F₁ gametophytes resulting from crosses within chemical races produced major metabolites characteristic of these races. F₁ tetrasporophytes derived from reciprocal interracial crosses produced: (i) both parental types of secondary metabolites; (ii) either of the parental types; or (iii) a further major compound in addition to both parental types or in addition to either of the parental types. The latter cases suggest that hybrid-specific products were formed by the combined enzymatic complements of the parents, as F₁ gametophytes derived from these interracial F₁ tetrasporophytes yielded one or other of their parental products in an approximate 1:1 ratio. The population structure was analyzed at localities in Hokkaido, where two of the chemical races occur sympatrically. At Usujiri (Minami-kayabe), where the prepacifenol race and the laureatin race were sym-patric, hybrid gametophytes (recombination type) were found in high frequency in addition to hybrid tetra sporophytes, which strongly suggests that a new, pre-pacifenol/laureatm race is beginning to be produced by natural hybridization and recombination. By contrast, at Oshoro Bay, where the laurencin race and the epi-lauraliene race grew together, the interracial hybrids were rare: only a few tetrasporophytes (probably F₁ generation) were found, suggesting that racial integrity may be retained by habitat segregation and/or the absence of recombination-type gametophytes.     

Sesquiterpenoid lactones from the liverwort Frullania tamarisci

Four isomeric sesquiterpenoid lactones have been isolated from the liverwort Frullania tamarisci They have been identified as the simple eudesmanolides (I–III) and costunolide (IV).     

Antimicrobial terpenoids of Gossypium: Hemigossypol, 6-methoxyhemigossypol and 6-deoxyhemigossypol

The sesquiterpenoid aldehydes, hemigossypol (1a), 6-methoxyhemigossypol (1b), and 6-deoxyhemigossypol (1c), were isolated and identified from Verticillium-infected stele tissue of Gossypium barbadense. Structures were established by spectral (UV, IR, NMR, MS) evidence and chemical transformations. This is the first report of (1b) and (1c) in nature, and of NMR and m.p. data for crystalline pure (1a). Compound (1a) occurred in diseased stele tissues of all 21 Gossypium species examined and in the genera, Cienfuegosia, Gossypioides, Hampea, and Thespesia; it was absent in three Hibiscus spp. Compound (1b) occurred in the same taxa as (1a), except that it was absent in species of two cytogenetic groups (A and B genome) of Gossypium. Compound (1c) occurred in trace quantities, or was not detected, in most species; however, its distribution appeared to besimilar to that