Asplenioideae Species as a Reservoir of Volatile Organic Compounds with Potential Therapeutic Properties.

Twelve French Asplenioideae ferns (genera Asplenium and subgenera Ceterach and Phyllitis) were investigated for the first time for volatile organic compounds (VOC) using GC-MS. Sixty-two VOC biosynthesized from the lipidic, shikimic, terpenic and carotenoid pathways were identified. Several VOC profiles can be highlighted from Asplenium jahandiezii and A. xalternifolium with exclusively lipidic derivatives to A. onopteris with an equal ratio of lipidic/shikimic compounds. Very few terpenes as caryophyllene derivatives were identified, but only in A. obovatum subsp. bilotii. The main odorous lipidic derivatives were (E)-2-decenal (waxy and fatty odor), nonanal (aldehydic and waxy odor with a fresh green nuance), (E)-2-heptenal (green odor with a fatty note) and 1-octen-3-ol (mushroom-like odor), reported for all species. A few VOC are present in several species in high content, i.e., 9-oxononanoic acid used as a precursor for biopolymers (19% in A. jahandiezii), 4-hydroxyacetophenone with a sweet and heavy floral odor (17.1% in A. onopteris), and 4-hydroxybenzoic acid used as a precursor in the synthesis of parabens (11.3% in A. foreziense). Most of the identified compounds have pharmacological activities, i.e., octanoic acid as antimicrobial, in particular against Salmonellas, with fatty and waxy odor (41.1% in A. petrarchae), tetradecanoic acid with trypanocidal activity (13.3% in A. obovatum subsp. bilotii), 4-hydroxybenzoic acid (8.7% in A. onopteris) with antimicrobial and anti-aging effects, 3,4-dihydroxybenzaldehyde as an inhibitor of growth of human cancer cells (6.7% in Ceterach officinarum), and phenylacetic acid with antifungal and antibacterial activities (5.8% in A. onopteris). Propionylfilicinic acid was identified in the twelve species. The broad spectrum of odorous and bioactive VOC identified from the Asplenium, Ceterach and Phyllitis species are indeed of great interest to the cosmetic and food industries.

Volatile organic compounds of six French Dryopteris species: natural odorous and bioactive resources.

Aerial parts of six Dryopteris species collected in France were investigated for volatile organic compounds (VOC) for the first time. Fifty-three biosynthesized VOC from the shikimic, lipidic and terpenic pathways were identified using gas chromatography/mass spectrometry. Many bioactive polyketide compounds as filicinic derivatives (from 8.5 to 23.5%) and phloroglucinol derivatives (from 8.2 to 53.8%) with various pharmacological activities were detected in high amount from five analysed Dryopteris species, in particular D. oreades and D. borreri, i.e., propionylfilicinic acid (> 10% in D. affinis and D. ardechensis) and 2,6-dihydroxy-4-methoxy-3-methylbutyrophenone (aspidinol) (19.1% and 14.6% in D. oreades and D. borreri, respectively). Several terpenic derivatives with a low odor threshold were identified, i.e., carota-5,8-diene (from 2.5 to 18.4%: floral, woody or fresh bark note), (E)-nerolidol (> 10% for D. borreri and D. cambrensis; floral or woody odor), alpha-selinene (> 7% for D. ardechensis; woody-spicy odor), and aristolene (12.8% in D. affinis; flower, sweet odor). The main isoprenoid derivatives were 4-hydroxy-5,6-epoxyionol, 3-oxo-alpha-ionol and 4-oxo-7,8-dihydro-beta-ionone (essentially in D. remota), whereas the main aromatic compound was 4-hydroxy-3-methoxyacetophenone (20.6% and 12.6% in D. cambrensis and D. borreri, respectively) and the main lipid derivative was 1-octen-3-ol with a mushroom-like odor (from 0.4 to 8.3%). Dryopteris species resources are of great interest as a reservoir of odorous and bioactive compounds.

Volatile composition of six horsetails: prospects and perspectives.

Six horsetails were investigated for volatile organic compounds (VOC) by GC-MS using organic solvent extraction. Seventy-five VOC biosynthesized from the shikimic, lipidic and terpenic pathways including isoprenoid derivatives were detected from these putative natural resources. E. palustre var. americana contained mainly lipidic derivatives, i.e., 1-octen-3-ol (mushroom-like odor), (E)-2-hexenoic acid (fruity odor) and (E)-2-hexenal (green odor). Many isoprenoid flavour precursors, i.e., 3-oxo-alpha-ionol (spicy odor) and (E,E)-pseudoionone (balsamic odor), as well as odorous benzenic derivatives, i.e, phenylethanal (hyacinth, lilac note) and 2-phenylethanol (rose odor) contributed to the odor of E. arvense. The volatile pattern of E. telmateia is dominated by high amounts of isoprenoids and benzenic derivatives. The complex volatile profiles of E. hyemale and E. ramosissimum are based on ferulic acid isomers, along with either (E)-2-heptenal (green vegetable-like odor) or 4-vinylguaiacol (spicy clove smoky odor) for E. hyemale and E. ramosissimum, respectively. The broad spectrum of E. scirpioides shows the lowest VOC content with high amount of isoprenoids (46.9%), mainly ionone derivatives. Equisetum resources are of great interest as bioactive litter and new potential functional feed ingredients.

Primary flavonoids in marigold dye: extraction, structure and involvement in the dyeing process.

Flavonoids extracted from marigold flowers were investigated for their dyeing potential. Patulitrin (1) and patuletin (2) were isolated and their structures established using NMR and HPLC-MS. These compounds were identified as the main flavonoids present in the dyeing bath. Following the dyeing process, it was demonstrated that aglycone 2 bound more strongly to wool fibres than its glucoside 1. Moreover, analysis focused on 1 and 2 dynamics during plant growth revealed that these components were only found in flowers during and after flowering. The influence of growing location was also investigated and it appeared that cultivation under Mediterranean conditions enhanced biosynthesis of 1 and 2 . Finally, several solvents were tested for their potential to extract the flavonoids: the use of a water-ethanol mixture gave a high extraction efficiency and allowed selective extraction of 1 and 2. The implications of these results are discussed in relation to the development of marigold as a potential dyeing plant.

Theoretical study of 31P, 31P coupling constants in cyclotriphosphazenes.

Several scalar coupling constants (mainly 31P, 31P) were calculated for 10 cyclotriphosphazenes and compared with experimental results when available. Although the experimental values cannot be reproduced, the calculated values are proportional to the experimental values. Some difficult cases, such as 19F, 19F couplings, are discussed.

Evidence for Nondissociative Ligand Exchange within [4+2]-Coordinate Phosphorus Species in Solution.

[4+2]-Coordinate phosphorus compounds, [bis(8-(dimethylamino)-1-naphthyl)]phenylphosphane, [bis(8-(dimethylamino)-1-naphthyl)]phenylphosphane sulfide, [bis(8-(dimethylamino)-1-naphthyl)]phenylphosphonium bromide, [bis(8-(dimethylamino)-1-naphthyl)]methylphosphane, and [bis(8-(dimethylamino)-1-naphthyl)]phosphane oxide, with two identical bidentate (8-(dimethylamino)-1-naphthyl) ligands have asymmetrical geometries in solution and undergo intramolecular nondissociative ligand exchange as shown by dynamic (1)H NMR studies. The DeltaG() values for this process were found to lie in the range 56.2-61.7 kJ mol(-)(1). The (1)H NMR study for bis[(8-(dimethylamino)-1-naphthyl)]phenylphosphane sulfide has revealed that two hexacoordinate isomers coexist in solution in a solvent dependent ratio. Their interconversion in solution is consistent with an intramolecular 1,2-shift of adjacent ligands.