Antiinflammatory and ulcerogenic activities of Salvia triloba extracts.

In continuation of our research on Salvia triloba, acute and chronic antiinflammatory and ulcerogenic activities of chloroform, ethanol, butanol and water extracts were detected at 25 mg/kg p.o. The chloroform extract showed the highest antiinflammatory activity in both acute and chronic models, while the ulcerogenic effects of all tested extracts were found to be less than that of acetyl salicylic acid.

Antioxidant galloylated flavonol glycosides from Calliandra haematocephala.

Three new acylated quercetin rhamnosides have been isolated from the leaves and stem of Calliandra haematocephala Hassk. (Fabaceae) and their structures were established as quercitrin 2''-O-caffeate (1), quercitrin 3''-O-gallate (2) and quercitrin 2'',3''-di-O-gallate (3). Also, 17 known compounds were identified as gallic acid (4), methyl gallate (5), caffeic acid (6), myricitrin (7), quercitrin (8), myricetin 3-O-beta-D-4C1-glucopyranoside (9), afzelin (10), isoquercitrin (11), myricetin 3-O-(6''-O-galloyl)-beta-D-glucopyranoside (12), myricitrin 2''-O-gallate (13), quercitrin 2''-O-gallate (14), afzelin 2''-O-gallate (15), myricitrin 3''-O-gallate (16), afzelin 3''-O-gallate (17), 1,2,3,4,6-penta-O-galloyl-beta-D-4C1-glucopyranose (18), myricitrin 2'',3''-di-O-gallate (19), quercetin 3-O-methyl ether (20), for the first time from the genus Calliandra except for 6. Compounds 7, 8, 13, 14, 16 and 19 exhibited moderate to strong radical scavenging properties on lipid peroxidation, hydroxyl radical, superoxide anion generation and DPPH radical in comparison with that of quercetin as a positive control in vitro. Compounds 7 and 8 exhibited lethal effect towards brine shrimp Artemia salina.

Antioxidant activity and two new flavonoids from Washingtonia filifera.

Two new flavonoids, 8-hydroxyisoscoparin (1) and luteolin 7-O-glucoside 4''-sulfate (2), along with eight known flavonoids, including luteolin 7-O-glucoside 2''-sulfate, were isolated and identified from Washingtonia filifera. All compounds were characterized by (1)H-NMR, (13)C-NMR, CI-MS, FABMS and UV. The antioxidant activities of various W. filifera extracts were determined.

Flavonol glycosides from Cephalocereus senilis.

A new flavonol tetraglycoside, together with two known flavonol glycosides, kaempferol 7-rhamnoside and kaempferol 3-rhamnosyl(1-->6) galactoside-7-rhamnoside, were isolated from fresh plant material of Cephalocereus senilis. The structure of the new compound was established as kaempferol 3-O-beta-D-glucopyranosyl(1-->2)-O-[alpha-L-rhamnopyranosyl (1-->6)]-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside based on spectroscopic data. The whole plant flavonoid chemistry was strikingly different from that found previously in chitin-treated cell suspension cultures of the same plant.

Nonprotein amino acids from Cycas revoluta.

Two nonprotein amino acids, cycasindene and cycasthioamide, along with eight known nonprotein amino acids, were isolated from the seeds of Cycas revoluta Thunb. The structures of cycasindene and cycasthioamide were elucidated as 3-[3'-amino-indenyl-2]-alanine (1) and N-[glycinyl-alaninyl-11-thio]-5-one-pipecolic acid (2) by chemical and spectral methods.

Sesquiterpene lactones and other constituents from Hymenoxys richardsonii and H. subintegra.

Two Hymenoxys species afforded, in addition to known compounds, three new pseudoguaianoloides, a new sesquiterpene glucoside and a new butyrolactone. This is the first report of an eudesmane from the genus Hymenoxys. The structures were elucidated by high-field NMR and chemical transformations.

An acylated flavone C-glycoside from Glycyrrhiza eurycarpa.

A new acylated flavone C-glycoside, apigenin 6-C-alpha-L-rhamnopyranoside-8-C-[6"-(3-hydroxy-3-methyl-glutaroyl )-beta-D-glucopyranoside], was isolated from rhizomes of Glycyrrhiza eurycarpa and its structure was established on the basis of spectroscopic data.

Clerodane diterpenoids, long chain esters of coumaric acid and other compounds from Baccharis myrsinites.

A new clerodane diterpenoid and two new long chain esters of trans- and cis-coumaric acid, in addition to known triterpenoids and one known clerodane diterpenoid, have been isolated and characterized from Baccharis myrsinites. The structures were determined by spectroscopic techniques.

Kaempferol triosides from Reseda muricata.

A flavonoid trioside and its coumaryl ester together with seven known flavonoids and five phenolic acids were isolated from the leaves of Reseda muricata. Their structures were elucidated by spectroscopic methods including UV, FAB MS, 1H, 13C and 2D-NMR, DEPT, HMBC and HMQC experiments. The two compounds were identified as kaempferol 3-O-beta-D-glucopyranosyl-(1''' --> 2'')-O-alpha-L-rhamnopyranoside 7-O-beta-D-glucopyranoside and kaempferol 3-O-beta-D-glucopyranosyl-(1''' --> 2'')-O-alpha-L rhamnopyranoside 7-O-beta-D-(6''''-O-E-coumarylglucopyranoside), respectively.

Nonprotein amino acids from seeds of Cycas circinalis and Phaseolus vulgaris.

Our chemical studies on Cycas circinalis seeds from Guam has provided two new nonprotein amino acids, N-(3'-one-5'-methyl)-hexylalanine and leucine betaine. N-methylisoleucine, previously reported as a component of naturally occurring peptides, has been isolated as a free amino acid from the seeds of Phaseolus vulgaris (pinto bean), together with S-methylcysteine, pipecolic acid and a dipeptide, gamma-glutamyl-leucine.

Gallotannins and flavonoids from Haematoxylon campechianum.

Two new compounds, 2,6-bis-O-digalloyl-3-O-galloylglucose and 2-O-trigalloyl-1,3,4,6-tetrakis-O-galloylglucose, along with four known gallotannins, were isolated and identified from the leaves of Haematoxylon campechianum. In addition, four known flavonoid and three simple phenolic compounds were also detected.

Eudesmane derivatives from Iva frutescens.

Re-investigation of the aerial parts of Iva frutescens resulted in the isolation of three sesquiterpenes, two of which are new natural products, and their structures were established by spectral data.

An unusual cycloartane triterpenoid from Cimicifuga foetida.

A new cycloartane triterpenoid glycoside has been isolated from the rhizomes of Cimicifuge foetida L. The spectroscopic characteristics of the new compound are different from previously described cycloartane triterpenoids because of the loss of the 24-isopropyl group as well as the presence of a 11 beta-OH group. Based on spectroscopic evidence, including a series of 2D-NMR analyses, the structure of the new triterpene is assigned as 24-des-isopropyl-7-ene-23-one-9,19; 16,24-dicycloart-3 beta,11 beta,16 alpha,24 alpha-tetraol 3-O-beta-D-xylopryanoside, named here as neocimiside. The structure of the aglycone of neocimiside was confirmed by X-ray analysis.

Identification of nonprotein amino acids from cycad seeds as N-ethoxycarbonyl ethyl ester derivatives by positive chemical-ionization gas chromatography-mass spectrometry.

Nonprotein amino acids from nine species of cycad seeds were analyzed as N-ethoxycarbonyl ethyl ester (ECEE) derivatives by positive chemical-ionization gas chromatography-mass spectrometry. Based on the retention times and mass spectrometry analyses, 12 nonprotein amino acids were identified in these seeds. In addition to the excitatory and putative neurotoxin beta-N-methylamino-L-alanine (BMAA), the known neurotoxin beta-N-oxalylamino-L-alanine (BOAA) was detected from the seeds of Macrozamia moorei and M. communis, and delta-N-oxalyl-ornithine was obtained from the Cycas revoluta seeds. A novel nonprotein amino acid named cycasindene, previously reported from C. revoluta, was also found in the seeds of members of the C. angulata and C. rumphii complex. Eight additional known nonprotein amino acids were also identified. This is the first report of the neurotoxin BOAA from cycad seeds.

Simultaneous gas chromatographic analysis of non-protein and protein amino acids as N(O,S)-isobutyloxycarbonyl tert.-butyldimethylsilyl derivatives.

A unique derivatization procedure is described for the simultaneous determination of protein and non-protein amino acids present in aqueous samples. This procedure involves N(O,S)-isobutyloxycarbonylation combined with solid-phase extraction with subsequent tert.-butyldimethylsilylation for gas chromatographic analysis. Using this combined procedure, linear responses were obtained in the range of 10-100 ppm, with correlation coefficients varying from 0.991 to 0.999, for the free amino acids studied except for homocysteine (0.922) and homoserine (0.982). The relative standard deviations ranged from 0.7 to 5% for most amino acids with a few exceptions. Temperature-programmed retention index (I) sets as measured on DB-5 and DB-17 dual-capillary columns were characteristic of each amino acid and thus useful for the screening of amino acids by computer I matching. The mass spectral patterns of amino acid derivatives, exhibiting characteristic [M-57]+, [M-113]+, [M-131]+, [M-159]+, [M-174]+ and other ions, permitted rapid structural confirmation. The present method allowed simultaneous screening of free protein and non-protein amino acids when applied to seed samples such as almond, walnut, and sunflower seeds.

Rapid gas chromatographic screening of edible seeds, nuts and beans for non-protein and protein amino acids.

Water extraction with subsequent picric acid treatment and solvent washing (ethyl acetate and diethyl ether) was employed for the rapid isolation of free amino acids from non-aqueous food samples. The isolated amino acids were subjected to N(O,S)-isobutyloxycarbonylation followed by solid-phase extraction and tert.-butyldimethylsilylation for direct analysis by gas chromatography and gas chromatography-mass spectrometry. When the present method was applied to nineteen food samples (common beans, seeds, and nuts), seventeen protein amino acids and fifteen non-protein amino acids were simultaneously screened. Eleven non-protein amino acids including gamma-aminobutyric acid, pipecolic acid, pyroglutamic acid, alpha-aminobutyric acid, alpha-aminoadipic acid, and beta-alanine were tentatively identified, and four compounds assumed to be non-protein amino acids remained unidentified.

The magical and medicinal usage of Stangeria eriopus in South Africa.

The underground caudex of the cycad Stangeria eriopus is used extensively by several ethnic groups in South Africa, mainly as an ingredient in magical potions but also as an emetic. An assessment of two main outlets showed that 3410 plants were sold in the month of July 1992; continued usage of this material now threatens the remaining plant populations. A proximate analysis of the caudex material gives high carbohydrate content with only small percentages of fat, protein, fibre and ash. An unusually high content of sodium sulphate may explain the efficacy of Stangeria-containing preparations as an emetic. The phytosterols sitosterol and stigmasterol are present in a 4:1 ratio while the fatty acid component comprises palmitic, oleic, stearic and arachidic acids. Twelve amino acids were identified in the material, including the non-protein amino acids beta-alanine, gamma-aminobutyric acid and pyroglutamic acid. The candidate neurotoxin beta-N-methylamino-L-alanine could not be detected but cycasin is present at the levels of 0.17% and 0.21% in fresh and dry caudex material, respectively and appears to be accompanied by the related toxin, macrozamin.

GC-MS analysis of nonprotein amino acids in Gymnocladus dioicus as N(O,S)-isobutyloxycarbonyl silyl derivatives.

Two different derivatives of novel nonprotein amino acids in Gymnocladus dioicus seeds are prepared for gas chromatographic (GC) and mass spectrometric (MS) analysis. The interfering components in a water extract of the seeds are removed by picric acid treatment and multistep washing with organic solvents followed by N(O,S)-isobutyloxycarbonylation combined with solid-phase extraction. The resulting N(O,S)-isobutyloxycarbonyl (isoBOC) amino acids are then converted to either tert-butyldimethylsilyl (TBDMS) or trimethylsilyl (TMS) derivatives, which are analyzed by dual capillary column GC and GC-MS. The characteristic ions in the mass spectra of N(O,S)-isoBOC TBDMS and N(O,S)-isoBOC TMS derivatives enable confirmation of molecular weight and existence of functional groups containing active protons. Temperature programmed retention index sets measured on DB-5 and DB-17 capillary columns (J&W Scientific; Folsom, CA) are useful for distinguishing among structural isomers. gamma-Methylglutamic acid, diastereoisomers of 3-hydroxy-4-methylglutamic acid, cis and trans isomers of 5-hydroxypipecolic acid, and some free protein amino acids are identified in Gymnocladus dioicus seeds.

Constituents from Salvia triloba.

Twelve hydrocarbons, four sterols, three triterpenes, nineteen fatty acids, two phenolic acids, and five flavonoids have been detected and identified in Salvia triloba. Among the isolated flavonoids, 8-methoxygenistein 7-O-alpha-L-rhamnoside 4'-O-beta-D-glucoside (1), is reported for the first time.

Phenolic constituents from the leaves of the carnivorous plant Nepenthes gracilis.

Plumbagin, isoshinanolone, epishinanolone, shinanolone, quercetin and kaempferol were isolated from the leaves of Nepenthes gracilis. Spectral data of shinanolone are presented.