Eryngial (trans-2-dodecenal), a bioactive compound from Eryngium foetidum: its identification, chemical isolation, characterization and comparison with ivermectin in vitro.

Methanol-water (4:1, v/v) crude extracts (50 mg mL(-1)) of 25 Jamaican medicinal plants were screened in vitro for anthelmintic activity using infective third-stage larvae of Strongyloides stercoralis. The most effective extract was further chemically scrutinized to isolate and identify the source of the bioactivity, and the efficacy of this compound was compared with ivermectin. Eosin exclusion (0.1 mg mL(-1)) served as the indicator of mortality in all bioassays. A crude extract of Eryngium foetidum (Apiaceae) was significantly (Probit Analysis, P<0.05) more potent than the other plant extracts, taking 18.9 h to kill 50% (LT50) of the larvae. Further, the petrol extract of E. foetidum was significantly more effective (Probit Analysis, P<0.05) at killing the larvae (LT50, 4.7 h) than either its methanol-water or dichloromethane extract. The latter two effected less than 1% larval mortality after 120 h. With bioassay-driven column chromatography of the petrol extract, trans-2-dodecenal (eryngial) was identified and chemically isolated as the main anthelmintic compound in E. foetidum. There was a significant difference between the 24 h LD50 values (mm) of trans-2-dodecenal (0.461) and ivermectin (2.251) but there was none between the 48 h LD50 values (mm): trans-2-dodecenal (0.411) and ivermectin (0.499) in vitro.

Biotransformation of cedrol by Curvularia lunata ATCC 12017.

Bioconversion of cedrol (1) with the Curvularia lunata was investigated in two different growth media. Five products were obtained in potato dextrose broth, whereas nine compounds were produced in a medium containing beef extract. Only three of the metabolites: 3beta-hydroxycedrol (2), 3alpha-hydroxycedrol (3) and 12-hydroxycedrol (4) were common to both media. They were also obtained as the major products in each case. Three new derivatives have also been identified.

Biotransformation of diterpenes and diterpene derivatives by Beauveria bassiana ATCC 7159.

The biohydroxylation of stemodin and stemodinone by Beauveria bassiana ATCC 7159 gave exclusively 2alpha,13,18-trihydroxystemodane and 13,18-dihydroxystemodan-2-one respectively. Stemarin was converted to the novel 1beta,13,19-trihydroxystemarane and 13-hydroxystemarane-19-carboxylic acid. The synthesis and biotransformation of various derivatives of stemodin have also been studied.

Biotransformation of cadinane sesquiterpenes by Beauveria bassiana ATCC 7159.

Incubation of cadina-4,10(15)-dien-3-one with Beauveria bassiana ATCC 7159 has resulted in the production of nine novel sesquiterpenes. These metabolites were identified as (4S)-cadin-10(15)-en-3-one, (4S)-3 alpha-hydroxycadin-10(15)-ene, (4R)-3 alpha-hydroxycadin-10(15)-ene, (4S)-3 beta-hydroxycadin-10(15)-ene, (4S)-3 beta-hydroxycadina-10(15),12(14)-diene, (4S)-13-hydroxycadin-10(15)-en-3-one, (4S)-12-hydroxycadin-10(15)-en-3-one, (4R)-3 beta, 14-dihydroxycadin-10(15)-ene and 3 alpha-hydroxycadina-4,10(15)-diene. The allylic alcohol 3 alpha-hydroxycadina-4,10(15)-diene was also biotransformed to afford cadina-4,10(15)-dien-3-one, (4S)-cadin-10(15)-en-3-one and (4S)-12-hydroxycadin-10(15)-en-3-one. The insecticidal potential and phytotoxicity of the isolated metabolites have been evaluated.

Biotransformation of squamulosone by Curvularia lunata ATCC 12017.

Squamulosone (aromadendr-1(10)-en-9-one), isolated in large quantity from the plant Hyptis verticillata Jacq. (Labiatae), was incubated with the fungus Curvularia lunata ATCC 12017 in two different growth media. Six metabolites were isolated from each medium. with five of the products being common to both fermentations. All seven metabolites are novel. The insecticidal activity of these aromadendranes was evaluated against the sweet potato weevil Cylas formicarius elegantus.

Acaricidal and insecticidal activities of cadina-4,10 (15)-dien-3-one.

The novel assignment of 13C and 1H NMR data for cadina-4,10(15)-dien-3-one obtained from Hyptis verticillata is presented. The study revealed that cadina-4,10(15)-dien-3-one possesses chemosterilant activities against the economically important cattle tick, Boophilus microplus, and toxic action against adult Cylas formicarius the most destructive pest of sweet potato (I pomoea sp.).

Remote functionalization reactions in steroids.

Work published over the last thirty years on the functionalization of unactivated positions in the steroid skeleton has been reviewed.

The effect of 4beta and 19 ester functionalities on some electrophilic addition reactions of delta5-steroids.

The reactions of 3beta-acyloxyandrost-5-enes with bromine/silver acetate (Petrow reaction) and mercury(II) trifluoroacetate (modified Treibs oxidation) have been used previously to effect allylic oxidation on these substrates en route to biologically active compounds. In both these reactions, which involve electrophilic addition to the delta5-bond, the 3-acyloxy substituent plays a significant role. In this report, the effect of introducing other substituents proximate to the delta5-bond has been studied by using derivatives of 3beta-acetoxyandrost-5-en-17-one (1), namely, 3beta,4beta-diacetoxyandrost-5-en-17-one (13), 3beta,19-diacetoxyandrost-5-en-17-one (14), 3beta-acetoxyandrost-5-ene-7,17-dione (15), and 3beta-acetoxy-4,4-dimethylandrost-5-en-17-one (17). Our results indicate that in both sets of reactions the effect of the introduced functional groups was pronounced. In the Petrow reaction, electrophilic addition rather than allylic oxidation on the diacetates was observed. With the Treibs reaction, allylic oxidation on the diacetates occurred. The 7-keto and 4,4-dimethyl steroids proved to be poor substrates in both reactions.

Steroid transformations with Exophiala jeanselmei var. lecanii-corni and Ceratocystis paradoxa.

The fungi Exophiala jeanselmei var. lecanii-corni [IMI (International Mycological Institute) 312989, UAMH (University of Alberta Microfungus Collection and Herbarium) 8783] and Ceratocystis paradoxa (IMI 374529, UAMH 8784) have been examined for their potential in steroid biotransformation. The study has determined that E. jeanselmei var. lecanii-corni effected overall anti-Markovnikov hydration on dehydroisoandrosterone, and side-chain degradation on a variety of pregnanes. Both ascomycetes were found to carry out redox reactions of alcohols and ketones as well as 1,4 reduction of alpha,beta-unsaturated carbonyl systems.

Steroid transformations with Fusarium oxysporum var. cubense and Colletotrichum musae.

The utility of two locally isolated fungi, pathogenic to banana, for steroid biotransformation has been studied. The deuteromycetes Fusarium oxysporum var. cubense (IMI 326069, UAMH 9013) and Colletotrichum musae (IMI 374528, UAMH 8929) had not been examined previously for this potential. In general, F. oxysporum var. cubense effected 7alpha hydroxylation on 3beta-hydroxy-delta5-steroids, 6beta, 12beta, and 15alpha hydroxylation on steroidal-4-ene-3-ones, side-chain degradation on 17alpha,21-dihydroxypregnene-3,20-diones, and 15alpha hydroxylation on estrone. Both strains were shown to perform redox reactions on alcohols and ketones.

The scope and limitations of the reaction of delta 5-steroids with mercury(II) trifluoroacetate.

The effect of the C-3 substituent on the reaction of androst-5-enes with mercury(II) trifluoroacetate in dichloromethane (modified Treibs oxidation) was investigated. 3 beta-Acyloxyandrost-5-en-17-ones gave 3 beta-acyloxy-6 beta-hydroxyandrost-4-en-17-ones accompanied by 3 beta-acyloxy-6-chloromercuriandrost-5-en-17-ones. 3 beta-Acetoxy-6 beta-trifluoroacetoxyandrost-4-en-17-one and 3 beta-acetoxy-4 beta-trifluoroacetoxyandrost-5-en-17-one were revealed to be intermediates in the reaction. The formation of the chloromercury steroids indicated participation in the reaction by the solvent. With 3 alpha-acetoxyandrost-5-en-17-one as substrate, a complete reversal in the product distribution was observed. 3 beta-Haloandrost-5-en-17-ones gave mainly products that reflected SN1 substitution of the halide. 3 beta-Hydroxy- and 3 beta-trifluoroacetoxyandrost-5-en-17-ones were formed. 3 beta-Methoxyandrost-5-en-17-one afforded in nearly identical yields androst-4-ene-3,17-dione, 3 beta-methoxy-6 beta-hydroxyandrost-4-en-17-one, 3 beta-methoxy-6-chloromercuriandrost-5-en-17-one and 6 beta-hydroxyandrost-4-ene-3,17-dione while androst-5-en-17-one yielded 3 beta,6 beta-dihydroxyandrost-4-en-17-one, androst-5-ene-7,17-dione and androst-4-ene-3,17-dione. The effects of solvent and other mercury salts on the reaction were also studied. Treibs oxidation was successful in chloroform, carbon tetrachloride, and dibromomethane, but not in other solvents tested. 3 beta-Acetoxy-6-bromomercuriandrost-5-en-17-one was obtained in dibromomethane. Replacement of the reagent by mercury(II) trichloroacetate altered the intermediates formed but not the products. Mercury(II) tribromoacetate was unreactive, however.

An intervention technique for children with autistic spectrum disorder: joint attentional routines.

Virtually all children with autism are deficient in joint attentional skills. The impact of this deficit may be understood in the context of pragmatically based explanations of language acquisition. In this view, each step in the ontongeny of joint attention is consequential for language development. Thus, it is important that speech-language pathologists understand the developmental course of joint attention so that intervention may start at the earliest step possible. In this article, we review the literature on joint attention and its relationship with other rule systems of language. We discuss the ontogeny of joint attention in typical children. Finally, we describe the developmental course of joint attention as a framework for language intervention through the study of one case.

New skeletal sesquiterpenoids, caprariolides A-D, from Capraria biflora and their insecticidal activity.

Four structurally novel isomeric sesquiterpenes have been isolated from the aerial parts of Capraria biflora. Caprariolides A (1), B (2), C (3), and D (4) have been determined by NMR spectroscopy experiments to be the (3S,5S,9R), (3R,5S,9R), (3R,5R,9R), and (3S,5R, 9R) isomers of 7-(furan-3'-yl)-3,9-dimethyl-1-oxaspiro[4. 5]dec-6-en-2-one, respectively. Both 1 and 2 were found to exhibit insecticidal activity against adult Cylas formicarius elegantulus, one of the most destructive insect pests of the sweet potato, Ipomoea sp.