Chemical composition and mosquito larvicidal activity of essential oils from leaves of different Cinnamomum osmophloeum provenances

Chemical compositions of leaf essential oils from eight provenances of indigenous cinnamon (Cinnamomum osmophloeum Kaneh.) were compared. According to GC-MS and cluster analyses, the leaf essential oils of the eight provenances and their relative contents were classified into five chemotypes-cinnamaldehyde type, linalool type, camphor type, cinnamaldehyde/cinnamyl acetate type, and mixed type. The larvicidal activities of leaf essential oils and their constituents from the five chemotypes of indigenous cinnamon trees were evaluated by mosquito larvicidal assay. Results of larvicidal tests demonstrated that the leaf essential oils of cinnamaldehyde type and cinnamaldehyde/cinnamyl acetate type had an excellent inhibitory effect against the fourth-instar larvae of Aedes aegypti. The LC(50) values for cinnamaldehyde type and cinnamaldehyde/cinnamyl acetate type against A. aegypti larvae in 24 h were 36 ppm (LC(90) = 79 ppm) and 44 ppm (LC(90) = 85 ppm), respectively. Results of the 24-h mosquito larvicidal assays also showed that the effective constituents in leaf essential oils were cinnamaldehyde, eugenol, anethole, and cinnamyl acetate and that the LC(50) values of these constituents against A. aegypti larvae were <50 ppm. Cinnamaldehyde had the best mosquito larvicidal activity, with an LC(50) of 29 ppm (LC(90) = 48 ppm) against A. aegypti. Comparisons of mosquito larvicidal activity of cinnamaldehyde congeners revealed that cinnamaldehyde exhibited the strongest mosquito larvicidal activity.     

Emodin isolated from Cassia obtusifolia (Leguminosae) seed shows larvicidal activity against three mosquito species

Mosquito larvicidal activity of Cassia obtusifolia (Leguminosae) seed-derived materials against the fourth-instar larvae of Aedes aegypti, Aedes togoi, and Culex pipiens pallens was examined. The chloroform fraction of C. obtusifolia extract showed a strong larvicidal activity of 100% mortality at 25 mg/L. The biologically active component of C. obtusifolia seeds was characterized as emodin by spectroscopic analyses. The LC(50) values of emodin were 1.4, 1.9, and 2.2 mg/L against C. pipiens pallens, A. aegypti, and A. togoi, respectively. Pirimiphos-methyl acts as a positive control directly compared to emodin. Pirimiphos-methyl was a much more potent mosquito larvicide than emodin. Nonetheless, emodin may be useful as a lead compound and new agent for a naturally occurring mosquito larvicidal agent. In tests with hydroxyanthraquinones, no activity was observed with alizarin, danthron, and quinizarin, but purpurin has an apparent LC(50) value of approximately 19.6 mg/L against A. aegypti.     

Insect antifeedant activity of tetranortriterpenoids from the Rutales. A perusal of structural relations

Structure-related insect antifeedant relationship of 56 limonoids (both natural and modified) from the plants belonging to the order Rutales was attempted considering substitution patterns, oxidation states, and hydrophobicity, as well as distant geometry derived through conformational analysis on molecular modeling. Orientation of the furan and hydroxylation at specific carbon sites have been shown to influence the antifeedancy against the fall armyworm, Spodoptera litura.     

Chemical composition and larvicidal activity of the essential oils from Eupatorium betonicaeforme (D.C.) Baker (Asteraceae)

The volatile composition of the essential oils from leaves and roots of Eupatorium betonicaeforme (D.C.) Baker was analyzed by GC-MS. A total of 12 compounds were identified. beta-Caryophyllene (12.4-41.7%), alpha-humulene (11.7-14.6%), gamma-muurolene (10.4-19.0%), bicyclogermacrene (15.0-17.5%), 2,2-dimethyl-6-vinylchroman-4-one (10.3-25.5%), and 2-senecioyl-4-vinylphenol (8.5-41.0%) were the most prominent constituents. The former two compounds were isolated and characterized by spectroscopic data. The essential oils and the isolated compounds were tested against Aedes aegypti larvae survival. The results obtained show that the essential oil from roots and 2,2-dimethyl-6-vinylchroman-4-one (10.3-25.5%) could be considered as natural larvicidal agents.     

A piperidine amide extracted from Piper longum L. fruit shows activity against Aedes aegypti mosquito larvae

Mosquito larvicidal activity of Piper longum fruit-derived materials against the fourth-instar larvae of Aedes aegypti was examined. A crude methanol extract of P. longum fruits was found to be active against the larvae, and the hexane fraction of the methanol extract showed a strong larvicidal activity of 100% mortality. The biologically active component of P. longum fruits was characterized as pipernonaline by spectroscopic analyses. The LC(50) value of pipernonaline was 0.25 mg/L. The toxicity of pipernonaline is comparable to that of pirimiphos-methyl as a mosquito larvicide. In tests with available components derived from P. longum, no activity was observed with piperettine, piperine, or piperlongumine.     

Isolation and identification of mosquito bite deterrent terpenoids from leaves of American (Callicarpa americana) and Japanese (Callicarpa japonica) beautyberry

Essential oil extracts from Callicarpa americana and Callicarpa japonica were investigated. Bioassay-guided fractionation of C. americana extracts using the yellow fever mosquito, Aedes aegypti, led to the isolation of alpha-humulene, humulene epoxide II, and intermedeol and a newly isolated terpenoid (callicarpenal). Similar work involving C. japonica resulted in the isolation of an additional compound, spathulenol, as well as the four compounds isolated from C. americana. Structure elucidation was performed on all isolated compounds using a combination of gas chromatography-mass spectrometry-electron ionization, high-resolution liquid chromatography-MS-electrospray ionization, and one- and two-dimensional NMR experiments. Heretofore, 13,14,15,16-tetranorclerodane, callicarpenal, has never been identified from natural sources. Complete (1)H and (13)C NMR assignment data are provided for this compound. In bite deterrent studies, spathulenol, intermedeol, and callicarpenal showed significant repellent activity against A. aegypti and Anopheles stephensi.     

New anthocyanidin and anthocyanin pigments from blue plumbago

Phytochemical investigations of blue plumbago ( Plumbago auriculata Poir. syn. Plumbago capensis Thunb.) flowers have led to the isolation of six new anthocyanins based on three new anthocyanidins with 5,7-dimethoxylated A-rings. Their structures were identified by 2D nuclear magnetic resonance and high-resolution mass spectrometry as the 3-O-β-galactopyranosides (1,2,4) and 3-O-α-rhamnopyranosides (3,5,6) of 5,7-dimethyldelphinidin, 5,7-dimethylpetunidin, and 5,7-dimethylmalvidin. Identification of 1-6 implies new structures for the previously reported anthocyanidins pulchellidin, europinidin, and capensinidin to be 5,7-dimethoxy-3,3',4',5'-tetrahydroxyflavylium, 5,7,3'-trimethoxy-3,4',5'-trihydroxyflavylium, and 5,7,3',5'-tetramethoxy-3,4'-dihydroxyflavylium cations, respectively. The anthocyanins (0.4 mg/g flowers) were accompanied by the dihydroflavonol taxifolin 3'-O-β-glucopyranoside (1.4 mg/g) and the flavonols 5-methylquercetin 3-O-α-rhamnopyranoside (8.8 mg/g) and 5-methylquercetin (0.4 mg/g). The anthocyanins 1-6 are the first reported natural anthocyanins with no free hydroxyl groups in their 5- and 7-positions on their A-rings. They have thus no possibility of forming the tautomeric quinonoidal bases (anhydrobases), which are related to the free hydroxyl groups in the 5- and 7-positions of previously reported anthocyanins. The genes behind the 5,7-dimethoxylated anthocyanins might be useful for making anthocyanins with special properties (colors, etc.).     

New multifunctional surfactants from natural phenolic acids

Several new multifunctional molecules derived from natural sources such as amino acids and hydroxycinnamic acids were synthesized. They exhibit various activities such as emulsifying, UV-protecting, and radical scavenging, thereby conforming to the latest requirements for cosmetic ingredients. The synthesis comprises only a few steps: (i) the amino acid, the acid groups of which are protected by esterification, is coupled with ferulic or caffeic acid; (ii) the p-hydroxyl group of the cinnamic derivative reacts with dodecyl bromide in the presence of potassium carbonate (the resulting compounds are highly lipophilic and tested as water/oil (W/O) emulsifiers); (iii) these molecules, by deprotonating the acid groups of the amino acids, with successive salification, are more hydrophilic, with stronger O/W emulsifying properties. The new multifunctional surfactants might prove useful for the treatment of multiple skin conditions, including loss of cellular antioxidants, damage from free radicals, damage from UV, and others.     

Isolation and identification of mosquito (Aedes aegypti ) biting deterrent fatty acids from male inflorescences of breadfruit (Artocarpus altilis (Parkinson) Fosberg)

Dried male inflorescences of breadfruit ( Artocarpus altilis , Moraceae) are burned in communities throughout Oceania to repel flying insects, including mosquitoes. This study was conducted to identify chemicals responsible for mosquito deterrence. Various crude extracts were evaluated, and the most active, the hydrodistillate, was used for bioassay-guided fractionation. The hydrodistillate and all fractions displayed significant deterrent activity. Exploratory GC-MS analysis revealed more than 100 distinctive peaks, and more than 30 compounds were putatively identified, including a mixture of terpenes, aldehydes, fatty acids, and aromatics. A systematic bioassay-directed study using adult Aedes aegypti females identified capric, undecanoic, and lauric acid as primary deterrent constituents. A synthetic mixture of fatty acids present in the most active fraction and individual fatty acids were all significantly more active than N,N-diethyl-m-toluamide (DEET). These results provide support for this traditional practice and indicate the potential of male breadfruit flowers and fatty acids as mosquito repellents.     

Cadmium leaching from some New Zealand pasture soils

Cadmium (Cd) inputs and losses from agricultural soils are of great importance because of the potential adverse effects Cd can pose to food quality, soil health and the environment in general. One important pathway for Cd losses from soil systems is by leaching. We investigated loss of Cd from a range of contrasting New Zealand pasture soils that had received Cd predominantly from repeated applications of phosphate fertilizer. Annual leaching losses of Cd ranged between 0.27 and 0.86 g ha^–l, which are less than most losses recorded elsewhere. These losses equate to between 5 and 15% of the Cd added to soil through a typical annual application of single superphosphate, which in New Zealand contains on average 280 mg Cd kg^?1 P. It appears that Cd added to soil from phosphate fertilizer is fairly immobile and Cd tends to accumulate in the topsoil. The pH of the leachate and the total volume of drainage to some extent control the amount of Cd leached. Additional factors, such as the soil sorption capacity, are also important in controlling Cd movement in these pasture soils. The prediction of the amount of Cd leached using the measured concentrations of Cd in the soil solution and rainfall data resulted in an overestimation of Cd losses. Cadmium concentrations in drainage water are substantially less than the current maximum acceptable value of 3 µg l^?1 for drinking water in New Zealand set by the Ministry of Health.     

New alkamides from maca (Lepidium meyenii)

Maca (Lepidium meyenii) has been used as a food in Peru for thousands of years. More recently a wide array of commercial maca products have gained popularity as dietary supplements, with claims of anabolic and aphrodisiac effects, although the biologically active principles are not fully known. In an earlier chemical investigation, two new alkamides and a novel fatty acid, as well as the N-hydroxypyridine derivative, macaridine, were isolated from L. meyenii. Further examination has led to the isolation of five additional new alkamides, namely, N-benzyl-9-oxo-12Z-octadecenamide (1), N-benzyl-9-oxo-12Z,15Z-octadecadienamide (2), N-benzyl-13-oxo-9E,11E-octadecadienamide (3), N-benzyl-15Z-tetracosenamide (4), and N-(m-methoxybenzyl)hexadecanamide (5). Their structures were established by spectrometric and spectroscopic methods including ESI-HRMS, EI-MS, (1)H, (13)C, and 2D NMR, as well as (1)H-(15)N 2D HMBC experiments. In addition, the identity of N-benzyl-15Z-tetracosenamide (4) was confirmed by synthesis. These compounds have been found from only L. meyenii and could be used as markers for authentication and standardization.     

New lignans from the perisperm of Sesamum indicum

A procedure, based on XAD-4 adsorption resin, which permits the obtainment of enriched polyphenolic extracts from Sesamum indicum perisperm (coat) has been developed. Chemical analysis of the obtained extracts led to the identification of 16 lignans. Among them, two new lignans, (+)-saminol and (+)-episesaminone-9-O-beta-D-sophoroside, have been isolated. Additionally, the relative stereochemistry of (-)-sesamolactol, previously reported as todolactol A epimer, has been unequivocally defined using X-ray crystallography. The structures of all new compounds were determined by spectroscopic methods, mainly by the concerted application of 1D and 2D NMR techniques (HMQC, HMBC, and NOESY) and mass spectroscopy.     

New analogue of gymnodimine from a Gymnodinium species

A spiroimine, gymnodimine B (1), was isolated from cells recovered by filtration from cultures of a marine dinoflagellate, Gymnodinium sp. Its structure was identified by one- and two-dimensional NMR spectroscopy and mass spectrometry. Gymnodimine B is similar in structure to gymnodimine (2) but contains an exocyclic methylene at C-17 and an allylic hydroxyl group at C-18.     

Decision making and the logging industry: An example from New Zealand

The West Taupo forests centred on Pureora are the last remaining, relatively unmodified lowland podocarp forests in the North Island of New Zealand. Since 1976, a vigorous campaign to preserve these forests, the home of the increasingly rare kokako, or blue wattled crow, has been mounted and has resulted in a three-year moratorium on logging from 1 January 1979. This article traces the main events which led to this decision, beginning with the first real show of strength by New Zealand conservationists in connection with the power scheme at Manapouri, and continuing with a survey of the changing attitudes of the New Zealand Forest Service to the remaining reserves of native timber. The implications of the West Taupo decision for the forests of the West Coast of the South Island are examined.     

New methodology for removing carbonyl compounds from sweet wines

Sweet white wines from botrytized grapes present high SO2 levels because of their high sulfur dioxide binding power. The objective of this work was to develop a new method for reducing this binding power by partially eliminating the carbonyl compounds naturally present in these wines that are responsible for this phenomenon. A selective liquid-solid removal technique was developed. Phenylsulfonylhydrazine was selected as the best candidate for removing carbonyl compounds. Its reactivity in the presence or absence of sulfur dioxide was verified in model media containing acetaldehyde, pyruvic acid, and 2-oxoglutaric acid, some of the main carbonyl compounds responsible for the SO2 binding power of sweet wines. The scavenging function was grafted on porous polymer supports, and its efficiency was evaluated in model wines. Dependent upon the supports used, different quantities of carbonyl compounds (over 90% in some cases) were removed in a few days. The presence of sulfur dioxide delayed removal without changing its quality. The results obtained showed that the method removed carbonyl compounds efficiently and was applicable to wines at any stage in winemaking.     

New dammarane-type saponins from the galls of Sapindus mukorossi

Five new dammarane-type saponins, 3beta,7beta,20(S),22-tetrahydroxydammar-24-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 3beta,7beta,20(S),22,23-pentahydroxydammar-24-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 3beta,7beta,20(S),22,25-pentahydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, 25-methoxy-3beta,7beta,20(S),22-tetrahydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, and 25-methoxy-3beta,7beta,20(R)-trihydroxydammar-23-ene-3-O-alpha-l-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside, named sapinmusaponins A (1), B (2), C (3), D (4), and E (5), respectively, together with three known phenylpropanoid glycosides (6-8), were isolated from the galls of Sapindus mukorossi. The structures of these saponins were elucidated on the basis of spectroscopic analyses and chemical methods. Preliminary bioassay data revealed that saponins 1 and 3-5 showed moderate cytotoxic activity (ED50 approximately 9-18 microg/mL) against human tumor cell lines (Hepa59T/VGH, NCI, HeLa, and Med) and that 1-5 were inactive in vitro against HIV replication in H9 lymphocytes.     

Composition of iron-manganese concretions from some New Zealand soils

A selection of iron-manganese concretions from five reference soil profiles and a buried loess deposit in New Zealand have been studied. Concretions appear to have developed by the precipitation of amorphous iron and manganese oxides among soil particles. X-ray fluorescence analysis shows that the concentrations of Fe, Mn, Co and Ba in the concretions are generally higher, and those of K, Ca, Si, and Al are generally lower, than in the soil materials surrounding the concretions, whereas Ti, Zn, S, and P show little variation. Other approximate analyses indicate that Cu, Ni, Mo, V, and Pb tend to be concentrated in concretions but for Ga, Zr, Sr, Li, and Rb there was no discernible trend. Electron probe microanalyses of some concretions show that Co and Ba are concentrated in Mn-rich phases rather than Fe-rich phases.Comparison with published results for concretions (Mn nodules) from the ocean floor and the floor of Lake Ontario indicates that, on average, marine concretions have higher Mn, and lower Si and Al concentrations than soil concretions, and that marine concretions have lower Fe concentrations than either Ontario or soil concretions.