Steven F. Vaughn

Evaluation of alkyl esters from Camelina sativa oil as biodiesel and as blend components in ultra low-sulfur diesel fuel ☆

Methyl and ethyl esters were prepared from camelina [Camelina sativa (L.) Crantz] oil by homogenous base-catalyzed transesterification for evaluation as biodiesel fuels. Camelina oil contained high percentages of linolenic (32.6 wt.%), linoleic (19.6 wt.%), and oleic (18.6 wt.%) acids. Consequently, camelina oil methyl and ethyl esters (CSME and CSEE) exhibited poor oxidative stabilities and high iodine values versus methyl esters prepared from canola, palm, and soybean oils (CME, PME, and SME). Other fuel properties of CSME and CSEE were similar to CME, PME, and SME, such as low temperature operability, acid value, cetane number, kinematic viscosity, lubricity, sulfur and phosphorous contents, as well as surface tension. As blend components in ultra low-sulfur diesel fuel, CSME and CSEE were essentially indistinguishable from SME and soybean oil ethyl ester blends with regard to low temperature operability, kinematic viscosity, lubricity, and surface tension.

Allelochemicals isolated from tissues of the invasive weed garlic mustard (Alliaria petiolata).

Garlic mustard (Alliaria petiolata) is a naturalized Eurasian species that has invaded woodlands and degraded habitats in the eastern United States and Canada. Several phytotoxic hydrolysis products of glucosinolates, principally allyl isothiocyanate (AITC) and benzyl isothiocyanate (BzITC), were isolated from dichloromethane extracts of garlic mustard tissues. AITC and BzITC were much more phytotoxic to wheat (Triticum aestivum) than their respective parent glucosinolates sinigrin and glucotropaeolin. However, garden cress (Lepidium sativum) growth was inhibited to a greater degree by glucotropaeolin than BzITC, possibly due to conversion to BzITC by endogenous myrosinase. Sinigrin and glucotropaeolin were not detected in leaf/stem tissues harvested at the initiation of flowering, but were present in leaves and stems harvested in the autumn. Sinigrin levels in roots were similar for both sampling dates, but autumn-harvested roots contained glucotropaeolin at levels over three times higher than spring-harvested roots. The dominance of garlic mustard in forest ecosystems may be attributable in part to release of these phytotoxins, especially from root tissues.

Volatile Allelochemicals Released by Crucifer Green Manures

Several members of the crucifer family (Brassicaceae), including white mustard (Brassica hirta Moench), brown mustard [B. juncea (L.) Coss], black mustard [B. nigra (L.) Koch], leafy turnip (B. campestris L.), rapeseed (B. napus L.), and garden cress (Lepidium sativum L.) were examined for their potential as allelopathic green manure crops. Hemp sesbania [Sesbania exaltata (Raf.) Rydb. Ex A. W. Hill] germination and fresh weight was inhibited by chopped leaf tissues of all green manures tested, including wheat (Triticum aestivum L.), when added to a sandy loam soil. Wheat seed germination was inhibited only by B. nigra, B. hirta, and L. sativum, although none of the treatments reduced fresh weight of germinated seedlings. The major volatiles released by chopped plants were determined by solid-phase microextraction sampling and identified by gas chromatography–mass spectrometry (GC-MS). Volatiles included allyl isothiocyanate (allyl-ITC), 3-butenyl isothiocyanate, benzyl isothiocyanate (benzyl-ITC), cis-3-hexen-1-ol, and trans-2-hexenal. These compounds, together with methyl-ITC (methyl-ITC), β-phenylethyl-ITC, benzaldehyde, β-ocimene, and α-farnesene were tested for inhibition of seed germination of several crop and weed species when applied as volatiles. Of these, allyl-ITC and methyl-ITC were the most inhibitory, completely inhibiting the germination of all species at a headspace gas concentration of 1 ppm in airtight glass containers. Selecting mustard green manures that release high levels of allyl-ITC would appear to be optimal for allelopathic activity, and plants that produce high levels of benzyl-ITC also appear promising.

Variation in Allyl Isothiocyanate Production Within Brassica Species and Correlation with Fungicidal Activity

Brassica nigra (black mustard) and B. juncea (Indian mustard) genotypes were tested for pathogen suppression and release of allyl isothiocyanate (AITC), a fungitoxic volatile produced in mustard tissue after enzymatic hydrolysis of allyl glucosinolate (sinigrin). In bioassays, 28 genotypes of B. nigra and 35 genotypes of B. juncea were screened for inhibition of the potato pathogens Helminthosporium solani and Verticillium dahliae by volatiles released from macerated leaf tissue. Release of AITC from plant tissue was quantified by gas chromatography; isothiocyanate profiles were determined by headspace analysis. All mustard genotypes produced compounds that suppressed radial growth of both fungi. Growth suppression and AITC release differed significantly (P < 0.001) among genotypes of B. nigra and B. juncea. Mustard treatments releasing >1.2 mg AITC/g plant tissue were fungicidal to both pathogens. Headspace analysis confirmed that allyl glucosinolate was the major glucosinolate in all genotypes of B. nigra tested; most genotypes also produced 2-phenylethyl-isothiocyanate (ITC). Brassica juncea genotypes produced variable amounts of AITC and other volatiles with antimicrobial activity, including 2-phenylethyl-ITC, benzyl-ITC, and 3-butenyl-ITC. Evaluating mustards from geographically diverse locations allowed selection of mustard genotypes that may be useful in breeding programs designed to develop disease-suppressing green manure cultivars.

Volatile monoterpenes inhibit potato tuber sprouting

Several volatile monoterpenes, which are among the major constituents of several easily obtainable essential oils, were phytotoxic in the gaseous phase to emerged potato tuber sprouts. Analyses of the more phytotoxic monoterpenes were conducted using a continuous-flow system in which the compounds were released as volatiles into the headspace surrounding the tubers. Several of these compounds, which have low mammalian toxicities and are currently used in large amounts as flavorings, over-the-counter medications and perfumes, effectively inhibited sprouting and fungal growth at relatively low molar concentrations.CompendioVarios monoterpenos volátiles, que se encuentran entre los principales constituyentes de diversos aceites esenciales fácilmente obtenibles, fueron fitotóxicos en estado gaseoso a los brotes del tubérculo de papa. Se condujeron análisis de los monoterpenos más tóxicos utilizando un sistema de flujo continuo en el cual los compuestos fueron liberados como gases en el espacio superior que rodeaba a los tubérculos. Varios de estos compuestos, que poseen bajas toxicidades para los mamíferos y son utilizados en la actualidad en grandes cantidades como condimentos, medicinas de venta libre y perfumes, inhibieron eficientemente el brotamiento y el crecimiento de hongos a concentraciones molares relativamente bajas.

Herbicidal activity of glucosinolate-containing seedmeals

Abstract Defatted seedmeals from 15 glucosinolate-containing plant species were analyzed for herbicidal activity by determining inhibition of seedling emergence when added to a sandy loam soil containing wheat and sicklepod seeds at concentrations of 0.1, 0.5, and 1% (w/w). In general, the seedmeals were more phytotoxic to wheat than sicklepod. For wheat, all of the seedmeals significantly inhibited seedling emergence at the 1.0% concentration. At the 0.1% concentration three of the seedmeals (Indian mustard, money plant, and field pennycress) completely inhibited wheat emergence. For sicklepod emergence, eight of the seedmeals were completely inhibitory at the 1% level (Indian mustard, field pennycress, garden rocket, Siberian wallflower, English wallflower, garden cress, sweet alyssum, and evening stock) and four were completely inhibitory at the 0.5% level (brown mustard, garden rocket, English wallflower, and sweet alyssum). Intact glucosinolates and their corresponding hydrolysis products varied among the seedmeals with the highest activity. Major hydrolysis products produced by the seedmeals with the most phytotoxicity, respectively, included 2-propenyl (allyl) isothiocyanate (AITC) by brown mustard seedmeal, allyl thiocyanate and AITC by field pennycress seedmeal, erucin (4-methylthiobutyl isothiocyanate) by arugula seedmeal, 3-butenyl isothiocyanate and lesquerellin (6-methylthiohexyl isothiocyanate) by sweet alyssum seedmeal, and isopropyl isothiocyanate by money plant seedmeal. From our data it appears that both the type and concentration of glucosinolates and their hydrolysis products present in the seedmeals affect seed-emergence inhibition. Nomenclature: English wallflower, Erysimum cheiri (L.) Crantz; evening stock, Matthiola longipetala (Vent.) DC. MTLLB; Field pennycress, Thlaspi arvense L. THLAR; garden cress, Lepidium sativum L. ‘Cressida’ LEPSA; garden rocket, Eruca vesicaria (L.) Cav. subsp. sativa (Mill.) Thell. ‘Astro’ ERUVE; Indian mustard, Brassica juncea (L.) Czern. ‘Southern Giant Curled,’ BRSJU; money plant, Lunaria annua L.; Siberian wallflower, Erysimum × allionii; sicklepod, Senna obtusifolia (L.) H. S. Irwin & Barneby CASOB; sweet alyssum, Lobularia maritima (L.) Desv. LOUMA; wheat, Triticum aestivum L. ‘Cardinal’.

Lipoxygenase-derived aldehydes inhibit fungi pathogenic on soybean.

Several unsaturated aldehydes are produced from polyunsaturated fatty acids via the lipoxygenase pathway when soybean (Glycine max) plants are wounded mechanically or by pathogens. The effects of four of these aldehydes were examined on the growth of isolated fungal cultures ofColletotrichum truncatum, Rhizoctonia solani, andSclerotium rolfsii. (E)-2-Hexenal, (E)-2-nonenal, and (Z)-3-nonenal inhibited the growth ofR. solani andS. rolfsii at 35 μmol added per liter or greater when applied as volatiles, although higher levels were required for inhibition ofC. truncatum. (E)-4-Hydroxy-2-nonenal was the most inhibitory compound when applied directly in the growth medium, but it had the least effect as a volatile.

Biofumigant compounds released by field pennycress (Thlaspi arvense) seedmeal.

Defatted field pennycress (Thlaspi arvense L.) seedmeal was found to completely inhibit seedling germination/emergence when added to a sandy loam soil containing wheat (Triticum aestivum L.) and arugula [Eruca vesicaria (L.) Cav. subsp. sativa (Mill.) Thell.] seeds at levels of 1.0% w/w or higher. Covering the pots with Petri dishes containing the soil-seedmeal mixture decreased germination of both species at the lowest application rate (0.5% w/w), suggesting that the some of the phytotoxins were volatile. CH2Cl2, MeOH, and water extracts of the wetted seedmeal were bioassayed against wheat and sicklepod (Senna obtusifolia (L.) H. S. Irwin & Barneby) radicle elongation. Only the CH2Cl2 extract was strongly inhibitory to both species. Fractionation of the CH2Cl2 extract yielded two major phytotoxins, identified by gas chromatography–mass spectrometry and NMR as 2-propen-1-yl (allyl) isothiocyanate (AITC) and allyl thiocyanate (ATC), which constituted 80.9 and 18.8%, respectively, of the active fraction. When seeds of wheat, arugula and sicklepod were exposed to volatilized AITC and ATC, germination of all three species was completely inhibited by both compounds at concentrations of 5 ppm or less. In field studies, where seedmeal was applied at 0.50, 1.25, and 2.50 kg/m2 and tarped with black plastic mulch, all of the treatments significantly reduced dry weight of bioassay plants compared to the tarped control, with the highest seedmeal rate decreasing dry matter to less than 10% of the control 30 d after seedmeal application. Field pennycress seedmeal appears to offer excellent potential as a biofumigant for high-value horticultural crops for both conventional and organic growers.

Cyclic lipopeptide profile of three Bacillus subtilis strains; antagonists of Fusarium head blight

The objective of the study was to identify the lipopetides associated with three Bacillus subtilis strains. The strains are antagonists of Gibberella zeae, and have been shown to be effective in reducing Fusarium head blight in wheat. The lipopeptide profile of three B. subtilis strains (AS43.3, AS43.4, and OH131.1) was determined using mass spectroscopy. Strains AS43.3 and AS43.4 produced the anti-fungal lipopeptides from the iturin and fengycin family during the stationary growth phase. All three strains produced the lipopeptide surfactin at different growth times. Strain OH131.1 only produced surfactin under these conditions. The antifungal activity of the culture supernatant and individual lipopeptides was determined by the inhibition of G. zeae. Cell-free supernatant from strains AS43.3 and AS43.4 demonstrated strong antibiosis of G. zeae, while strain OH131.1 had no antibiosis activity. These results suggest a different mechanism of antagonism for strain OH131.1, relative to AS43.3 and AS43.4.

Isolation and identification of (3-methoxyphenyl)acetonitrile as a phytotoxin from meadowfoam (Limnanthes alba) seedmeal

Ethyl ether, ethanol, and water extracts of meadowfoam (Limnanthes alba Hartweg ex. Benth.) seedmeal were prepared and bioassayed against velvetleaf (Abutilon theophrasti Medicus) and wheat (Triticum aestivum L. “Cardinal”). Both the ethyl ether and ethanol fractions, but not the water extract, inhibited velvetleaf and wheat radicle elongation. Fractionation of the extracts indicated that (3-methoxyphenyl)acetonitrile (3-MPAN) was the active compound from both extracts, comprising >97% of the active ethanol fraction. 3-Methoxybenzyl isothiocyanate, which had been previously shown to be the major breakdown product of glucolimnanthin, the majorL. alba glucosinolate, was not detected in either extract. Radicle elongation of velvetleaf and wheat were inhibited by 3-MPAN with I50 (the concentration required to inhibit growth by 50%) values of approximately 4 × 10−4 M (velvetleaf) and 7×10−4 M (wheat).