Synthetic molecular mimics of naturally occurring cyclopentenones exhibit antifungal activity towards pathogenic fungi

The naturally occurring reactive electrophilic species 12-oxo-phytodienoic acid (12-oxo-PDA) is a potent antifungal agent, whereas the plant growth regulator jasmonic acid, which is synthesized from 12-oxo-PDA, is ineffective. To address what structural features of the molecule endow it with antifungal activity, we synthesized a series of molecular mimics of 12-oxo-PDA varying in the length of the alkyl chain at its C-4 ring position. The octyl analogue (4-octyl cyclopentenone) was the most effective at suppressing spore germination and subsequent mycelial growth of a range of fungal pathogens and was particularly effective against Cladosporium herbarum and Botrytis cinerea, with minimum fungicidal concentrations in the range 100-200 µM. Introduction of a carboxyl group to the end of the chain, mimicking natural fatty acids, markedly reduced antifungal efficacy. Electrolyte leakage, indicative of membrane perturbation, was evident in both C. herbarum and B. cinerea exposed to 4-octyl cyclopentenone. Lipid composition analysis of the fungal spores revealed that those species with a high oil content, namely Fusarium oxysporum and Alternaria brassicicola, were less sensitive to 4-octyl cyclopentenone. The comparable hydrophobicity of 4-octyl cyclopentenone and 12-oxo-PDA accounts for the similar spore suppression activity of these two compounds. The relative ease of synthesis of 4-octyl cyclopentenone makes it an attractive compound for potential use as an antifungal agent. © 2011 SGM.

The fabrication of biodegradable nanospheres from novel hydroxalkanoates for the delivery of actives of pharmaceutical and agricultural interest

This work describes the fabrication of nanospheres from a range of novel polyhydroxyalkanoates supplied by Monsanto, St Louis, Missouri, USA for the delivery of selected actives of both pharmaceutical and agricultural interest. Initial evaluation of established microsphere and nanosphere fabrication techniques resulted in the adoption and optimisation of a double sonication solvent evaporation method involving the synperonic surfactant F68. Nanospheres could be consistently generated with this method. Studies on the incorporation and release of the surrogate protein Bovine Serum Albumin V demonstrated that BSA could be loaded with between 10-40% w/w BSA without nanosphere destabilisation. BSA release from nanospheres into Hanks Balanced Salts Solution, pH 7.4, could be monitored for up to 28 days at 37°C. The incorporation and release of the Monsanto actives - the insecticide Admire® ({ 1-[(6-chloro-3-pyridinyl)methyIJ-N-nitro-2-imidazolidinimine}) and the plant growth hormone potassium salt Gibberellic acid (GA3K) from physico-chemically characterised polymer nanospheres was monitored for up to 37 days and 28 days respectively, at both 4°C and 23°C. Release data was subsequently fitted to established kinetic models to elaborate the possible mechanisms of release of actives from the nanospheres. The exposure of unloaded nanospheres to a range of physiological media and rural rainwater has been used to investigate the role polymer biodegradation by enzymatic and chemical means might play in the in vivo release of actives and agricultural applications. The potential environmental biodegradation of Monsanto polymers has been investigated using a composting study (International Standard ISO/FDIS 14855) in which the ultimate aerobic biodegradation of the polymers has been monitored by the analysis of evolved carbon dioxide. These studies demonstrated the potential of the polymers for use in the environment, for example as a pesticide delivery system.

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.

Biomass production in short rotation effluent-irrigated plantations in North-West India

This study estimates above-ground biomass in high density plantations of six important semi-arid tree species at Palwal (70 km from Delhi) irrigated with secondary treated sewage water at the rate of 0, 25, 50 and 100% of daily net evaporation potential (EP). In 2.5 y old plantations (plant spacing, 2 m x 2 m for single stem species and 2 m x 1 m for multi-stem species), Melia azedarach showed fairly high biomass production (38.4 t/ha) followed by Ailanthus excelsa (27.2 t/ha). Order of biomass production (kg / tree) was: Eucalyptus tereticornis (24.1) > A. excelsa (21.8) > M. azedarach (12.6) > Populus deltoides clone G 48 (8.3) > Alstonia scholaris (6.6)> Pongamia pinnata (3.7). Survival of plants after 2.5 y ranged from 25.2% in P. deltoides to 71.7% in P. pinnata, and had a significant effect on biomass production per unit area. ANOVA shows that levels of irrigation (0 - 100%) did not have statistically significant effect on plant growth. Correlation between diameter and biomass was found highly significant (p< 0.01) with R2 nearing to 1.

Biological activities of compounds from Piper species

It is well established that secondary metabolites play an important role in plant chemical defense. In an effort to find natural herbicides research on plant growth regulatory activity of secondary metabolites has received more and more attention recently. The genus Piper has been an important source for useful secondary metabolites.^ Crude extracts from Piper species inhibited gram-positive bacteria and higher plant growth under laboratory conditions. Bioassay-guided isolation and purification lead to the identification of safrole, a phenylpropene, as the responsible agent for the inhibitory activity. Safrole was found to leach from naturally fallen leaves with water. Mechanisms of plant growth inhibition by safrole were investigated. Disassociation of cell membrane from cell walls was determined to be a major cause.^ Phenylpropenes structurally similar to safrole had similar phytogrowth inhibitory activity. It is postulated that phenylpropanoids are an important group of naturally occurring secondary metabolites in plant-plant interactions. ^

The importance of marine subsidies for terrestrial consumers in coastal Peru

The Peruvian coast is one the best examples of cross-ecosystem food web exchanges, in which resources from one of the richest marine ecosystems subsidize consumers in one of the driest deserts on Earth. Marine subsidies are resources that originate in the marine ecosystem, and that contribute to increase the density of consumers in the recipient ecosystem. I examined the effects of marine subsidies on animal populations in the Peruvian coastal desert. ^ I combined several approaches to study the linkages between marine resources and terrestrial consumers, such as surveying the spatial distribution and estimating the relative abundance of terrestrial consumers, studying the diet of geckos and lizards through stomach content analyses, and examining the desert food web with carbon and nitrogen stable isotope analyses. ^ I found that the distribution and diet of desert consumers were tightly coupled to the availability of marine subsidies. I revealed linkages along two pathways of nutrient fluxes: tidal action that washes ashore macroalgae and cadavers of marine organisms, and animal transport in places where pinnipeds and seabirds congregate for reproduction. In the first pathway, intertidal algivivores made marine resources available to terrestrial consumers by moving between the intertidal and supratidal zone. The relative contribution of terrestrial and algal carbon sources varied among terrestrial consumers, because scorpions assimilated a lower proportion of energy from macroalgae than did geckos and solifuges. In the second pathway, I found that pinniped colonies influenced the diet of desert consumers, and contributed to support large populations of lizards and geckos. By combining field observations, and stomach and stable isotope analyses, I constructed a simplified food web for a large sea lion colony, showing the number of trophic levels that originate from pinniped-derived nutrients. ^ My study demonstrates the enormous importance of marine resources for the diet of desert consumers. The near absence of rainfall along the Peruvian coast promotes an extreme dependence of terrestrial consumers on marine resources, and causes permanent food web effects that are affected by temporal variability in marine productivity, rather then temporal patterns of desert plant growth. ^

Modeling Nymphoides architecture: A morphological analysis of Nymphoides aquatica (Menyanthaceae)

• Premise of the study: Species in the aquatic genus Nymphoides have inflorescences that appear to arise from the petioles of floating leaves. The inflorescence-floating leaf complex can produce vegetative propagules and/or additional inflorescences and leaves. We analyzed the morphology of N. aquatica to determine how this complex relates to whole plant architecture and whether whole plant growth is sympodial or monopodial. • Methods: We used dissections, measurements, and microscopic observations of field-collected plants and plants cultivated for 2 years in outdoor tanks in south Florida, USA. • Key results: Nymphoides aquatica had a submerged plagiotropic rhizome that produced floating leaves in an alternate/spiral phyllotaxy. Rhizomes were composed of successive sympodial units that varied in the number of leaves produced before the apex terminated. The basic sympodial unit had a prophyll that subtended a renewal-shoot bud, a short-petioled leaf (SPL) with floating lamina, and an inflorescence; the SPL axillary bud expanded as a vegetative propagule. Plants produced either successive basic sympodial units or expanded sympodia that intercalated long-petioled leaves between the prophyll and the SPL. • Conclusions: Nymphoides aquatica grows sympodially, forming a rhizome composed of successive basic sympodia and expanded sympodial units. Variations on these types of sympodial growth help explain the branching patterns and leaf morphologies described for other Nymphoides species. Monitoring how these two sympodial phases are affected by water depth provides an ecologically meaningful way to assess N. aquatica’s responses to altered hydrology.

Hydro-physical characterization of media used in agricultural systems to develop the best management practices for operation of an environmentally sustainable agricultural enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise