Factors affecting production of COS and CS2 in Leucaena and Mimosa species

Carbon disulfide (CS₂) and carbonyl sulfide (COS) are colorless, foul-smelling, volatile sulfur compounds with biocidal properties. Some plants produce CS₂ or COS or both. When used as an intercrop or forecrop, these plants may have agronomic potential in protecting other plants. Most of the factors which affect production of these plant-generated organic sulfides are unknown. We determined the effects of sulfate concentration, plant age, nitrogen fixation, drought stress, root injury (through cutting), and undisturbed growth on COS production in Leucaena retusa or Leucaena leucocephala and the effect of some of these factors on CS₂ production in Mimosa pudica. In addition, we determined if organic sulfides were produced in all Leucaena species. When L. retusa and M. pudica seedlings were grown in a plant nutrient medium with different sulfate concentrations (50 to 450 mg SL^-1), COS or CS₂ from crushed roots generally increased with increasing sulfate concentration. COS production was highest (74 ng mg^-1 dry root) for young L. retusa seedlings and declined to low amounts (<5 ng mg^-1 dry root) for older seedlings. Nitrogen fixation reduced the amounts of COS or CS₂ produced in L. leucocephala and M. pudica. Under conditions of undisturbed growth, root cutting, or drought stress, no COS production was detected in 4-to 8-weeks-old L. retusa plants. COS or CS₂ or both was obtained from crushed roots or shoots of all 13 known Leucaena species.     

Modeling of nitrogen transformations and translocations

Different submodels within complex model packages on N regimes-for plant N-uptake, net N-mineralization, nitrate leaching and microbial N immobilization-are critically reviewed mainly with regard to their prediction ability on the basis of three comparative papers. Only for some of the processes adequate statistical evaluation of the models was possible. Compared to the other statistically evaluable process, nitrate leaching, modeling of plant N-uptake yields the better results. Most models for mineralization use arbitrary approaches rather than empirical ones. Although only approximate estimates of N mineralisation were at hand, the models generally behave expectedly poor. Only one model-DAISY-out of 16 involved in the comparison uses an explicit microbial biomass sub-model including microbial growth, decline and maintenance terms. So DAISY is the only model coupling C and N cycles. But what is true for an individual model describing the C and N transformation of a lab incubation experiment seems to be valid for most of the complex simulation work on the C and N regimes: this model was said to be overparameterized with respect to the available data.     

Elicitation of volatile compounds in photomixotrophic cell culture of Petroselinum crispum

Photomixotrophic cells of Petroselinum crispum accumulated >500 mg chlorophyll per kg wet weight and grew well in a broad range of phytoeffector conditions. Autoclaved fungal cells were lethal for photoheterotrophic cells, but induced in photomixotrophic cells the formation of volatile n-alkanes, phthalides, coumarins, and elemicine. Most of the compounds elicited reached a concentration maximum between 20 and 30 h after addition of the mycelium, whereas the group of n-alkanes increased steadily during the 90 h monitored. Maximum concentrations were: 12 mg of graveolone, 1 mg of bergapten, 0.5 mg of sedanenolide, and 0.5 mg of n-tetradecane per 1 nutrient medium. A dose/effect relationship was found; 10 to 25 g of fungal wet weight per 1 culture medium resulted in maximum accumulation of volatiles. The formation of volatiles by photomixotrophic in vitro cells is discussed as an integral part of plant responses to ecological stress.     

Past vegetation changes in the Brazilian Pantanal arboreal–grassy savanna ecotone by using carbon isotopes in the soil organic matter

Measurements of the organic carbon inventory, its stable isotopic composition and radiocarbon content were used to deduce vegetation history from two soil profiles in arboreal and grassy savanna ecotones in the Brazilian Pantanal. The Pantanal is a large floodplain area with grass-dominated lowlands subject to seasonal flooding, and arboreal savanna uplands which are only rarely flooded. Organic carbon inventories were lower in the grassy savanna site than in the upland arboreal savanna site, with carbon decreasing exponentially with depth from the surface in both profiles. Changes in ¹³C of soil organic matter (SOM) with depth differed markedly between the two sites. Differences in surface SOM ¹³C values reflect the change from C₃ to C₄ plants between the sites, as confirmed by measurements of ¹³C of vegetation and the soil surface along a transect between the upland closed-canopy forest and lowland grassy savanna. Changes of ¹³C in SOM with depth at both sites are larger than the 3–4 per mil increases expected from fractionation associated with organic matter decomposition. We interpret these as recording past changes in the relative abundance of C₃ and C₄ plants at these sites. Mass balances with ¹⁴C and ¹³C suggest that past vegetational changes from C₃ to C₄ plants in the grassy savanna, and in the deeper part of the arboreal savanna, occurred between 4600 and 11 400 BP, when major climatic changes were also observed in several places of the South American Continent. The change from C₄ to C₃, observed only in the upper part of the arboreal savanna, was much more recent (1400 BP), and was probably caused by a local change in the flooding regime.     

Review: Biocatalytic transformations of ferulic acid: An abundant aromatic natural product

In this review we examine the fascinating array of microbial and enzymatic transformations of ferulic acid. Ferulic acid is an extremely abundant, preformed phenolic aromatic chemical found widely in nature. Ferulic acid is viewed as a commodity scale, renewable chemical feedstock for biocatalytic conversion to other useful aromatic chemicals. Most attention is focused on bioconversions of ferulic acid itself. Topics covered include cinnamoyl side-chain cleavage; nonoxidative decarboxylation; mechanistic details of styrene formation; purification and characterization of ferulic acid decarboxylase; conversion of ferulic acid to vanillin;O-demethylation; and reduction reactions. Biotransformations of vinylgualacol are discussed, and selected biotransformations of vanillic acid including oxidative and nonoxidative decarboxylation are surveyed. Finally, enzymatic oxidative dimerization and polymerization reactions are reviewed.     

Long-term effects of metals in sewage sludge on soils,microorganisms and plants

Summary This paper reviews the evidence for impacts of metals on the growth of selected plants and on the effects of metals on soil microbial activity and soil fertility in the long-term. Less is known about adverse long-term effects of metals on soil microorganisms than on crop yields and metal uptake. This is not surprising, since the effects of metals added to soils in sewage sludge are difficult to assess, and few long-term experiments exist. Controlled field experiments with sewage sludges exist in the UK, Sweden, Germany and the USA and the data presented here are from these long-term field experiments only. Microbial activity and populations of cyanobacteria,Rhizobium leguminosarum bv.trifolii, mycorrhizae and the total microbial biomass have been adversely affected by metal concentrations which, in some cases, are below the European Community's maximum allowable concentration limits for metals in sludge-treated soils. For example, N₂-fixation by free living heterotrophic bacteria was found to be inhibited at soil metal concentrations of (mg kg^–1): 127 Zn, 37 Cu, 21 Ni, 3.4 Cd, 52 Cr and 71 Pb. N₂-fixation by free-living cyanobacteria was reduced by 50% at metal concentrations of (mg kg^–1): 114 Zn, 33 Cu, 17 Ni, 2.9 Cd, 80 Cr and 40 Pb.Rhizobium leguminosarum bv.trifolii numbers decreased by several orders of magnitude at soil metal concentrations of (mg kg^–1): 130–200 Zn, 27–48 Cu, 11–15 Ni, and 0.8–1.0 Cd. Soil texture and pH were found to influence the concentrations at which toxicity occurred to both microorganisms and plants. Higher pH, and increased contents of clay and organic carbon reduced metal toxicity considerably. The evidence suggests that adverse effects on soil microbial parameters were generally found at surpringly modest concentrations of metals in soils. It is concluded that prevention of adverse effects on soil microbial processes and ultimately soil fertility, should be a factor which influences soil protection legislation.     

Prediction of the Reaction Equilibrium of Biocatalytic Reactions in Aqueous-Organic Two-Phase Systems

Biocatalytic reactions can be carried out in aqueous-organic two-phase systems. Several models to describe the thermodynamically-determined equilibrium position in such systems have appeared in the literature. Some of these models are only valid for dilute systems, whereas others can also be used for nondilute systems. In this paper, these models are described and compared. It is explained in what way the equilibrium constants of each model can be used to predict the product concentration in different organic solvents.     

The use of N-urethane-protected N-carboxyanhydrides (UNCAs) in amino acid and peptide synthesis

N-Urethane-protected N-carboxyanhydrides (UNCAs) are very reactives. They have been successfully used in peptide synthesis, in both solution and solid phase. We have demonstrated that UNCAs are interesting starting materials for the synthesis of various amino acid derivatives. Chemoselective reduction of UNCAs with sodium borohydride led the corresponding N-protected β amino alcohols. Reaction of UNCAs with Meldrum's acid, followed by cyclisation, yielded enantiomerially pure tetramic acid derivatives. Diastereoselective reduction of tetramic acid derivatives produced (4S,5S)-N-alkoxycarbonyl-4-hydroxy-5-alkylpyrrolidin-2-ones derived from amino acids, which after hydrolysis yielded statine and statine analogues. Tetramic acid derivatives could also be obtained by reaction of UNCAs with benzyl ethyl followed by hydrogenolytic deprotection and decarboxylation. UNCAs also reacted with phosphoranes to produce the ketophosphorane in excellent yields. Subsequent oxidation with oxone or with [bis(acetoxy)-iodol]-benzene produced vicinal tricarbonyl derivatives. These reactions usually proceeded smoothly and with high yields.     

Changes in organic matter composition of forest soil treated with a large amount of urea to promote ammonia fungi and the abilities of these fungi to decompose organic matter

Organic matter composition (lignin, holocellulose, 50% (v/v) methanol extract, water-soluble carbohydrate (WSC) and phenolics (WSP), petroleum ether extract, and ash) of A₀ layer soil treated with 700 g/m² of urea to promote ammonia fungi was investigated in a Japanese red pine (Pinus densiflora) forest. Nine species of fungi were found during the study period of 18 months after the treatment. Of these, seven species belong to the ammonia fungi. WSC content of the treated soil was lower than that of the control. Methanol extract content increased initially after the treatment, then decreased to below the control level. There were no consistent differences in other components between the treated plot and the control. The abilities to decompose cellulose, lignin, chitin, protein and lipid in 18 strains in 10 species of the ammonia fungi were also screened. Cellulose was not lysed byPseudombrophila deerata, Hebeloma spp. andLaccaria bicolor. Strong lignolytic activity was shown byLyophyllum tylicolor, Coprinus echinosporus andP. deerata. Chitin was decomposed byAmblyosporium botrytis, L. tylicolor, C. echinosporus andHebeloma vinosophyllum. All strains possessed proteolytic and lipolytic activities. Supply of glucose to the culture media resulted in weaker enzyme activities except for lignolytic ability.     

Effect of support material and enzyme pretreatment on enantioselectivity of immobilized subtilisin in organic solvents

Subtilisin Carlsberg was covalently attached to five macroporous acrylic supports of varying aquaphilicity (a measure of hydrophilicity). Kinetic parameters of the transesterification of S and R enantiomers of secphenethyl alcohol with vinyl butyrate, catalyzed by various immobilized subtilisins, were determined in anhydrous dioxane and acetonitrile. Enzyme enantioselectivity in acetonitrile, but not in dioxane, correlated with the aquaphilicity of the support; a mechanistic rationale for this phenomenon was proposed. Although the catalytic activity of immobilized subtilisin in anhydrous solvents strongly depended on enzyme pretreatment, the enantioselectivity was essential conserved. (c) 1994 John Wiley & Sons, Inc.