几种吡啶类化合物对土壤硝化的抑制作用比较

为了探明吡啶类化合物对土壤硝化作用的抑制效应,采用室内微宇宙试验,研究了2-氯-6(三氯甲基)硫酸盐、2-氯-6(三氯甲基)盐酸盐、吡啶混合物和吡啶X类化合物对潮土、红壤和水稻土中铵态氮硝化的抑制作用。结果表明,在35 d培养期内,吡啶类化合物处理土壤硝态氮含量明显低于对照(未添加吡啶类化合物),吡啶类化合物对土壤中铵态氮的硝化抑制率介于2.91%~91.92%,抑制强度先逐渐升高后降低,在培养21 d时抑制强度达到峰值。不同类型吡啶类化合物对土壤中铵态氮的硝化抑制效果存在差异,吡啶盐酸盐类化合物优于其他几类化合物;吡啶类化合物对土壤中铵态氮的硝化抑制作用与土壤类型有关,对3种土壤中铵态氮的硝化抑制作用表现为潮土>水稻土>红壤。就同一土壤而言,硝化抑制强度随着吡啶类化合物用量的增加而增加。     

Inhibition of nitrification in soils by volatile sulfur compounds

Carbon disulfide, dimethyl disulfide, methyl mercaptan, dimethyl sulfide, and hydrogen sulfide retard nitrification of ammonium in soils incubated in closed systems. The inhibitory effects of these volatile sulfur compounds on nitrification decrease in the order listed. Hydrogen sulfide is a relatively weak inhibitor of nitrification, but carbon disulfide is considerably more effective than patented nitrification inhibitors (N-Serve. AM, and ST) for inhibition of nitrification in closed systems.It is concluded from the work reported that the inhibitory effects of methionine, cystine, cysteine, and other nonvolatile organic sulfur compounds on nitrification in soils may be at least partly due to decomposition of these compounds by soil microorganisms with formation of volatile sulfur compounds that retard nitrification.     

Synthesis and quantitative structure-activity relationships of fluorine-containing 4,4-dihydroxylmethyl-2-aryliminooxazo(thiazo)lidines as trehalase inhibitors.

Five fluorine-containing 4,4-dihydroxylmethyl-2-aryliminooxazolidines and five 4,4-dihydroxylmethyl-2-aryliminothiazolidines were synthesized and evaluated for their inhibitory activity against trehalase in vitro. All these compounds were very readily synthesized compared with the natural trehalase inhibitors. They had moderate inhibitory activity toward trehalase, and showed larvicidal activity and inhibition action to insect flight. The steric parameters and semiempirical quantum parameters of these compounds were acquired by using the molecular modeling method and the PM3-SCF-MO method, respectively. A quantitative structure-activity relationship between half-inhibitory concentrations toward trehalase and the above parameters was established.     

芳香族化合物对土壤硝化作用的抑制研究

Aromatic compounds (ACs) in soil can induce competitive inhibition for soil NH₃ oxidation, and nitrification inhibitors can be used to this end. A laboratory incubation experiment was performed with 12 nitroaromatic compounds (NACs), 15 amidoaromatic compounds (AACs) and 20 hydroxyaromatic compounds (HACs) to assess the inhibitory effects of ACs on soil nitrification. Based on these results, the critical and optimal concentrations of ACs were determined for better inhibitory effects. Most of the test ACs were able to inhibit soil nitrification; the effectiveness differed with soil type. Among the ACs, the NACs with m-nitryl, amino or hydroxyl and the AACs with a nitro group or a chlorine atom on aromatic ring or with a p-hydroxyl were more effective. 3-nitroaniline, 4-aminophenol and 3-nitrophenol showed the greatest potential as nitrification inhibitors. The critical concentration of these compounds in brown soil and cinnamon soil was found to be 0.5 mg kg^-1 soil. Due to the toxicity, carcinogenicity and mutagenicity of ACs, further toxicological and ecotoxicological research is necessary before ACs are used as nitrification inhibitors in agricultural and horticultural practices.     

Protective effects of synthetic hydroxytyrosol acetyl derivatives against oxidative stress in human cells

Chemically stable di- and triacetyl derivatives of the natural o-diphenol antioxidant hydroxytyrosol were synthesized, and their chemical and biological antioxidant activities were assessed in comparison with that of the native synthetic compound. The chemical antioxidant activity of the selected compounds was evaluated by measuring the ferric reducing antioxidant power (FRAP). The data clearly indicate that, as expected, the hydroxytyrosol analogues, modified in the o-diphenolic ring, are devoid of any chemical antioxidant activity. On the contrary, both acetyl derivatives, at micromolar concentrations, equally protect against tert-butylhydroperoxide-induced oxidative damages in Caco-2 cells and human erythrocytes. This paper for the first time reports that chemically stable hydroxytyrosol acetyl derivatives, although devoid of chemical antioxidant activity, are as effective as the parent compound in protecting human cells from oxidative stress-induced cytotoxicity, after metabolization by esterases at the intestinal level, suggesting their possible utilization in either nutritional (functional food), cosmetic, or pharmaceutical preparations.     

Biological nitrification inhibition by Brachiaria humidicola roots varies with soil type and inhibits nitrifying bacteria, but not other major soil microorganisms

The tropical pasture grass Brachiaria humidiola (Rendle) Schweick releases nitrification inhibitory compounds from its roots, a phenomenon termed 'biological nitrification inhibition' (BNI). We investigated the influence of root exudates of B. humidicola on nitrification, major soil microorganisms and plant growth promoting microorganisms using two contrasting soil types, Andosol and Cambisol. The addition of root exudates (containing BNI activity that is expressed in Allylthiourea unit (ATU) was standardized in a bioassay against a synthetic inhibitor of nitrification, allylthiourea, and their function in soil was compared to inhibition caused by the synthetic nitrification inhibitor dicyandiamide. At 30 and 40 ATU g⁻¹soil, root exudates inhibited nitrification by 95% in fresh Cambisol after 60 days. Nitrification was also similarly inhibited in rhizosphere soils of Cambisol where B. humidicola was grown for 6 months. Root exudates did not inhibit other soil microorganisms, including gram-negative bacteria, total cultivable bacteria and fluorescent pseudomonads. Root exudates, when added to pure cultures of Nitrosomonas europaea , inhibited their growth, but did not inhibit the growth of several plant growth promoting microorganisms, Azospirillum lipoferum , Rhizobium leguminosarum and Azotobacter chroococcum. Our results indicate that the nitrification inhibitors released by B. humidicola roots inhibited nitrifying bacteria, but did not negatively affect other major soil microorganisms and the effectiveness of the inhibitory effect varied with soil type.     

pH对闽江河口湿地沉积物氮素转化关键过程的影响

以闽江河口湿地沉积物为研究对象,通过单变量的沉积物培养试验(pH=2.5,3.5,4.5,5.5,6.5),研究pH对湿地沉积物氮元素硝化、反硝化、矿化3个关键过程的影响。结果表明:低pH(pH=2.5)对硝化活性有明显的抑制作用,其余pH对沉积物的硝化速率影响不大,硝化细菌的数量和活性在强酸条件下限制明显。随时间推移,沉积物反硝化速率减小,反硝化活性增强。偏酸条件对反硝化活性有一定抑制作用,主要由于沉积物中反硝化细菌在酸性条件下不活跃或耐酸细菌数偏少。不同pH条件下,矿化速率基本无规律可循,表明pH对湿地沉积物矿化过程无直接影响。     

Nitrification inhibitors from the roots of Leucaena leucocephala

The nitrification inhibition (NI) bioassay guided fractionation of the methanol extract of lyophilized and milled roots of Leuceana leucocephala resulted in the isolation of four compounds, 1-4, as confirmed from their 1H and 13C NMR spectral data. Compound 1, gallocatechin, was the most active NI inhibitor at 12 microg/mL. Epigallocatechin, 2, and epicatechin, 4, isolated as mixtures, were not assayed individually for their NI inhibitory activities against the nitrification bacterium Nitrosomonas europaea.     

三种吡唑类硝化抑制剂对黑土中尿素氮转化的抑制效果研究

通过室内培养试验,研究了3种吡唑类硝化抑制剂CMP(1-甲氨甲酰-3-甲基吡唑);DMPP(3,4-二甲基吡唑磷酸盐);DMP(3,5-二甲基吡唑)在黑土上的抑制效果。其结果表明:在相同质量浓度下,3种吡唑类硝化抑制剂的硝化抑制顺序为CMP>DMPP>DMP。CMP是一种高效的硝化抑制剂,0.1%尿素添加量下强烈抑制了铵态氮的转化。DMP的抑制效果最差,在整个培养的第40 d,硝态氮的含量甚至超过了CK。     

Modes of action of nitrification inhibitors

 In recent years, substantial progress has been made towards understanding the modes of action for the specific inhibition of autotrophic NH₃ oxidation. This has included demonstrating that NH₃ monooxygenase (AMO) has a broad substrate range for catalytic oxidation, and the inhibitory effects of many compounds are due to competition for the active site. Other compounds, such as acetylenes, are oxidized by the normal catalytic cycle of AMO to highly reactive products which covalently bind the enzyme causing irreversible inhibition. Substantial evidence has shown the important role of Cu in the activity of AMO, and indicated that a large class of compounds containing thiono-S inhibit AMO activity by binding with Cu within the active site. Heterocyclic N compounds form another important class of nitrification inhibitors with little known about their mode of action, although evidence suggests that their inhibitory influence is closely related to the presence of ring N. Received: 21 July 1998     

Synthesis and antityrosinase mechanism of benzaldehyde thiosemicarbazones: novel tyrosinase inhibitors

p-Hydroxybenzaldehyde thiosemicarbazone (HBT) and p-methoxybenzaldehyde thiosemicarbazone (MBT) were synthesized and established by (1)H NMR and mass spectra. Both compounds were evaluated for their inhibition activities on mushroom tyrosinase and free-cell tyrosinase and melanoma production from B(16) mouse melanoma cells. Results showed that both compounds exhibited significant inhibitory effects on the enzyme activities. HBT and MBT decreased the steady state of the monophenolase activity sharply, and the IC(50) values were estimated as 0.76 and 7.0 μM, respectively. MBT lengthened the lag time, but HBT could not. HBT and MBT inhibited diphenolase activity dose-dependently, and their IC(50) values were estimated as 3.80 and 2.62 μM, respectively. Kinetic analyses showed that inhibition type by both compounds was reversible and their mechanisms were mixed-type. Their inhibition constants were also determined and compared. The research may supply the basis for the development of new food preservatives and cosmetic additives.     

Effects of urease inhibitors on nitrification in soils

The effects of 10 urease inhibitors on nitrification in soils were studied by determining the effects of 10 and 50 parts/10⁶ (soil basis) of each inhibitor on the amounts of nitrate and nitrite produced when soils treated with ammonium sulfate (200 μg of ammonium N/g of soil) were incubated (30°C) under aerobic conditions for 14 days. The urease inhibitors used (catechol. hydroquinone, p-benzoquinone, 2,3-dimethyl-p-benzoquinone, 2,5-dimethyl-p-benzoquinone. 2,6-dimethyl-p-benzoquinone. 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone. sodium p-chloromercuribenzoate, and phenylmercuric acetate) were those found most effective in previous work to evaluate more than 130 compounds as soil urease inhibitors. Their effects on nitrification were compared with those of three compounds patented as soil nitrification inhibitors (N-Serve. AM. and ST).Most of the urease inhibitors studied had little effect on nitrification when applied at the rate of 10 μg/g of soil. but had marked inhibitory effects when applied at the rate of 50 μg/g of soil. None inhibited nitrification as effectively as N-Serve. but phenylmercuric acetate inhibited nitrification more effectively than did AM or ST when applied at the rate of 10 μg/g of soil. Phenylmercuric acetate, 2,5-dimethyl-p-benzoquinone, and 2,6-dimethyl-p-benzoquinone had very marked effects on nitrification when applied at the rate of 50 μg/g of soil.     

Some furfural derivatives as nitrification inhibitors

Three series of furfural derivatives, namely N-O-furfural oxime ethers, furfural Schiff bases (furfurylidene anilines), and furfural chalcones, have been synthesized and evaluated for nitrification inhibition activity in laboratory incubation studies in typic Ustocrept soil. Furfural oxime ethers and furfural Schiff bases showed potential activity, but furfural chalcones were only mildly active. N-O-ethyl furfural oxime among the oxime ethers, and furfurylidine-4-chloroaniline among the furfural Schiff bases, performed the best. These two compounds showed more than 50% nitrification inhibition on the 45th day at 5% dose as compared to 73% inhibition by nitrapyrin. Activity of furfural oxime ethers decreased with an increase in carbon atoms in the N-O-alkyl side chain. Introduction of a chlorine atom in the phenyl ring of furfurylidene anilines increased the persistence of their activity. N-O-Ethyl furfural oxime and furfurylidine-4-chloroaniline coated urea performed at par with their application in solution form. Ethyl and N-O-isopropyl oxime, as well as chloro- and nitro- substituted Schiff bases, did not reveal any phytotoxicity (adverse effect on germination) on chickpea seeds (Cicer arietinum) even at the highest dose (40 ppm, soil basis).     

Studies of O,O-dimethyl α-(2,4-dichlorophenoxyacetoxy)ethylphosphonate (HW02) as a new herbicide. 1. Synthesis and herbicidal activity of HW02 and analogues as novel inhibitors of pyruvate dehydrogenase complex

On the basis of the previous work for optimization of O,O-diethyl α-(substituted phenoxyacetoxy)alkylphosphonates, further extensive synthetic modifications were made to the substituents in alkylphosphonate and phenoxy moieties of the title compounds. New O,O-dimethyl α-(substituted phenoxyacetoxy)alkylphosphonates were synthesized as potential inhibitors of pyruvate dehydorogenase complex (PDHc). Their herbicidal activity and efficacy in vitro against PDHc were examined. Some of these compounds exhibited significant herbicidal activity and were demonstrated to be effective inhibitors of PDHc from three different plants. The structure-activity relationships of these compounds including previously reported analogous compounds were studied by examining their herbicidal activities. Both inhibitory potency against PDHc and herbicidal activity of title compounds could be increased greatly by optimizing substituent groups of the title compounds. O,O-Dimethyl α-(2,4-dichlorophenoxyacetoxy)ethylphosphonate (I-5), which acted as a competitive inhibitor of PDHc with much higher inhibitory potency against PDHc from Pisum sativum and Phaseolus radiatus than from Oryza sativa , was found to be the most effective compound against broadleaf weeds and showed potential utility as herbicide.     

Nitrogen mineralization and nitrate reduction in forests

The mineralization of soil nitrogen was studied in four forests growing on krasnozem soils. Soils from Silver Wattle (Acacia dealbata Link.) and Mountain Ash (Eucalyptus regnans F. Muell.) forests showed considerable nitrification in laboratory incubations. Messmate (Eucalyptus obliqua L'Herit) and Monterey Pine (Pinus radiata D. Don) forest soils were predominantly ammonifiers. Forests having significant soil nitrification were found to have considerable nitrate reductase activity (NRA) in root or leaf tissue or both. NRA may therefore be useful as an indication of soil nitrification in natural ecosystems. The occurrence of nitrification in Australian forests appears to be predominantly related to the amount of N present and its rate of turnover rather than to inhibitory effects.     

Design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors

The design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors to reduce the loss of ammonia has been carried out. Forty phosphorus derivatives were synthesized and their inhibitory activities evaluated against that of jack bean urease. In addition, in vivo assays have been carried out. All of the compounds were characterized by IR, (1)H NMR, MS, and elemental microanalysis. In some cases, detailed molecular modeling studies were carried out, and these highlighted the interaction between the enzyme active center and the compounds and also the characteristics related to their activity as urease inhibitors. According to the IC(50) values for in vitro inhibitory activity, 12 compounds showed values below 1 microM and 8 of them represent improvements of activity in comparison to the commercial urease inhibitor N-n-butylthiophosphorictriamide (NBPT) (100 nM) (AGROTAIN). On the basis of the activity results and the conclusions of the molecular modeling study, a structural model for new potential inhibitors has been defined.     

Laboratory evaluation of dicyandiamide as a soil nitrification inhibitor

Abstract

Laboratory studies to evaluate dicyandiamide (DCD) as a soil nitrification inhibitor showed that it is considerably more effective than several compounds that have been patented or proposed as fertilizer amendments for retarding nitrification of fertilizer nitrogen (N) in soil, but is considerably less effective than 2‐ethynylpyridine, nitrapyrin (N‐Serve), etridiazole (Dwell), 3‐methylpyrazole‐l‐carboxamide (MPC), or 4‐amino‐l,2,4‐triazole (ATC). Other findings in studies reported were as follows: a) DCD is more effective for inhibiting nitrification of ammonium‐N than of urea‐N; b) the effectiveness of DCD as a nitrification inhibitor is markedly affected by soil temperature and soil type and is limited by the susceptibility of DCD to leaching; c) DCD has very little, if any, effect on urea hydrolysis, denitrification, or seed germination in soil; d) products of DCD decomposition in soil (guanylurea and guanidine) have little, if any, effect on nitrification compared with DCD; e) in the absence of leaching, the persistence of the inhibitory effect of DCD on nitrification decreases with increase in soil temperature from 10 to 30°C, but the inhibitory effect of 50 μg DCD g^‐1 soil is substantial even after incubation of DCD‐treated soils at 20 or 30°C for 24 weeks.     

Persistence of effects of nitrification inhibitors added to soils

Abstract

The persistence of the effects of four nitrification inhibitors (2‐ethynylpyridine, nitrapyrin, etridiazole, 3‐methylpyrazole‐l‐carboxamide) on nitrification in soil was assessed by measuring the ability of two soils to nitrify NH₄ ⁺ [added as (NH₄)₂SO₄] after they had been treated with 5 μg inhibitor g^‐1 soil and incubated at 10, 20, or 30°C for 0, 21, 42, 84, 126, or 168 days. The soils used differed markedly in organic‐matter content (1.2 and 4.2% organic C). The data obtained showed that the persistence of the effects of the inhibitors studied decreased markedly with increase in soil temperature from 10 to 30°C and that, whereas the initial inhibitory effects of the test compounds on nitrification were greatest with the soil having the lower organic‐matter content, the persistence of their effects at 20 or 30°C was greatest with the soil having the higher organic‐matter content. The inhibitory effects of 2‐ethynylpyridine and etridiazole on nitrification were considerably more persistent than those of nitrapyrin or 3‐methylpyrazole‐l‐carboxamide and were significant even after incubation of inhibitor‐treated soil at 20°C for 168 days.     

Crop yield and soil nitrogen dynamics in an intermittently flooded rice field affected by nitrification inhibitors

A field experiment was conducted to study yield and soil N dynamics in an irrigated, intermittently submerged rice field at New Delhi, India, where chemically synthesized as well as neem derived urea coating nitrification inhibitors with prilled urea were applied. Rice (var. IR-32) was grown on a Typic Ustochrept alluvial soil. No nitrogen (control), prilled urea alone, prilled urea mixed with dicyandiamide (DCD), neem (powdered Azadirachta indica Juss. seeds) coated urea and Nimin (commercial derivative of neem) coated urea were tested for their efficacy in regulating yield and conservation of N. None of the inhibitors could increase biomass or grain yield over urea. But all the inhibitors were able to conserve soil ammonium and DCD was the most efficient nitrification inhibitor followed by Nimin coated urea. N-uptake, recovery, physiological and agronomic efficiencies were highest in urea treated plots. The performances of all the inhibitors were against the popular trend where crop yield and N-uptake were enhanced by their application. But, more studies are required on the performance of these inhibitors in rice fields to come to a stronger conclusion.     

Crude extract of Astragalus mongholicus root inhibits crop seed germination and soil nitrifying activity

Astragalus mongholicus has been of medicinal use within the traditional Chinese system for centuries. However, little information is available on its allelopathic effects on other crop plants and soil biochemical properties. Field experiment showed that the extracted residues of A. mongholicus root inhibited seed germination of wheat. Inhibition of seed germination was further confirmed in laboratory using the same crude extract. When the crude extract was applied to soil at various rates and incubated for 30 days, soil urease activity and denitrifying enzyme activity were significantly increased while soil nitrification rate was significantly decreased at 10% amendment rate as compared to the control. Soil respiration rate was significantly increased by the crude extract when measured at the start of incubation but returned to basal levels after 30 days of incubation. The crude extract supplemented to NB medium significantly decreased the colony numbers of Agrobacterium tumefaciens C58, Paraccocus denitrificans and soil bacteria. The stimulating effects of crude extract observed in the amended soil was attributed to the easily-available carbohydrates in the extract, which might served as external energy sources for heterotrophic microbial activities. It was concluded that A. mongholicus contained some compounds that inhibited seed germination, soil nitrification and bacterial growth in general. Possible links between allelochemicals responsible for the inhibitory effects observed in the present study and the medically bioactive compounds are discussed based on information reported in other fields. Further work is needed to specify and verify the allelochemicals produced by this herbal plant.