Metabolism and selectivity of rice herbicides in plants

Chemical weed control with effective and highly active herbicides has been very useful and convenient means. It has contributed to stable crop production and is labor saving. Recent herbicides have had characteristics such as high effectiveness without causing environmental pollution or harmful effects, and appropriate herbicides having high activity, low toxicity, high selectivity and being non-persistent have been developed. The metabolism of rice herbicides used mainly in Japan, such as sulfonylurea, chloroacetamide, acylamide, urea, thiocarbamate, pyrazole, triazine, diphenyl ether, phthalimide, phenoxy, aryloxyphenoxypropionate, etc., is reviewed, and its involvement in selectivity is also discussed. The metabolism of herbicides is closely related to their activity and selectivity. Differential herbicide metabolism in plants is a contributing factor of selectivity between crops and weeds. Chemicals that are more detoxified in crops and/or more activated or less detoxified in weeds are considered as being effective and selective herbicides. The metabolism of various types of rice herbicides includes: oxidative reaction (ring and chain hydroxylation, O - and N -dealkylation), hydrolysis and subsequent glucose conjugation, and glutathione conjugation in rice. These detoxicative activities are much higher in rice than weeds in paddies, and this leads to the selectivity of herbicides. Enzymes, oxidase, P-450 mono-oxygenase, esterase, acylamidase, glucosyl transferase, glutathione transferase, etc., play important roles in herbicide metabolism and selectivity.     

植物病原真菌对甾醇脱甲基抑制剂类杀菌剂抗性分子机制研究进展

甾醇脱甲基抑制剂 (DMI) 可通过抑制病原真菌的14α-去甲基化酶(CYP51)而干扰或阻断细胞膜麦角甾醇的生物合成,造成有毒甾醇积累,从而影响细胞膜的结构及功能,进而发挥抗菌作用。随着DMI类杀菌剂的广泛应用,病原菌对其的抗性问题日益严重。本文从抗药性分子机制出发,总结出病原菌对DMI类杀菌剂产生抗性的主要原因为:CYP51氨基酸突变引起其与杀菌剂间的亲和力下降;启动子区域基因片段的插入引起CYP51基因过表达;转录因子激活突变或启动子区域基因片段插入导致外排蛋白基因过表达。本文基于杀菌剂的作用方式及病原菌抗性机制研究展开综述,可为杀菌化合物的结构修饰与优化、新靶点改进和研发以及病原真菌的抗药性治理提供参考。     

The chemical environment of leaf surfaces with special reference to spore germination of pathogenic fungi

The release of diffusible substances from plant leaves, fungal spores or from pollen into water droplets on the surface of leaves is discussed in relation to (1) direct and indirect effects on spores of pathogens and (2) the effect on the growth of saprophytic micro-organisms. Evidence suggests that competition for nutrients in droplets on leaves may limit germination of spores of some pathogens. Modification of the chemical environment of leaf surfaces by saprophytic micro-organisms is discussed in relation to lytic enzyme and antibiotic production, cuticle degradation, production of growth substances and fixation of nitrogen. Examples are given of the effect on pathogenic fungi of diffusible toxins from leaves and inhibitors associated with surface wax. Treatments of leaves that remove or reduce surface wax can result in a stimulation of spore germination of some pathogenic fungi. The possible occurrence of phytoalexins on leaf surfaces prior to entry of pathogens into leaves is discussed in relation to differences in host-pathogen interaction.     

Diagnosis of viruses in ornamental plants with special reference to serological methods: new developments

In support of the work of the EPPO Panel on Certification of Pathogen-tested Ornamentals, new techniques of diagnosis (since 1980) are presented for viruses of carnation, chrysanthemum, iris, lily, narcissus and pelargonium.     

Chemical structure-activity relationships of the inhibition of sterol biosynthesis by N-substituted morpholines in higher plants

Tridemorph and fenpropimorph as well as several related N-alkyl morpholines have been tested in vitro on the cycloeucalenol-obtusifoliol isomerase, a microsomal enzyme involved in higher plant sterol biosynthesis. The results showed that N-substituted morpholines inhibit powerfully the enzyme (I₅₀ = 0.4 μM for fenpropimorph). The following important molecular parameters of the inhibition could be determined: (i) the inhibitory capacity was probably related to the presence of a positive charge on the nitrogen atom, (ii) the length of the alkyl group was critical, with a maximum activity for n = 13 carbons in the case of a linear hydrocarbon chain, (iii) the presence of bulky substituents at the proximity of the nitrogen atom led to a strong decrease of the inhibitory power, (iv) in the fenpropimorph series where a chiral center is present at C-2 of the alkyl chain, a remarkable enantiomeric selectivity of the inhibition was observed, (v) the N-oxide derivative of fenpropimorph was shown to be as active as the parent compound. The N-alkyl morpholines have been also assayed on suspension cultures of bramble cells and led to a strong accumulation of 9β, 19-cyclopropyl- and Δ⁸-sterols. This result confirmed that the cycloeucalenol-obtusifoliol isomerase was a major target of the N-substituted morpholines and suggested that the Δ⁸ → Δ⁷-sterol isomerase was also a target for these chemicals. The molecular parameters implied in the in vivo accumulation of 9β, 19-cyclopropyl sterols were very similar to those resulting from the in vitro study. The chemical structure-inhibitory activity relationship of N-alkyl morpholines was discussed with respect to their fungicidal activity which has been described in a previous study [E. H. Pommer, Pestic. Sci. 15, 285 (1984)]. The comparison revealed that the better the inhibitory capacity on the cycloeucalenol-obtusifoliol isomerase was, the higher was the fungicidal activity in vivo.     

A comparison of the potency of some fungicides as inhibitors of sterol 14-demethylation

An enzymatic assay system has been developed to measure the relative potency of fungicides such as triadimefon, triarimol, triforine, and buthiobate as inhibitors of sterol 14-demethylation. The enzyme preparation used is the 8000g supernatant derived from a homogenate of an aerobically adapted, anaerobically grown, high sterol strain of Saccharomyces cerevisiae. After incubation of the enzyme with [2-¹⁴C]mevalonic acid and the fungicide the ratio, radioactivity in 4,4-dimethyl sterols/radioactivity in 4-demethyl sterols is determined. The higher this ratio is, the more efficient is the fungicide as an inhibitor of fungal sterol 14-demethylation. The ratio has been determined for a number of commercial fungicides and two series of triazole compounds. A similar assay system based on the 10,000g supernatant from a rat liver homogenate was also tested but gave an inaccurate assessment of the relative potency of fungicides as inhibitors of fungal sterol 14-demethylation.     

Metabolism of fungicidal cyanooximes, cymoxanil and analogues in various strains of Botrytis cinerea

BACKGROUND: The metabolism of cymoxanil [1‐(2‐cyano‐2‐methoxyiminoacetyl)‐3‐ethylurea] and fungicidal cyanooxime analogues was monitored on three phenotypes of Botrytis cinerea Pers. ex Fr. differing in their sensitivity towards cymoxanil. For this purpose, labelled [2‐¹⁴C]cymoxanil was added either to the culture medium of these strains or to its cell‐free extract. RESULTS: In the culture medium of the most sensitive strain, four main metabolites were detected. Three were isolated and identified. Cymoxanil was quickly metabolised by at least three concurrent enzymatic pathways: (i) cyclisation leading, after hydrolysis, to ethylparabanic acid, (ii) reduction giving demethoxylated cymoxanil, (iii) hydrolysis followed by reduction and then acetylation leading to N‐acetylcyanoglycine. In the cell‐free extract of the same strain, only the first and the second of these enzymatic reactions occurred. By comparing the metabolic profile of the most sensitive strain with that of the less sensitive ones, it was shown that the decrease in sensitivity to cymoxanil correlates with a reduced acetylcyanoglycine formation. Among all metabolites, only N‐acetylcyanoglycine is active against the most sensitive strain. Moreover, in a culture of this strain, two other fungicidal cyanooximes were also metabolised into this metabolite. CONCLUSION: The formation of N‐acetylcyanoglycine may play an important role in the fungitoxicity of cymoxanil and cyanooxime derivatives. Copyright © 2008 Society of Chemical Industry     

Affinity and mobility of fungicidal dialkyl dithiolanylidenemalonates in rice plants

The affinity of certain fungicide analogs to rice plant varied progressively, showing a linear decrease with decreasing length of, or branching of, the alkyl chains, and correlated well with the hydrophobic parameter, log P. The more hydrophobic the compound was, the higher was the affinity to rice plant. Compound mobility in rice plant also varied regularly. The resulting relationship between hydrophobicity and mobility of these fungicide analogs suggested that the situation in rice plant is quite analogous to rice-plant column chromatography, by which the affinity to rice plant was determined. The major factor preventing movement within the plants seems to be interaction with sites in the rice plant leading to partition or binding and the resulting loss from the transpiration stream.     

The role of translocation in selectivity of herbicides with reference to MCPA and MCPB

The distribution of 2.5 mM-[¹⁴C]MCPA

1 MCPA = (2-methyl-4-chlorophenoxyacetic acid).

and [¹⁴C]MCPB

2 MCPB = (4-(2-methyI-4-chlorophenoxy) butyric acid).

formulated as sodium salts with 0.05% tergitol, have been investigated when applied to an isolated leaf/agar block sink system of Vicia faba L. Results are presented which show the effect on absorption and translocation of method of application, age of treatment leaf, treatment period, pretreatment with 5 μM ATP and removal of cuticle wax by chloroform wipe treatment. Significant negative correlations between cuticle wax fixation/translocation and leaf tissue content/translocation were recorded for both compounds, particularly MCPB, suggesting the involvement of both physicochemical and metabolic components in the process of absorption and translocation. The nature of the mechanisms involved was further investigated using isolated cuticle/epidermal systems and tightly-coupled mitochondria isolated from roots of V. faba L. The results suggest that non-movement of MCPB in this species is largely due to its enhanced retention within the cuticle and to the fact that it is a more effective uncoupler of oxidative phosphorylation than MCPA. The importance of these findings in terms of the relative efficiency of translocation of MCPA and MCPB when applied in vivo is discussed.     

Use of linear free energy related and other parameters in the study of fungicidal selectivity

The modulation of fungicidal activity in a congeneric series of compounds is dependent on several processes taking place in the biological object which may be influenced by the different hydrophobic, electronic and steric properties of the members of the series. These possible influences can be studied in a quantitative way with multiple regression analysis using substituent constants for the properties mentioned. The comparative study of the resulting regression equations for the activity on different fungi or on a fungus and another biological subject may contribute to an understanding of fungicidal selectivity. This is illustrated in studies on the fungitoxicity of isophthalonitriles, 2-chlorobenzonitriles, arylsulphonyl- and arylsulphinyl-alkylthio-cyanates, acetylenic sulphones, methyl benzimidazol-2-ylcarbamates and phosphorus compounds derived from 3-amino-1,2,4-triazole. In these studies new steric parameters were used, which have been introduced recently.     

Chemotherapy of experimental toxoplasmosis with special reference to robenidine

Robenidine as an anticoccidial agent alone (in doses of 50 and 100 mg/kg) or in association with two other antiprotozoal compounds--pyrimethamine and sulfadoxine (in doses of 2.5 and 250 mg/kg, respectively) were tested in the treatment of chronically infected mice with an avirulent cyst-forming HF strain of Toxoplasma gondii. The efficacy of the used drugs was evaluated by the cysts number in the brains of treated mice versus control group, antibody level and viability of survived cysts by the consecutive infection of mice. According to these criteria none of the tested drugs alone or combined exhibited to be able to produce an effective cure of cyst-stage of toxoplasmosis in experimental mice.     

The diastereomeric ratio in the triadimenol produced by fungal metabolism of triadimefon,and its role in fungicidal selectivity

The ratio of the two diastereomeric forms of triadimenol, produced by the reduction of triadimefon in various fungi, was studied. The reduction of triadimefon in fungi seems to be a concentration-dependent process, the virtual irreversibility of which is proved. Not only the degree of triadimefon reduction, but also the ratio of the triadimenol diastereomers produced, was characteristic for each of the fungal species. A direct correlation, between the production of the more active diastereomeric form and the sensitivity of the fungal species to triadimefon, was observed.     

On the biochemistry of interference with normal plant development,with special reference to growth regulators

The precisely “tuned” balance between regulatory mechanisms at various levels, which in fact forms the base of normal development, differentiation and growth of plants, can be disturbed by very different factors.These may be chemical (toxic) agents, either applied intentionally (herbicides, growthretardants) or introduced by pathogenic microorganisms (cf. wilting caused by parasites), plant viruses and different, mostly unknown factors, which in combination with an essential wounding process, may induce plant tumors.Apart from these, physical factors e.g. variations in light intensity and temperature have to be considered.It is analyzed to what extent these seemingly divergent problems may be put on a common biochemical (physiological) base, especially because of the fact that the morphologically perceptible effects evidently often are concerned with a shift in the normal pattern of interrelationships of growth regulators (auxins).     

Charcoal rot in common bean with special reference to Kenya

Abstract

Charcoal rot caused by Macrophomina phaseolina (Deuteromycetes: Coelomycetes) is found throughout the tropics and subtropics and has a wide host range. Together with most of the legume crops, the common bean (Phaseolus vulgaris) Is a good host for the fungus which causes a range of symptoms, depending on environmental conditions and age of the plant. In addition to charcoal rot, which is a stem or stalk rot disease, the pathogen also causes damping‐off and seedling blight in beans. Charcoal rot in the mature plant is associated with senescence which is accelerated by water stress. The disease is most damaging in areas of unreliable rainfall and high temperature. In Kenya, beans are usually grown in mixed stands with maize, sorghum or millet. Population pressure has led to the cultivation of beans on land prone to drought. M. phaseolina is one of the most important pathogens affecting all the main crops of the farming systems in the semi‐arid areas of eastern Kenya and resistance to charcoal rot is a priority if beans are to be increasingly grown in these areas. The paper reviews the literature on charcoal rot of beans and on other crops where similar work has not been reported specifically for beans.     

Effect of the fungicide fenitropan on the metabolism of some higher plants and Fusarium oxysporum

The effect of fenitropan [(1RS, 2RS)-2-nitro-1-phenyltrimethylene di(acetate)], a new fungicide from EGYT Pharmacochemical Works, on the photosynthetic activity, respiration, RNA content and protein synthesis of some higher plants and Fusarium oxysporum, was investigated. The effect on the aminoacylation of tRNAs suggests that fenitropan is an inhibitor of the aminoacyl tRNA ligases accepting aromatic amino acids.     

Pathology of Pinus radiata in ecuador with special reference to Dothistroma

Abstract

Scirrhía pini Funk & Parker (Dothistroma septospora (Dorog.) Morelet) is reported for the first time from Ecuador. Dothistroma needle blight was recorded on Pinus radiata in both nurseries and plantations (2–9 years old), from various high altitude localities in the Sierra. Infection was particularly severe in plantations situated between 2500–3000 m a.s.l. Pinus patula showed a resistant reaction to the fungus as did some older P. radiata trees. Several associated fungi are also listed together with those facultative fungal pathogens isolated from necrotic needles and stem cankers.     

Use and misuse of calorimetry with special reference to muscle physiology

Calorimetric experiments, on their own, can be extremely dangerous to biologists, for there are usually several possible, but alternative interpretations. The simplest interpretation is often not correct. The best way to use biological calorimetry on its own is to indicate good targets for biochemical investigations of a tissue. Even when biochemical investigations are carried out in parallel with calorimetry, dangers remain. In particular it is easy to assume that the heat observed is necessarily derived from the biochemical process measured. The way to avoid this error is to make an energy balance study. In most cases such a study requires calorimetric measurements on cell-free systems of known composition to establish ΔH values for in vivo conditions. Used in this way biological calorimetry is much more than a mere indicator that something is happening; it can lead to the most important statement about what is happening: that we do not yet understand it!     

Spermidine metabolism in parasitic protozoa--a comparison to the situation in prokaryotes,viruses, plants and fungi

Targeting polyamines of parasitic protozoa in chemotherapy has attracted attention because polyamines might reveal novel drug targets for antiparasite therapies (Müller et al. 2001). The biological function of the triamine spermidine in parasitic protozoa has not been studied in great detail although the results obtained mainly imply three different functions, i.e., cell proliferation, cell differentiation, and biosynthesis of macromolecules. Sequence information from the malaria genome project databases and inhibitor studies provide evidence that the current status of spermidine research has to be extended since enzymes of spermidine metabolism are present in the parasite (Kaiser et al. 2001). Isolation and characterisation of these enzymes, i.e., deoxyhypusine synthase (EC 1.1.1.249) (DHS) and homospermidine synthase (EC 2.5.1.44) (HSS) might lead to valuable new targets in drug therapy. Currently research on spermidine metabolism is based on the deposition of the deoxyhypusine synthase nucleic acid sequence in GenBank while the activity of homospermidine synthase was deduced from inhibitor studies. Spermidine biosynthesis is catalyzed by spermidine synthase (EC 2.5.1.16) which transfers an aminopropyl moiety from decarboxylated S-adenosylmethionine to putrescine. Spermidine is also an important precursor in the biosynthesis of the unusual amino acid hypusine (Wolff et al. 1995) and the uncommon triamine homospermidine in eukaryotes, in particular in pyrrolizidine alkaloid-producing plants (Ober and Hartmann 2000). Hypusine is formed by a two-step enzymatic mechanism starting with the transfer of an aminobutyl moiety from spermidine to the epsilon-amino group of one of the lysine residues in the precursor protein of eukaryotic initiation factor eIF5A by DHS (Lee and Park 2000). The second step of hypusinylation is completed by deoxyhypusine hydroxylase (EC 1.14.9929) (Abbruzzese et al. 1985). Homospermidine formation in eukaryotes parallels deoxyhypusine formation in the way that in an NAD(+)-dependent reaction an aminobutyl moiety is transferred from spermidine. In the case of homospermidine synthase, however the acceptor is putrescine. Thus the triamine homospermidine consists of two symmetric aminobutyl moieties while there is one aminobutyl and one aminopropyl moiety present in spermidine. Here, we review the metabolism of the triamine spermidine with particular focus on the biosynthesis of hypusine and homospermidine in parasitic protozoa, i.e., Plasmodium, Trypanosoma and Leishmania, compared to that in prokaryotes i.e., Escherichia coli, a phytopathogenic virus and pyrrolizidine alkaloid-producing plants (Asteraceae) and fungi.     

Advances and prospects in potato virology with special reference to virus resistance

Knowledge of the nucleotide sequences in the genomic nucleic acid of several potato viruses has enabled the open reading frames to be identified. These open reading frames are expressed by a variety of strategies, to produce proteins with functions in virus nucleic acid replication, virus particle production, cell-to-cell transport of virus and virus transmission by vectors. The activity of such proteins depends on their interactions with other viral or non-viral materials.Several other biological properties of plant viruses can also be related to individual viral gene products. For example, in plants co-infected with a specific pair of unrelated viruses, one virus can benefit from an ability to use the gene product of the second virus in replication, cell-to-cell transport or transmission by vectors. Similarly, different host resistance genes are targeted against viral replicase, movement protein or coat protein. Thus it is becoming possible to relate gene-for-gene (or more accurately, viral gene domain-host gene) interactions to events at the molecular level. Genetically engineered resistance to plant viruses likewise can be targeted against individual viral genes, and probably also against viral regulatory sequences. Such transgenic resistance seems likely to be as durable as conventional host resistance but durability should be improved by producing plants with combinations of resistances of different kinds, either conventional or genetically engineered, or both.     

Time-dose-response relationships of pyrethroid insecticides with special reference to knockdown

The relationship between incoordination, knockdown and mortality was investigated by following the course of poisoning in Schistocerca gregaria of two synthetic pyrethroids, bioresmethrin and bioallethrin. Kinetics describing theonset of these responses as a function of dose are interpreted in terms of the dynamics of penetration and detoxication. The possibility of the same site of action for knockdown and kill is briefly discussed.