Weeds are known to cause enormous losses due to their interference in agroecosystems. Because of environmental and human health concerns, worldwide efforts are being made to reduce the heavy reliance on synthetic herbicides that are used to control weeds. In this regard the phenomenon of allelopathy, which is expressed through the release of chemicals by a plant, has been suggested to be one of the possible alternatives for achieving sustainable weed management. The use of allelopathy for controlling weeds could be either through directly utilizing natural allelopathic interactions, particularly of crop plants, or by using allelochemicals as natural herbicides. In the former case, a number of crop plants with allelopathic potential can be used as cover, smother, and green manure crops for managing weeds by making desired manipulations in the cultural practices and cropping patterns. These can be suitably rotated or intercropped with main crops to manage the target weeds (including parasitic ones) selectively. Even the crop mulch/residues can also give desirable benefits. Not only the terrestrial weeds, even allelopathy can be suitably manipulated for the management of aquatic weeds. The allelochemicals present in the higher plants as well as in the microbes can be directly used for weed management on the pattern of herbicides. Their bioefficacy can be enhanced by structural changes or the synthesis of chemical analogues based on them. Further, in order to enhance the potential of allelopathic crops, several improvements can be made with the use of biotechnology or genomics and proteomics. In this context either the production of allelochemicals can be enhanced or the transgenics with foreign genes encoding for a particular weed-suppressing allelochemical could be produced. In the former, both conventional breeding and molecular genetical techniques are useful. However, with conventional breeding being slow and difficult, more emphasis is laid on the use of modern techniques such as molecular markers and the selection aided by them. Although the progress in this regard is slow, nevertheless some promising results are coming and more are expected in future. This review attempts to discuss all these aspects of allelopathy for the sustainable management of weeds.

Allelopathic Interactions and Allelochemicals: New Possibilities for Sustainable Weed Management

The interactions between phytohormones are crucial for plants to adapt to complex environmental changes. One example is the ethylene-regulated local auxin biosynthesis in roots, which partly contributes to ethylene-directed root development and gravitropism. Using a chemical biology approach, we identified a small molecule, l-kynurenine (Kyn), which effectively inhibited ethylene responses in Arabidopsis thaliana root tissues. Kyn application repressed nuclear accumulation of the ETHYLENE INSENSITIVE3 (EIN3) transcription factor. Moreover, Kyn application decreased ethylene-induced auxin biosynthesis in roots, and TRYPTOPHAN AMINOTRANSFERASE OF ARABIDOPSIS1/TRYPTOPHAN AMINOTRANSFERASE RELATEDs (TAA1/TARs), the key enzymes in the indole-3-pyruvic acid pathway of auxin biosynthesis, were identified as the molecular targets of Kyn. Further biochemical and phenotypic analyses revealed that Kyn, being an alternate substrate, competitively inhibits TAA1/TAR activity, and Kyn treatment mimicked the loss of TAA1/TAR functions. Molecular modeling and sequence alignments suggested that Kyn effectively and selectively binds to the substrate pocket of TAA1/TAR proteins but not those of other families of aminotransferases. To elucidate the destabilizing effect of Kyn on EIN3, we further found that auxin enhanced EIN3 nuclear accumulation in an EIN3 BINDING F-BOX PROTEIN1 (EBF1)/EBF2-dependent manner, suggesting the existence of a positive feedback loop between auxin biosynthesis and ethylene signaling. Thus, our study not only reveals a new level of interactions between ethylene and auxin pathways but also offers an efficient method to explore and exploit TAA1/TAR-dependent auxin biosynthesis.

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A Small-Molecule Screen Identifies l-Kynurenine as a Competitive Inhibitor of TAA1/TAR Activity in Ethylene-Directed Auxin Biosynthesis and Root Growth in Arabidopsis

Green plants, within certain limitations, can adapt to a wide variety of unfavourable conditions such as drought, temperature changes, light variations, infectious attacks, air pollution and soil contamination. Depending on the strength of the individual impact(s), fluent or abrupt changes in visible or measurable stress symptoms indicate the deviation from normal metabolic conditions. Most of the visible or measurable symptoms are connected with altered oxygen metabolism principally concerning the transition from mostly heterolytic (two-electron transition) to increased homolytic (one-electron transition) processes. Homolytic reactions within metabolic sequences create, however, free radicals and have to be counteracted by the increase in radical-scavenging processes or compounds, thus warranting reaction sequences under metabolic control. At later states of stress episodes, the above control is gradually lost and more or less chaotic radical processes take over. Finally, cellular decompartmentalisations induce lytic and necrotic processes which are visible as the collapse of darkening cells or tissues. Every episode during this process is governed by a more or less denned balance between pro- and antioxidative capacities, including photosynthetic (strongly under metabolic and oxygen-detoxifying control) and photodynamic (only controlled by scavenger- and/or quencher-availability) reactions. This (theoretical) sequence of events in most cases can only be characterised punctually by strongly defined (analytical) indicator reactions (ESR) and is certainly species- and organ-specific.

Mechanisms of oxygen activation during plant stress

Publisher Summary
Protoporphyrinogen oxidase-inhibiting herbicides, also referred to as Protox- or PPO-inhibiting herbicides, were commercialized in the 1960s. Nitrofen was the first Protox-inhibiting herbicide to be introduced for commercial use in 1964. This diphenyl ether (DPE) herbicide was eventually recognized as a relatively weak inhibitor of Protox, but it was a lead compound of an entire class of structurally related herbicides that were much more active. Several DPE herbicides have been successfully commercialized. Numerous nonoxygen-bridged compounds with this same site of action have also been discovered. Before glyphosate-resistant crops, there were several reasons for the high level of interest among agrochemical companies in the discovery and development of new Protox inhibitors. Protox is a particularly good target that can be inhibited by structurally diverse classes of herbicides, allowing for the development of a new chemistry not yet patented by other companies. These compounds are effective at very low application rates and have generally good ecotoxicology and human toxicology profiles at recommended application rates. Many are highly compatible with the trend toward no-tillage agriculture. Furthermore, unlike with some of the other herbicide classes, weeds do not readily evolve resistance at this particular site of action, although the discovery of a Protox inhibitor-resistant Amaranthus rudis biotype suggests that resistance can and will occur if the selection pressure is sufficient. The relatively low dose rates required for herbicidal activity may be far below the dose needed to adversely affect porphyrin metabolism in animals in field situations or in humans as a result of exposures in food, water, air, or during application.

Protoporphyrinogen Oxidase-Inhibiting Herbicides

Microbial metabolites attract increasing attention as potential pesticides. They are expected to overcome the resistance and pollution that have accompanied the use of synthetic pesticides. Several microbial metabolites, such as avermectin, have proved useful as agroactive agents. In this review, we attempt to identify newer agroactive microbial metabolites with feasible activity or interesting action sites from those reported in recent years. In addition, microbial and chemical modifications of existing microbial agrochemicals are discussed to illustrate the usefulness of these technologies in potentiating agroactivity and stability. We discuss the possibility of future discovery of excellent microbial agrochemicals, and the importance of efforts to promote positive public perception and public acceptance of pesticide chemicals.

https://www.annualreviews.org/doi/pdf/10.1146/annurev.mi.47.100193.000421

Agroactive Compounds of Microbial Origin

An insect growth regulator, pyriproxyfen, has been used for the control of a range of pest insects, including mosquitoes. Pyriproxyfen is effective in inhibiting adult emergence and sterilizing adult females. The Asian tiger mosquito, Aedes albopictus (Skuse), is an important vector of dengue and chikungunya, and is expanding its distribution throughout Europe and the Americas. In the present study, we evaluated the impact of pyriproxyfen-treated bed nets on population growth of Ae. albopictus under semi-field conditions, using 6 small microcosms. We created microcosms containing breeding sites to simulate the natural ecosystem of vector mosquito and installing miniature bed net treated with 350 mg/m2 pyriproxyfen in Experiment I and 35 mg/m2 in Experiment II. For each experiment, we also established microcosms installing untreated polyethylene net (untreated control). The installing nets were provided with artificially torn holes, to simulate damage and allow mosquitoes to penetrate. We released 100 pairs of Ae. albopictus into each microcosm, and allowed them to feed on a mouse under the bed nets at approximately 1-week intervals. In comparison with the untreated control microcosms, the number of eggs laid by the released adults in the pyriproxyfen-treated microcosms was significantly lower in both Experiment I and II. Moreover, egg hatchability was significantly suppressed and pupal mortality was increased. Our results indicate that tarsal contact with pyriproxyfen has been shown to suppress egg production and hatchability in adult females and the auto-dissemination of pyriproxyfen into larval breeding sites by adult mosquitoes, through contact with pyriproxyfen-treated polyethylene bed nets, may suppress the mosquito population density.

http://naosite.lb.nagasaki-u.ac.jp/dspace/bitstream/10069/33417/1/PLoS8_67045.pdf

The Effect of Pyriproxyfen as a “Population Growth Regulator” against Aedes albopictus under Semi-Field Conditions

Pyrethroid-resistant malaria vectors have become a serious threat for malaria control, and bed nets that reduce the development of resistance are urgently needed. Here, we tested the effects of bed nets treated with the insect growth regulator pyriproxyfen against adult female Anopheles gambiae Giles (Diptera: Culicidae) under laboratory conditions. Noninsecticidal nets made of 195 denier monofilament polyethylene with a mesh size of 75 holes per square inch (equivalent to the Olyset Net) were dipped in a 0.1, 0.01, or 0.001% (wt:vol) alcohol solution of pyriproxyfen and dried overnight. Adult females of an insecticide-susceptible An. gambiae strain were exposed to treated and untreated nets before and after a bloodmeal. Bioassays showed that females were completely sterilized after exposure to 0.1% (35 mg [AI]/m2) and 0.01% pyriproxyfen-treated nets both before and after a bloodmeal. In addition, adult longevity decreased after exposure to the pyriproxyfen-treated nets in a concentration-dependent manner. The sterilizing and life-shortening effects of pyriproxyfen on the vector mosquito indicate that the combined use of pyriproxyfen and pyrethroids on bed nets has the potential to provide better malaria control and prevent the further development of pyrethroid resistance in malaria vectors.

https://bioone.org/journals/journal-of-medical-entomology/volume-49/issue-5/ME12006/Efficacy-of-Pyriproxyfen-Treated-Nets-in-Sterilizing-and-Shortening-the/10.1603/ME12006.pdf

Efficacy of pyriproxyfen-treated nets in sterilizing and shortening the longevity of Anopheles gambiae (Diptera: Culicidae).

Two forms of L-tryptophan aminotransferases (L-TAT-1 and L-TAT-2) and one D-tryptophan aminotransferase (D-TAT) were separated from maize coleoptiles by using L- and D-tryptophan as amino group donors. The enzymes were partially purlfied by hydrophobic and gel filtration column chromatographies. L-TAT-1 and L-TAT-2 had similar properties, showing optimum pH at 8–9 and a high optimum temperature of 50–60 C for catalytic activity. As the amino group acceptor for these two enzymes, α-keto glutaric acid was more effective than pyruvic, oxaloacetic and glyoxylic acids. The molecular masses of L-TAT-1 and L-TAT-2 estimated by gel filtration were approximately 80 kDa and 45 kDa, respectively. D-TAT had an optimum pH similar to those of L-TATs, but the optimum temperature was conslderably lower (30 C). Pyruvic acid was an effective amino group acceptor for D-TAT, whereas oxaloacetic and α-keto glutaric acids were not. D-Cycloserine completely inhibited the activity. The molecular mass of D-TAT was approximately 55 kDa. These three TATs required pyridoxal-5-phosphate for their catalytic activities.

L- and D-tryptophan aminotransferases from maize coleoptiles

In vitro mode of action of N-Phenylimide photobleaching herbicides

A group of highly active N -phenylimide photobleaching herbicides have been synthesized. These N -phenylimide herbicides as well as diphenyl ether herbicides induce protoporphyrin IX accumulation and inhibit protoporphyrinogen oxidase activity at extremely low concentrations in higher plants. The binding of a 14C -labeled N -phenylimide herbicide S-23121 [N-[4-chloro- 2-fluoro-5-[(1-m ethyl-2-propynyl)oxy]phenyl]-3,4,5,6-tetrahydrophthalimide] to the solubilized plastid fractions of greening corn seedlings is competed by the diphenyl ether herbicide acifluorfen-ethyl, but not by diuron, an inhibitor of photosynthetic electron transport. These results indicate a similar mode of action for both N -phenylimide and diphenyl ether herbicides. In order to investigate the mechanism of photobleaching herbicides at the molecular level, a strain of Chlamydomonas reinhardtii RS-3 resistant to N -phenylimide S-23142 [N -(4-chloro- 2-fluoro-5-propargyloxyphenyl)-3,4,5,6-tetrahydrophthalimide] was isolated by mutagenesis with N -m ethyl-N′-nitro-N -nitrosoguanidine. The 90% inhibition concentration of N -phenylimide S-23142 for growth of RS-3 was 100 times higher than that for wild type. Maximum accumulation of protoporphyrin IX was reached at 0.03 μᴍ of S-23142 for the wild type and 3 μᴍ for RS-3. RS-3 was resistant to oxadiazon, oxyfluorfen and acifluorfen-ethyl which had been shown to have the same mechanism of action as N -phenylimide herbicides, but not to paraquat, diuron or fluridone. Genetic analysis of RS-3 strain showed that the resistance results from a dominant mutation ( rs-3) in the nuclear genome. The magnesium protoporphyrin IX synthesizing activity from 5-am inolevulinic acid in chloroplast fragments isolated from RS-3 was less sensitive to S-23142 than that from wild type (CC-407). Protoporphyrinogen oxidase activity in Percoll™ -purified chloroplasts from RS-3 was also less sensitive to S-23142 than that from wild type. These results indicate that the resistance of RS-3 is specific for photobleaching herbicides, and that the mutation is related to protoporphyrinogen oxidase, the primary site of the photobleaching herbicide action.

Nobuaki Mito

Papers

The Effect of Pyriproxyfen as a “Population Growth Regulator” against Aedes albopictus under Semi-Field Conditions

Efficacy of pyriproxyfen-treated nets in sterilizing and shortening the longevity of Anopheles gambiae (Diptera: Culicidae).

L- and D-tryptophan aminotransferases from maize coleoptiles

In vitro mode of action of N-Phenylimide photobleaching herbicides

Isolation and Characterization of a Chlamydomonas reinhardtii Mutant Resistant to Photobleaching Herbicides