Allelopathy studies the interactions among plants, fungi, algae and bacteria with the organisms living in a certain ecosystem, interactions that are mediated by the secondary metabolites produced and exuded into the environment. Consequently, allelopathy is a multidisciplinary science where ecologists, chemists, soil scientists, agronomists, biologists, plant physiologists and molecular biologists offer their skills to give an overall view of the complex interactions occurring in a certain ecosystem. As a result of these studies, applications in weed and pest management are expected in such different fields as development of new agrochemicals, cultural methods, developing of allelopathic crops with increased weed resistance, etc. The present paper will focus on the chemical aspects of allelopathy, pointing out the most recent advances in the chemicals disclosed, their mode of action and their fate in the ecosystem. Also, attention will be paid to achievements in genomics and proteomics, two emerging fields in allelopathy. Rather than being exhaustive, this paper is intended to reflect a critical vision of the current state of allelopathy and to point to future lines of research where in the authors' opinion the main advances and applications could and should be expected.

In the search for a standard bioassay of phytotoxicity for allelochemicals, 22 commercial varieties of eight plant species [four dicotyledons: lettuce (Compositae), carrot (Umbelliferae), cress (Cruciferae), tomato (Solanaceae); and four monocotyledons: onion (Liliaceae), barley, wheat, and corn (Gramineae)] proposed as models for the most common weed families have been tested at different pH and solution volumes per set conditions. Nine commercial varieties selected as standard target species (STS) were tested with standard commercial herbicides to ensure their sensitivity to phytotoxic compounds. Results are discussed to establish the proper growth requirements, and sensitivity of commercial seeds of STS and to find the most suitable commercial herbicides that allow comparison with an internal standard to validate the response of potential allelochemicals.

Benzoxazinoids have been described as important allelochemicals from Gramineae as well as Acanthaceae, Rannunculaceae, and Scrophulariaceae plants. Several bioactivities have been described and evaluated for these compounds, including fungistatic, antifeedant, and phytotoxic. In ongoing studies about allelochemicals as natural herbicide models, the description of soil dynamics in phytotoxic agents has high importance, because the possible biotransformations developed by soil microorganisms could yield compounds with modified biological properties, affecting the overall allelopathic capability of the producer plant in a direct manner. Thus, a complete degradation study has been carried out for 2,4-dihydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA) and 6-methoxybenzoxazolin-2(3H)-one (MBOA) in two soils cultivated with Triticum aestivum L. varieties (cv. Astron and cv. Ritmo). The main purpose was to identify degradation products and to elucidate biotransformation dynamics. Results show DIMBOA to degrade rapidly, yielding MBOA in both studied soils at different doses (t 1/2 ) 31 ( 1 h, n ) 12) and reaching high conversions (80 ( 4 h, n ) 42). MBOA, an intermediate in the degradation pathway from DIMBOA to 2-amino-7-methoxy-3H-phenoxazin-3-one (AMPO), was more resistant toward biodegradation (t 1/2 ) 5 ( 1 days, n ) 6). MBOA showed maximum conversions at a dose of 250 mg/kg of soil (36 ( 3 days, n ) 6). Soil belonging to T. aestivum cv. Ritmo crops showed higher degradation capacity than cv. Astron soil. AMPO was the final degradation product observed for DIMBOA in the soils and experimental conditions selected. Consequences for activity and stability of these compounds in relation to allelopathy are discussed.

The allelopathic potency of rye (Secale cereale L.) is due mainly to the presence of phytotoxic benzoxazinones-compounds whose biosynthesis is developmentally regulated, with the highest accumulation in young tissue and a dependency on cultivar and environmental influences. Benzoxazinones can be released from residues of greenhouse-grown rye at levels between 12 and 20 kg/ha, with lower amounts exuded by living plants. In soil, benzoxazinones are subject to a cascade of transformation reactions, and levels in the range 0.5-5 kg/ha have been reported. Starting with the accumulation of less toxic benzoxazolinones, the transformation reactions in soil primarily lead to the production of phenoxazinones, acetamides, and malonamic acids. These reactions are associated with microbial activity in the soil. In addition to benzoxazinones, benzoxazolin-2(3H)-one (BOA) has been investigated for phytotoxic effects in weeds and crops. Exposure to BOA affects transcriptome, proteome, and metabolome patterns of the seedlings, inhibits germination and growth, and can induce death of sensitive species. Differences in the sensitivity of cultivars and ecotypes are due to different species-dependent strategies that have evolved to cope with BOA. These strategies include the rapid activation of detoxification reactions and extrusion of detoxified compounds. In contrast to sensitive ecotypes, tolerant ecotypes are less affected by exposure to BOA. Like the original compounds BOA and MBOA, all exuded detoxification products are converted to phenoxazinones, which can be degraded by several specialized fungi via the Fenton reaction. Because of their selectivity, specific activity, and presumably limited persistence in the soil, benzoxazinoids or rye residues are suitable means for weed control. In fact, rye is one of the best cool season cover crops and widely used because of its excellent weed suppressive potential. Breeding of benzoxazinoid resistant crops and of rye with high benzoxazinoid contents, as well as a better understanding of the soil persistence of phenoxazinones, of the weed resistance against benzoxazinoids, and of how allelopathic interactions are influenced by cultural practices, would provide the means to include allelopathic rye varieties in organic cropping systems for weed control.

Benzoxazinones 2,4-dihydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA) and 2,4-dihydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA) have been considered key compounds for understanding allelopathic phenomena in Gramineae crop plants such as corn (Zea mays L.), wheat (Triticum aestivum L.), and rye (Secale cereale L.). The degradation processes in the environment observed for these compounds, in which soil microbes are directly involved, could affect potential allelopathic activity of these plants. We present in this work a complete structure-activity relationships study based on the phytotoxic effects observed for DIMBOA, DIBOA, and their main degradation products, in addition to several synthetic analogues of them. Their effects were evaluated on standard target species (STS), which include Triticum aestivum L. . They showed high inhibitory activity over almost all species growth. The fact that APO is a degradation product from DIBOA with high phytotoxicity and stability makes it possible to assign an important ecological role regarding plant defense mechanisms. 2-Deoxy derivatives of natural benzoxazinones display a wide range of activities that allow proposing them as new leads for natural herbicide models with a 1,4-benzoxazine skeleton.