Mode of action of herbicidal derivatives of aminomethylenebisphosphonic acid. I. Physiologic activity and inhibition of anthocyanin biosynthesis
N-Pyridylaminomethylenebisphosphonic acids constitute a class of promising herbicides. Since their mode of action at the cellular level is still poorly understood, we studied the influence of N-pyridylaminomethylenebisphosphonic acids on plant growth, at the whole plant and undifferentiated tissue levels, using seedlings and cell suspension cultures of mono- and dicotyledonous species. These compounds exhibited strong herbicidal properties, being equipotent with the popular herbicide glyphosate. Since they also depressed buckweed anthocyanin biosynthesis, the shikimate pathway could represent a site of action of N-pyridylaminomethylenebisphosphonic acids.
Phosphonate degradation by Spirulina strains: cyanobacterial biofilters for the removal of anticorrosive polyphosphonates from wastewater
The ability of Spirulina spp. to metabolize the recalcitrant xenobiotic Dequest 2054(®) [hexamethylenediamine-N,N,N',N'-tetrakis(methylphosphonic acid)], a CaSO(4) inhibitor used for boiler treatment and reverse osmosis desalination, was investigated. The compound served as sole source of phosphorus, but not of nitrogen, for cyanobacterial growth. In vivo utilization was followed by (31)P NMR analysis. The disappearance of the polyphosphonate proceeded only with actively dividing cells, and no release of inorganic phosphate was evident. However, no difference was found between P-starved and P-fed cultures. Maximal utilization reached 1.0 ± 0.2 mmoll(-1), corresponding to 0.56 ± 0.11 mmol g(…
The aminophosphonate glyphosine enhances phycobiliprotein yields from selected cyanobacterial cultures
Among added-value products obtained from cyanobacterial cultures are phycobiliproteins, photosynthetic pigments that have found an increasing number of applications as natural dyes for food, cosmetics, pharmaceuticals, and antioxidants. To obtain sustainable production, we aimed at maximizing phycobilin yield through the increase of either the final biomass or the specific content of these pigments by varying culture parameters, such as chemical composition and pH of the medium or quality and intensity of the light. Here, we report that the addition to the culture medium of millimolar or submillimolar concentrations of the aminophosphonate glyphosine [(N,N-bis(phosphonomethyl)glycine], form…
Phosphorus NMR as a tool to study mineralization of organophosphonates—The ability of Spirulina spp. to degrade glyphosate
Abstract A commercially available mixed culture of Spirulina spp. exhibited a remarkable ability to degrade the widely used organophosphorus herbicide glyphosate, that served as sole source of either phosphorus or nitrogen for cyanobacterial growth. 31P NMR analysis of spent media appeared to be an effective and simple technique to follow disappearance of the phosphonate and release of inorganic phosphate in biodegradation process(es).
Biodegradation of the aminopolyphosphonate DTPMP by the cyanobacteriumAnabaena variabilisproceeds via a C-P lyase-independent pathway
Cyanobacteria, the only prokaryotes capable of oxygenic photosynthesis, play a major role in carbon, nitrogen and phosphorus global cycling. Under conditions of increased P availability and nutrient loading, some cyanobacteria are capable of blooming, rapidly multiplying and possibly altering the ecological structure of the ecosystem. Because of their ability of using non-conventional P sources, these microalgae can be used for bioremediation purposes. Under this perspective, the metabolization of the polyphosphonate diethylenetriaminepenta(methylenephosphonic) acid (DTPMP) by the strain CCALA 007 of Anabaena variabilis was investigated using 31 P NMR analysis. Results showed a quantitative…
Mode of action of herbicidal derivatives of aminomethylenebisphosphonic acid. Part II. Reversal of herbicidal action by aromatic amino acids
The herbicidal action of N-pyridylaminomethylenebisphosphonic acids is accompanied by an impairment of anthocyanin biosynthesis. This suggests that they might act as inhibitors of some steps in aromatic amino acid biosynthesis. Herbicidal effects were reversed by aromatic amino acids using both bacterial and plant models, a finding that strongly supports this hypothesis. Structural features of these compounds suggest the sixth enzyme in the shikimate pathway 5-enol-pyruvoylshikimate-3-phosphate (EPSP) synthase as a possible target, since a strong structural similarity exists between aminomethylenebisphosphonic acid and an inhibitor of EPSP synthase, the herbicide glyphosate. This is, howeve…
Amino polyphosphonates - chemical features and practical uses, environmental durability and biodegradation
Growing concerns about the quality of the environment led to the introduction of complex system of safety assessment of synthetically manufactured and commonly applied chemicals. Sometimes, however, our knowledge of consequences that result from the usage of these substances, appears far later, than at the beginning of their application. Such situation is observed in the case of aminopolyphosphonates being an important subgroup of organophosphorus compounds. The increasing industrial and household applications, led to introduce thousand tons of polyphosphonates every year into the environment. These substances are difficult to determine in environmental samples because of lack of appropriat…
Herbicidal derivatives of aminomethylenebisphosphonic acid. Part III. Structure-activity relationship.
Derivatives of aminomethylenebisphosphonic acids constitute a class of promising herbicides. More than 40 N-substituted aminomethylenephosphonic acids were synthesized and evaluated for their herbicidal activity on common cress (Lepidium sativum L.) and cucumber (Cucumis sativus L.). Some of the tested compounds were found to exhibit strong herbicidal properties being equal in activity with the popular herbicide glyphosate as well as parent N-pyridylaminomethylenephosphonic acids. N-Substituted iminodi(methylenephosphonic) acids, which may be considered as close analog of glyphosate, were inactive toward test plants.
Biochemical bases for a widespread tolerance of cyanobacteria to the phosphonate herbicide glyphosate
Possible non-target effects of the widely used, non-selective herbicide glyphosate were examined in six cyanobacterial strains, and the basis of their resistance was investigated. All cyanobacteria showed a remarkable tolerance to the herbicide up to millimolar levels. Two of them were found to possess an insensitive form of glyphosate target, the shikimate pathway enzyme 5-enol-pyruvyl-shikimate-3-phosphate synthase. Four strains were able to use the phosphonate as the only phosphorus source. Low uptake rates were measured only under phosphorus deprivation. Experimental evidence for glyphosate metabolism was also obtained in strains apparently unable to use the phosphonate. Results suggest…
Herbicidally Active Derivatives of Aminomethylenebis-Phosphonic Acid-Mode of Action and Structure - Activity Relationship
Abstract: (N-pyridylamino)methylenebisphosphonates exhibit strong herbicidal activity which may be reversed by supplementation of the growth media with aromatic amino acids. They appeare to be the inhibitors of aromatic amino acids biosynthesis acting as inhibitors of DAHP synthase the first enzyme of shikimate pathway. Over 40 analogues of these acids were synthesized in order to determine the structure-activity relationship.
Recent advances in the research on herbicidally active aminomethylelebisphosphonic acids.
Influence of the mode of application of herbicidally active N-pyridylaminomethylenebi-sphosphonic acids on their uptake by plants was studied in some detail. The experimental evidence is given that accounts for a multiple mode of action of these herbicides.