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Utility of Nuclear Magnetic Resonance for Determining the Molecular Influence of Citric Acid and an Organosilicone Adjuvant on Glyphosate Activity

Published online by Cambridge University Press:  12 June 2017

Kurt D. Thelen ,
Evelyn P. Jackson  and
Donald Penner
Kurt D. Thelen
Affiliation:
Michigan Dep. Agric. P.O. Box 30017, Lansing, MI 48909
Evelyn P. Jackson
Affiliation:
Dep. Chemistry and Max T. Rogers NMR Facility
Donald Penner
Affiliation:
Dep. Crop & Soil Sci., Michigan State Univ., East Lansing, MI 48824
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Abstract

In the discipline of Weed Science, nuclear magnetic resonance (NMR) has been used extensively for obtaining structural information on herbicide compounds in the areas of herbicide synthesis, metabolism, and environmental degradation. However, little research has been published with regard to the utilization of NMR in determining molecular interactions in the spray solution. The molecular influence of citric add and an organosilicone adjuvant on glyphosate was analyzed with NMR spectrometry. 14C-glyphosate absorption studies showed a decrease in glyphosate absorption by sunflower when Ca2+ was added to the spray solution. This absorption antagonism was overcome with the inclusion of an organosilicone adjuvant. 1H-NMR was used to stow that the organosilicone adjuvant did not directly interact with the glyphosate molecule nor did it prevent the formation of Ca-glyphosate. Citric add was effective in overcoming the Cat2+ antagonism of glyphosate activity when the citric add concentration was 2× or 4× the Ca2+ molar concentration based on plant fresh weight and plant height, respectively. 1H-NMR was utilized to show that citric acid reacted with Ca2+ in solution to produce Ca-citrate and prevent the formation of Ca-glyphosate. NMR was an effective technique for characterizing chemical interactions among the spray solution components.

Keywords

Glyphosate, N-(phosphonomethyl)glycinesunflower, Helianthus annuus L., HELANAntagonisminteractions
Type
Physiology, Chemistry, and Biochemistry
Information
Weed Science , Volume 43 , Issue 4 , December 1995 , pp. 566 - 571
Copyright
Copyright © 1995 by the Weed Science Society of America 

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References

LITERATURE CITED

1. Allwood, B. L., Shahriari-Zavareh, H., Stoddart, J. F., and Williams, D. J. 1987. Complexation of paraquat and diquat by a bismethaphenylene-32-crown-10 derivative. J. Chem. Soc. Chem. Commun. 1058–1061.Google Scholar
2. Ashton, P. R., Slawin, A.M.Z., Spencer, N., Stoddart, J. F., and Williams, D. J. 1987. Complex formation between bisparaphenlyene-(3n + 4)-crown-n ethers and the paraquat and diquat dications. J. Chem. Soc. Chem. Commun. 1066–1069.Google Scholar
3. Babczinski, P., Dorgerloh, M., Lobberding, A., Santel, J., Schmidt, R. R., Schmitt, P., and Wunsche, C. 1991. Herbicidal activity and mode of action of vulgamycin. Pestic. Sci. 33:439–446.Google Scholar
4. Castellino, S., Leo, G. C., Sammons, D., and Sikorski, J. A. 1989. 31P,15, and 13C NMR of glyphosate: comparison of pH titrations to the herbicidal dead-end complex with 5-enolpyruvoylshikimate-3-phosphate synthase. Biochemistry 28:3856–3868.CrossRefGoogle Scholar
5. Chrystal, E. J. T., Haines, A. H., and Patel, R. 1990. Studies into the mode of action of herbicides derived from 4-[(Benzyloxy)methyl}-1,3-dioxolanes and benzyl methyl ethers of poly(ethylene glycols). J. Agric. Food Chem. 38:870–874.Google Scholar
6. Field, R. J. and Bishop, N. C. 1988. Promotion of stomatal infiltration of glyphosate by an organosilicone surfactant reduces the initial rainfall period. Pestic. Sci. 224:55–62.CrossRefGoogle Scholar
7. Frear, D. S., Swanson, H. R., Tanaka, F. S. 1993. Metabolism of flumetsulam (DE-498) in wheat, corn, and barley. Pestic. Biochem. Physiol. 45:178–192.CrossRefGoogle Scholar
8. Garbow, J. R. and Gaede, B. J. 1992. Analysis of a phenyl ether herbicidecyclodextrin inclusion complex by CPMAS 13C NMR. J. Agric. Food Chem. 40:156–159.Google Scholar
9. Glass, R. L. 1984. Metal complex formation by glyphosate. J. Agric. Food Chem. 32:1249–1253.Google Scholar
10. Haque, R., Coshow, W. R., and Johnson, L. F. 1969. Nuclear magnetic resonance studies of diquat, paraquat, and their charge-transfer complexes. J. Amer. Chem. Soc. 91:3822–3827.CrossRefGoogle Scholar
11. Hayashi, Y. and Kouji, H. 1990. Synthesis and herbicidal activity of geometrical isomers of methyl 1-5-2-chloro-4-(trifluoromethyl)phenoxy-2-nitrophenyl-2-methoxyethylidene, aminooxyacetate (AKH-7088). J. Agric. Food Chem. 38:845–850.Google Scholar
12. Hoagland, D. R. and Arnon, D. I. 1938. The water-culture method for growing plants without soil. University of California, College of Agriculture, Agricultural Experiment Station Berkeley, CA. Circular 347.Google Scholar
13. Jakajima, M., Itoi, K., Takamatsu, Y., Kinoshita, T., Okazaki, T., Kawakubo, K., Shindo, M., Honma, T., Tohjigamori, M., and Haneishi, T. 1991. Hydantocidin: a new compound with herbicidal activity from Streptomyces hygroscopicus . Journal of Antibiotics 44:293–300.CrossRefGoogle Scholar
14. Kelly, I. D., and Smith, S. 1986. Chromatographic purification and identification of polar metabolites of benazolin-ethyl from soybean. International J. Environ. Analytical Chem. 25:135–149.Google Scholar
15. Kissel, C. L., Brady, J. L., Guerra, A. M., Pau, J. K., Rockie, B. A., and Caserio, F. F. Jr. 1978. Analysis of acrolein in aged aqueous media. Comparison of various analytical methods with bioassays. J. Agric. Food Chem. 26:1338–1343.Google Scholar
16. Krause, A., Hancock, W. G., Minard, R. D., Freyer, A. J., Honeycutt, R. C., LeBaron, H. M., Paulson, D. L., Liu, S. Y., and Bollag, J. M. 1985. Microbial transformation of the herbicide metolachlor by a soil actinomycete. J. Agric. Food Chem. 33:584–589.CrossRefGoogle Scholar
17. Lamoureux, G. L., Rusness, D. G., and Tanaka, F. S. 1991. Chlorimuron ethyl metabolism in corn. Pesticide Biochemistry and Physiology. 41:66–81.Google Scholar
18. Leung, L. Y., Lyga, J. W., and Robinson, R. A. 1991. Metabolism and distribution of the experimental triazolone herbicide F6285 1-2,4-dichloro-5-N-(methylsulfonyl)aminophenyl-1,4-dihydro-3-methyl-4-(difluoromethyl)-5H-triazol-5-one in the rat goat and hen. J. Agric. Food Chem. 39:1509–1514.Google Scholar
19. Lynch, M. P., Beck, J. R., Tao, E. V. P., Aikins, J., Babbitt, G. E., Rizzo, J. R., and Waldrep, T. W. 1991. 1-alkyl-5-cyano-1H-pyrazole-4-carboxamides. Synthesis and herbicidal activity. ACS Symposium Series. (No. 443): 144–157.Google Scholar
20. Motekaitis, R. J. and Martell, A. E. 1985. Metal chelate formation by N-phosphonomethylglycine and related ligands. J. Coord. Chem. 14:139–149.Google Scholar
21. Nalewaja, J. D. and Matysiak, R. 1991. Salt antagonism of glyphosate. Weed Sci. 39:622–628.Google Scholar
22. Nishizawa, Y., Ogura, K., and Momo, H. 1989. Establishment of quick multiple analytical method for inert ingredients of pesticide formulation (part 1). Bulletin of the Agricultural Chemicals Inspection Station, Tokyo. 29:17–22.Google Scholar
23. Philp, D., Slawin, A.M.Z., Spencer, N., Stoddart, J. F., and Williams, D. J. 1991. The complexation of tetrathiafulvalene by cyclobis(paraquat-p-phenylene). J. Chem. Soc. Chem. Commun. 1584–1586.CrossRefGoogle Scholar
24. Pothuluri, J. V., Freeman, J. P., Evans, F. E., Moorman, T. B., and Cerniglia, G. E., 1993. Metabolism of alachlor by the fungus Cunninghamella elegans . J. Agric. Food Chem. 41:483–488.Google Scholar
25. Reddy, K. N. and Singh, M. 1992. Organosilicone adjuvant effects on glyphosate efficacy and rainfastness. Weed Technol. 6:361–365.Google Scholar
26. Retjo, M., Saltzman, S., Archer, A. J., and Muszkat, L. 1983. Identification of sensitized photooxidation products of s-triazine herbicides in water. J. Agric. Food Chem. 31:138–142.Google Scholar
27. Roggenbuck, F. C., Rowe, L., Penner, D., Petroff, L. and Burow, R. 1990. Increasing postemergence herbicide efficacy and rainfastness with silicone adjuvants. Weed Technol. 4:576–580.Google Scholar
28. Roggenbuck, F. C., Burow, R. F., and Penner, D. 1994. Relationship of leaf position to herbicide absorption and organosilicone adjuvant efficacy. Weed Technol. 8:582–585.Google Scholar
29. Rueppel, M. L., Brightwell, B. B., Schaefer, J., and Marvel, J. T. 1977. Metabolism and degradation of glyphosate in soil and water. J. Agric. Food Chem. 25:517–528.Google Scholar
30. Sato, K., Kato, Y., Maki, S., Matano, O., and Goto, S. 1979. Identification of urinary metabolites of 1-(alpha, alpha-dimethylbenzyl)-3-(p-tolyl)urea, dymrone in rats. J. Pestic. Sci., Japan 4:11–16.Google Scholar
31. Shea, P. J. and Tupy, D. R. 1984. Reversal of cation-induced reduction in glyphosate activity with EDTA. Weed Sci. 32:802–806.CrossRefGoogle Scholar
32. Stearman, G. K., Lewis, R. J., Tortorelli, L. J., and Tyler, D. D. 1989. Herbicide reactivity of soil organic matter fractions in no-tilled and tilled cotton. Soil Sci. Soc. Amer. J. 53:1690–1694.Google Scholar
33. Subramaniam, V. and Hoggard, P. E. 1988. Metal complexes of glyphosate. J. Agric. Food Chem. 336:1326–1329.CrossRefGoogle Scholar
34. Thelen, K. D., Jackson, E. P., and Penner, D. The basis for the hard-water antagonism of glyphosate activity. Weed Sci. (In press).Google Scholar
35. Yamamoto, S., Fujita, Y., Okujo, N., Minami, C., Matsuura, S., and Shinoda, S. 1992. Isolation and partial characterization of a compound with siderophore activity from Vibrio parahaemolyticus . FEMS Microbiology Letters 94:181–186.Google Scholar