Transformation of Iodosulfuron-Methyl into Ionic Liquids Enables Elimination of Additional Surfactants in Commercial Formulations of Sulfonylureas

Efficient use of herbicides for plant protection requires the application of auxiliary substances such as surfactants, stabilizers, wetting or anti-foaming agents, and absorption enhancers, which can be more problematic for environment than the herbicides themselves. We hypothesized that the combination of sulfonylurea (iodosulfuron-methyl) anion with inexpensive, commercially available quaternary tetraalkylammonium cations could lead to biologically active ionic liquids (ILs) that could become a convenient and environment-friendly alternative to adjuvants. A simple one-step synthesis allowed for synthesizing iodosulfuron-methyl based ILs with high yields ranging from 88 to 96% as confirmed by UV, FTIR, and NMR. The obtained ILs were found to possess several favorable properties compared to the currently used sodium salt iodosulfuron-methyl, such as adjustable hydrophobicity (octanol-water partition coefficient) and enhanced stability in aqueous solutions, which was supported by molecular calculations showing cation–anion interaction energies. In addition, soil mobility and volatility of ILs were more beneficial compared to the parental herbicide. Herbicidal activity tests toward oil-seed rape and cornflower revealed that ILs comprising at least one alkyl chain in the decyl to octadecyl range had similar or better efficacy compared to the commercial preparation without addition of any adjuvant. Furthermore, results of antimicrobial activity indicated that they were practically harmless or slightly toxic toward model soil microorganisms such as Pseudomonas putida and Bacillus cereus.

[1]  J. Pernak,et al.  Choline-based ionic liquids as adjuvants in pesticide formulation , 2020 .

[2]  Łukasz Sobiech,et al.  Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy , 2020, Journal of agricultural and food chemistry.

[3]  K. Materna,et al.  Double-Action Herbicidal Ionic Liquids Based on Dicamba Esterquats with 4-CPA, 2,4-D, MCPA, MCPP, and Clopyralid Anions , 2020 .

[4]  Gang Tang,et al.  Development of Poly(ionic liquids) Based on Mepiquat Chloride with Improved Rainfastness and Long-Lasting Activity on Growth Regulation of Cotton Plant , 2020 .

[5]  J. Pernak,et al.  Herbicidal Ionic Liquids: A Promising Future for Old Herbicides? Review on Synthesis, Toxicity, Biodegradation, and Efficacy Studies , 2020, Journal of agricultural and food chemistry.

[6]  P. McNamara,et al.  Increased Use of Quaternary Ammonium Compounds during the SARS-CoV-2 Pandemic and Beyond: Consideration of Environmental Implications , 2020, Environmental science & technology letters.

[7]  A. Borkowski,et al.  Transformation of herbicides into dual function quaternary tropinium salts , 2020 .

[8]  Wenbing Zhang,et al.  Preparation of acifluorfen-based ionic liquids with fluorescent properties for enhancing biological activities and reducing the risk to the aquatic environment. , 2020, Journal of agricultural and food chemistry.

[9]  J. Pernak,et al.  Quantifying the Mineralization of 13C-Labeled Cations and Anions Reveals Differences in Microbial Biodegradation of Herbicidal Ionic Liquids between Water and Soil , 2020 .

[10]  J. Feder-Kubis,et al.  Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products , 2020 .

[11]  You Liang,et al.  Ionic Liquid Forms of Mesotrione with Enhanced Stability and Reduced Leaching Risk , 2019, ACS Sustainable Chemistry & Engineering.

[12]  You Liang,et al.  Novel herbicide ionic liquids based on nicosulfuron with increased efficacy , 2019, New Journal of Chemistry.

[13]  V. Joshi,et al.  Role of organic amendments in reducing leaching of sulfosulfuron through wheat crop cultivated soil , 2019, Emerging Contaminants.

[14]  Rafal Kukawka,et al.  Ionic liquids as bioactive chemical tools for use in agriculture and the preservation of agricultural products , 2018 .

[15]  Gang Tang,et al.  Dicationic Ionic Liquids of Herbicide 2,4-Dichlorophenoxyacetic Acid with Reduced Negative Effects on Environment. , 2018, Journal of agricultural and food chemistry.

[16]  D. Kurasiak-Popowska,et al.  Ammonium bio-ionic liquids based on camelina oil as potential novel agrochemicals , 2018, RSC advances.

[17]  M. Joly,et al.  Biodegradation and toxicity of a maize herbicide mixture: mesotrione, nicosulfuron and S-metolachlor. , 2018, Journal of hazardous materials.

[18]  J. Pernak,et al.  Synthesis and Structure-Property Relationships in Herbicidal Ionic Liquids and their Double Salts. , 2018, ChemPlusChem.

[19]  R. Mesnage,et al.  Ignoring Adjuvant Toxicity Falsifies the Safety Profile of Commercial Pesticides , 2018, Front. Public Health.

[20]  J. Pernak,et al.  Bioherbicidal Ionic Liquids , 2017 .

[21]  C. Mattea,et al.  Cation Dynamics in Supercooled and Solid Alkyl Methylimidazolium Bromide Ionic Liquids. , 2017, The journal of physical chemistry. B.

[22]  J. Pernak,et al.  Alkyl(C16, C18, C22)trimethylammonium-Based Herbicidal Ionic Liquids. , 2017, Journal of agricultural and food chemistry.

[23]  K. Materna,et al.  Synthesis, properties and evaluation of biological activity of herbicidal ionic liquids with 4-(4-chloro-2-methylphenoxy)butanoate anion , 2016 .

[24]  Yao Liu,et al.  Ionic liquid forms of clopyralid with increased efficacy against weeds and reduced leaching from soils , 2015 .

[25]  E. Bartoli,et al.  Sulfonylureas and their use in clinical practice , 2015, Archives of medical science : AMS.

[26]  R. Atkin,et al.  Structure and nanostructure in ionic liquids. , 2015, Chemical reviews.

[27]  Julia L. Shamshina,et al.  Metsulfuron-methyl-based herbicidal ionic liquids. , 2015, Journal of agricultural and food chemistry.

[28]  K. Spokas,et al.  Influence of soil biochar aging on sorption of the herbicides MCPA, nicosulfuron, terbuthylazine, indaziflam, and fluoroethyldiaminotriazine. , 2014, Journal of agricultural and food chemistry.

[29]  John D. Hayler,et al.  A survey of solvent selection guides , 2014 .

[30]  E. Harasim,et al.  The effect of reduced rates of crop protection agents and adjuvants on productivity, weed infestation and health of spring barley (Hordeum sativum L.) , 2013 .

[31]  H. Weingärtner,et al.  The ion speciation of ionic liquids in molecular solvents of low and medium polarity. , 2012, Faraday discussions.

[32]  R. Prado,et al.  White mustard (Sinapis alba) resistance to ALS-inhibiting herbicides and alternative herbicides for control in Spain , 2011 .

[33]  K. Materna,et al.  Ionic liquids with herbicidal anions , 2011 .

[34]  S. Sandler,et al.  A Predictive Model for the Solubility and Octanol-Water Partition Coefficient of Pharmaceuticals , 2011 .

[35]  A. Arnoldi,et al.  Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide. , 2007, Chemosphere.

[36]  Qingxiang Zhou,et al.  Preconcentration and determination of nicosulfuron, thifensulfuron-methyl and metsulfuron-methyl in water samples using carbon nanotubes packed cartridge in combination with high performance liquid chromatography , 2006 .

[37]  M. Stadtherr,et al.  Octanol–water partition coefficients of imidazolium-based ionic liquids , 2005 .

[38]  J. A. Vale,et al.  Glyphosate Poisoning , 2022, Toxicological reviews.

[39]  Герхард Шнабель,et al.  The oil suspension concentrate , 2004 .

[40]  P. Hauser,et al.  3 – Softening finishes , 2004 .

[41]  R. Bulcke,et al.  Persistence of the sulfonylurea herbicide iodosulfuron-methyl in the soil of winter wheat crops , 2003 .

[42]  Jerry M. Green,et al.  Enhancing the Biological Activity of Nicosulfuron with pH Adjusters1 , 2003, Weed Technology.

[43]  Jm Green,et al.  Enhancing the Biological Activity of Nicosulfuron with Silicone Adjuvants and pH Adjusters , 2003 .

[44]  A. Sarmah,et al.  Hydrolysis of sulfonylurea herbicides in soils and aqueous solutions: a review. , 2002, Journal of agricultural and food chemistry.

[45]  R. Rogers,et al.  Green chemistry and ionic liquids: Synergies and ironies , 2002 .

[46]  W. Battaglin,et al.  Occurrence of sulfonylurea, sulfonamide, imidazolinone, and other herbicides in rivers, reservoirs and ground water in the Midwestern United States, 1998. , 2000, The Science of the total environment.

[47]  C. Jacobsen,et al.  Different toxic effects of the sulfonylurea herbicides metsulfuron methyl, chlorsulfuron and thifensulfuron methyl on fluorescent pseudomonads isolated from an agricultural soil , 1998 .

[48]  N. Wolfe,et al.  Hydrolysis and biodegradation of sulfonylurea herbicides in aqueous buffers and anaerobic water‐sediment systems: Assessing fate pathways using molecular descriptors , 1996 .

[49]  J. W. COOK,et al.  A Text-Book of Practical Organic Chemistry , 1948, Nature.