{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T13:49:09Z","timestamp":1785419349821,"version":"3.56.0"},"reference-count":59,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2021,7,21]],"date-time":"2021-07-21T00:00:00Z","timestamp":1626825600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100004281","name":"Narodowe Centrum Nauki","doi-asserted-by":"publisher","award":["2018\/31\/D\/ST5\/01057 AND DEC-2018\/29\/B\/NZ9\/01136"],"award-info":[{"award-number":["2018\/31\/D\/ST5\/01057 AND DEC-2018\/29\/B\/NZ9\/01136"]}],"id":[{"id":"10.13039\/501100004281","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>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\u2013anion 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.<\/jats:p>","DOI":"10.3390\/molecules26154396","type":"journal-article","created":{"date-parts":[[2021,7,22]],"date-time":"2021-07-22T22:35:31Z","timestamp":1626993331000},"page":"4396","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Transformation of Iodosulfuron-Methyl into Ionic Liquids Enables Elimination of Additional Surfactants in Commercial Formulations of Sulfonylureas"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6484-4507","authenticated-orcid":false,"given":"Witold","family":"Stachowiak","sequence":"first","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rados\u0142aw","family":"Szumski","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jan","family":"Homa","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4461-6785","authenticated-orcid":false,"given":"Marta","family":"Wo\u017aniak-Karczewska","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2061-1031","authenticated-orcid":false,"given":"Anna","family":"Parus","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Beata","family":"Strzemiecka","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2171-4913","authenticated-orcid":false,"given":"\u0141ukasz","family":"Chrzanowski","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4364-8267","authenticated-orcid":false,"given":"Micha\u0142","family":"Niemczak","sequence":"additional","affiliation":[{"name":"Department of Chemical Technology, Poznan University of Technology, 60-965 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"840","DOI":"10.5114\/aoms.2015.53304","article-title":"Sulfonylureas and their use in clinical practice","volume":"11","author":"Sola","year":"2015","journal-title":"Arch. Med. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"6253","DOI":"10.1021\/jf025575p","article-title":"Hydrolysis of sulfonylurea herbicides in soils and aqueous solutions: A review","volume":"50","author":"Sarmah","year":"2002","journal-title":"J. Agric. Food Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"10362","DOI":"10.1021\/acs.jafc.8b02584","article-title":"Dicationic Ionic Liquids of Herbicide 2,4-Dichlorophenoxyacetic Acid with Reduced Negative Effects on Environment","volume":"66","author":"Niu","year":"2018","journal-title":"J. Agric. Food Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4838","DOI":"10.1016\/j.tet.2011.05.016","article-title":"Ionic liquids with herbicidal anions","volume":"67","author":"Pernak","year":"2011","journal-title":"Tetrahedron"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1111\/j.1574-6968.1998.tb12925.x","article-title":"Different toxic effects of the sulfonylurea herbicides metsulfuron methyl, chlorsulfuron and thifensulfuron methyl on fluorescent pseudomonads isolated from an agricultural soil","volume":"161","author":"Boldt","year":"1998","journal-title":"FEMS Microbiol. Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1312","DOI":"10.1016\/j.chemosphere.2007.01.036","article-title":"Hydrolytic degradation of azimsulfuron, a sulfonylurea herbicide","volume":"68","author":"Boschin","year":"2007","journal-title":"Chemosphere"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"13661","DOI":"10.1021\/acs.jafc.0c05850","article-title":"Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy","volume":"68","author":"Niemczak","year":"2020","journal-title":"J. Agric. Food Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"57","DOI":"10.1016\/j.eja.2011.03.002","article-title":"White mustard (Sinapis alba) resistance to ALS-inhibiting herbicides and alternative herbicides for control in Spain","volume":"35","author":"Rosario","year":"2011","journal-title":"Eur. J. Agron."},{"key":"ref_9","unstructured":"(2021, February 16). FAOSTAT Pesticides Use. Available online: http:\/\/www.fao.org\/faostat\/en\/#data\/RP."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"103","DOI":"10.1080\/02772240410001665409","article-title":"Persistence of the sulfonylurea herbicide iodosulfuron-methyl in the soil of winter wheat crops","volume":"85","author":"Rouchaud","year":"2003","journal-title":"Toxicol. Environ. Chem."},{"key":"ref_11","unstructured":"Roechling, A., and Akyuez, A. (2017). Chemical Stabilization of Iodosulfuron-Methyl Sodium Salt by Hydroxystearates. (9,763,450), U.S. Patent."},{"key":"ref_12","unstructured":"Deckwer, R., Haase, D., Krause, H.-P., and Schnabel, G. (2004). Oil Suspension Concentrate. (No. PCT\/EP2003\/013389), International Application."},{"key":"ref_13","unstructured":"Reap, J., and Beestman, G. (2009). Liquid Sulfonylurea Herbicide Formulations. (Application 11\/990,090), U.S. Patent."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"827","DOI":"10.1039\/C8NJ05903A","article-title":"Novel herbicide ionic liquids based on nicosulfuron with increased efficacy","volume":"43","author":"Wang","year":"2019","journal-title":"New J. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"3357","DOI":"10.1021\/jf505782p","article-title":"Metsulfuron-Methyl-Based Herbicidal Ionic Liquids","volume":"63","author":"Pernak","year":"2015","journal-title":"J. Agric. Food Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"28676","DOI":"10.1039\/C8RA03519A","article-title":"Ammonium bio-ionic liquids based on camelina oil as potential novel agrochemicals","volume":"8","author":"Pernak","year":"2018","journal-title":"RSC Adv."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Green, J.M., and Cahill, W.R. (2003). Enhancing the biological activity of nicosulfuron with silicone adjuvants and pH adjusters. ASTM Spec. Tech. Publ., 115\u2013124.","DOI":"10.1520\/STP11200S"},{"key":"ref_18","first-page":"1500","article-title":"Hydrolysis and biodegradation of sulfonylurea herbicides in aqueous buffers and anaerobic water-sediment systems: Assessing fate pathways using molecular descriptors","volume":"15","author":"Berger","year":"1996","journal-title":"Environ. Toxicol. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"103","DOI":"10.5586\/aa.2013.044","article-title":"The effect of reduced rates of crop protection agents and adjuvants on productivity, weed infestation and health of spring barley (Hordeum sativum L.)","volume":"66","author":"Kwiatkowski","year":"2013","journal-title":"Acta Agrobot."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"4764","DOI":"10.1039\/C8GC01424H","article-title":"Ionic liquids as bioactive chemical tools for use in agriculture and the preservation of agricultural products","volume":"20","author":"Zajac","year":"2018","journal-title":"Green Chem."},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Mesnage, R., and Antoniou, M.N. (2018). Ignoring Adjuvant Toxicity Falsifies the Safety Profile of Commercial Pesticides. Front. Public Health, 5.","DOI":"10.3389\/fpubh.2017.00361"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"159","DOI":"10.2165\/00139709-200423030-00003","article-title":"Glyphosate poisoning","volume":"23","author":"Bradberry","year":"2004","journal-title":"Toxicol. Rev."},{"key":"ref_23","unstructured":"(2021, February 16). Huzar Activ 387 OD MSDS. Available online: https:\/\/www.agro.bayer.com.pl\/produkty\/srodki-ochrony-roslin\/huzar-activ-387-od."},{"key":"ref_24","unstructured":"(2021, February 16). Hussar\u00ae Selective Herbicide MSDS. Available online: https:\/\/resources.bayer.com.au\/resources\/uploads\/msds\/file7357.pdf."},{"key":"ref_25","unstructured":"(2021, February 16). Huzar 05 WG label, Available online: https:\/\/gov.pl\/documents\/912055\/913531\/Huzar+05+WG.pdf."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"14996","DOI":"10.1021\/acssuschemeng.0c05419","article-title":"Development of Poly(ionic liquids) Based on Mepiquat Chloride with Improved Rainfastness and Long-Lasting Activity on Growth Regulation of Cotton Plant","volume":"8","author":"Tang","year":"2020","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"10456","DOI":"10.1021\/acs.jafc.0c02894","article-title":"Herbicidal ionic liquids: A promising future for old herbicides? Review on synthesis, toxicity, biodegradation, and efficacy studies","volume":"68","author":"Wilms","year":"2020","journal-title":"J. Agric. Food Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"114792","DOI":"10.1016\/j.molliq.2020.114792","article-title":"Choline-based ionic liquids as adjuvants in pesticide formulation","volume":"327","author":"Kaczmarek","year":"2020","journal-title":"J. Mol. Liq."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"529","DOI":"10.1002\/cplu.201800251","article-title":"Synthesis and Structure\u2013Property Relationships in Herbicidal Ionic Liquids and their Double Salts","volume":"83","author":"Niemczak","year":"2018","journal-title":"Chempluschem"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"842","DOI":"10.1021\/acssuschemeng.9b04859","article-title":"Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products","volume":"8","author":"Czerwoniec","year":"2020","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"3412","DOI":"10.1021\/acssuschemeng.9b07598","article-title":"Quantifying the Mineralization of 13C-Labeled Cations and Anions Reveals Differences in Microbial Biodegradation of Herbicidal Ionic Liquids between Water and Soil","volume":"8","author":"Wilms","year":"2020","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"6048","DOI":"10.1021\/acs.jafc.0c00842","article-title":"Preparation of Acifluorfen-Based Ionic Liquids with Fluorescent Properties for Enhancing Biological Activities and Reducing the Risk to the Aquatic Environment","volume":"68","author":"Tang","year":"2020","journal-title":"J. Agric. Food Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"16620","DOI":"10.1021\/acssuschemeng.9b03948","article-title":"Ionic Liquid Forms of Mesotrione with Enhanced Stability and Reduced Leaching Risk","volume":"7","author":"Wang","year":"2019","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"622","DOI":"10.1021\/acs.estlett.0c00437","article-title":"Increased Use of Quaternary Ammonium Compounds during the SARS-CoV-2 Pandemic and Beyond: Consideration of Environmental Implications","volume":"7","author":"Hora","year":"2020","journal-title":"Environ. Sci. Technol. Lett."},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Schindler, W.D., and Hauser, P.J. (2004). 3\u2014Softening finishes. Chemical Finishing of Textiles, Woodhead Publishing.","DOI":"10.1201\/9781439823477"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"260","DOI":"10.1021\/acs.jafc.6b04528","article-title":"Alkyl(C16, C18, C22)trimethylammonium-Based Herbicidal Ionic Liquids","volume":"65","author":"Pernak","year":"2017","journal-title":"J. Agric. Food Chem."},{"key":"ref_37","unstructured":"(2020, December 16). Annex 5 List of Preservatives Allowed in Cosmetic Products. Available online: https:\/\/ec.europa.eu\/growth\/tools-databases\/cosing\/pdf\/COSING_Annex V_v2.pdf."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"472","DOI":"10.1016\/j.cej.2015.05.025","article-title":"Ionic liquid forms of clopyralid with increased efficacy against weeds and reduced leaching from soils","volume":"279","author":"Zhu","year":"2015","journal-title":"Chem. Eng. J."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2741","DOI":"10.1021\/acssuschemeng.7b04382","article-title":"Bioherbicidal Ionic Liquids","volume":"6","author":"Pernak","year":"2018","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"4546","DOI":"10.1039\/C4GC01149J","article-title":"A survey of solvent selection guides","volume":"16","author":"Prat","year":"2014","journal-title":"Green Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1021\/bk-2002-0818.ch001","article-title":"Green Chemistry and Ionic Liquids: Synergies and Ironies","volume":"818","author":"Holbrey","year":"2002","journal-title":"ACS Symp. Ser."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"5363","DOI":"10.1021\/acs.jpcb.7b01712","article-title":"Cation Dynamics in Supercooled and Solid Alkyl Methylimidazolium Bromide Ionic Liquids","volume":"121","author":"Stapf","year":"2017","journal-title":"J. Phys. Chem. B"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"6357","DOI":"10.1021\/cr500411q","article-title":"Structure and Nanostructure in Ionic Liquids","volume":"115","author":"Hayes","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"7330","DOI":"10.1039\/C5RA23997D","article-title":"Synthesis, properties and evaluation of biological activity of herbicidal ionic liquids with 4-(4-chloro-2-methylphenoxy)butanoate anion","volume":"6","author":"Pernak","year":"2016","journal-title":"RSC Adv."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"391","DOI":"10.1039\/C1FD00075F","article-title":"The ion speciation of ionic liquids in molecular solvents of low and medium polarity","volume":"154","author":"Jiang","year":"2012","journal-title":"Faraday Discuss."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"4","DOI":"10.1016\/j.emcon.2018.12.002","article-title":"Role of organic amendments in reducing leaching of sulfosulfuron through wheat crop cultivated soil","volume":"5","author":"Joshi","year":"2019","journal-title":"Emerg. Contam."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"936","DOI":"10.1021\/je1008872","article-title":"A predictive model for the solubility and octanol-water partition coefficient of pharmaceuticals","volume":"56","author":"Hsieh","year":"2011","journal-title":"J. Chem. Eng. Data"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1039\/B410891D","article-title":"Octanol-water partition coefficients of imidazolium-based ionic liquids","volume":"7","author":"Ropel","year":"2005","journal-title":"Green Chem."},{"key":"ref_49","unstructured":"Crookes, M.J., and Fisk, P. (2018). Evaluation of Using Mobility of Chemicals in the Environment to Fulfil Bioaccumulation Criteria of the Stockholm Convention, Peter Fisk Associates."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"338","DOI":"10.1614\/0890-037X(2003)017[0338:ETBAON]2.0.CO;2","article-title":"Enhancing the Biological Activity of Nicosulfuron with pH Adjusters 1","volume":"17","author":"Green","year":"2003","journal-title":"Weed Technol."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"8869","DOI":"10.1039\/D0NJ01597K","article-title":"Transformation of herbicides into dual function quaternary tropinium salts","volume":"44","author":"Parus","year":"2020","journal-title":"New J. Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"10855","DOI":"10.1021\/jf5034398","article-title":"Influence of soil biochar aging on sorption of the herbicides MCPA, nicosulfuron, terbuthylazine, indaziflam, and fluoroethyldiaminotriazine","volume":"62","author":"Trigo","year":"2014","journal-title":"J. Agric. Food Chem."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"42","DOI":"10.1016\/j.jhazmat.2018.04.045","article-title":"Biodegradation and toxicity of a maize herbicide mixture: Mesotrione, nicosulfuron and S-metolachlor","volume":"354","author":"Carles","year":"2018","journal-title":"J. Hazard. Mater."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1016\/j.aca.2005.11.079","article-title":"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","volume":"559","author":"Zhou","year":"2006","journal-title":"Anal. Chim. Acta"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1016\/S0048-9697(99)00536-7","article-title":"Occurrence of sulfonylurea, sulfonamide, imidazolinone, and other herbicides in rivers, reservoirs and ground water in the Midwestern United States, 1998","volume":"248","author":"Battaglin","year":"2000","journal-title":"Sci. Total Environ."},{"key":"ref_56","unstructured":"Vogel, A.I. (1991). Textbook of Practical Organic Chemistry, John Wiley & Sons."},{"key":"ref_57","unstructured":"OECD (1995). Water Solubility No. 105, OECD."},{"key":"ref_58","doi-asserted-by":"crossref","unstructured":"OECD (1995). Partition Coefficient (n-Octanol\/Water), Shake Flask Method, No. 107, OECD.","DOI":"10.1787\/9789264069626-en"},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"14584","DOI":"10.1021\/acssuschemeng.0c05603","article-title":"Double-Action Herbicidal Ionic Liquids Based on Dicamba Esterquats with 4-CPA, 2,4-D, MCPA, MCPP, and Clopyralid Anions","volume":"8","author":"Syguda","year":"2020","journal-title":"ACS Sustain. Chem. Eng."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/15\/4396\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:32:45Z","timestamp":1760164365000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/15\/4396"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,21]]},"references-count":59,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2021,8]]}},"alternative-id":["molecules26154396"],"URL":"https:\/\/doi.org\/10.3390\/molecules26154396","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,21]]}}}