TY - JOUR

T1 - Identification of structure-biodegradability relationships for ionic liquids - clustering of a dataset based on structural similarity

AU - Amsel, Ann Kathrin

AU - Olsson, Oliver

AU - Kümmerer, Klaus

N1 - Funding Information: We would like to thank the German Federal Ministry for the Environment, Nature Conservation, Nuclear Safety and Consumer Protection (BMUV) and the German Umweltbundesamt (UBA) for their support with the International Sustainable Chemistry Collaborative Centre (ISC3) activities. We thank our colleagues Stefanie Lorenz and Morten Suk for fruitful discussions on the biodegradability of ILs and on clustering compounds. Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/9/29

Y1 - 2023/9/29

N2 - Environmentally open applications as herbicides or active pharmaceutical ingredients are discussed for ionic liquids (ILs). Since most of the ILs are not readily biodegradable in the environment, they may persist there. To prevent the accumulation of persistent and toxic ILs, both the cation and anion need to be designed to completely mineralise in the environment. Several studies summarised structure-biodegradability relationships (SBRs) and gained rules of thumb for ILs’ biodegradability based on the available literature data. However, no study systematically analysed a dataset using an in silico tool. Therefore, to identify SBRs a dataset on the ready biodegradability of 508 ILs was clustered according to IL similarity by using the software Canvas by Schrödinger. The biodegradability was divided into three classes (biodegradation rates 0-19%, 20-59% and ≥60%). The identified SBRs were compared with the available rules of thumb from the literature. The results show that the cholinium cation and its derivatives acetylcholine, betaine and carnitine are promising candidates for designing environmentally mineralising ILs if a good biodegradable anion is chosen. Imidazolium and phosphonium ILs should be avoided. For pyrrolidinium and quaternary ammonium compounds cations containing ester or carboxyl groups in side chains and alkylsulphate anions should be tested to close gaps in SBRs and possibly design a mineralising IL. Due to the limited data of morpholinium, 1,4-diazabicyclo[2.2.2]octanium (DABCO), piperidinium, prolinium, piperazinium and thiazolium ILs, SBRs could not be clearly identified. Further research is needed on whether structural adjustments according to the findings can increase the biodegradability of not yet fully degrading (20-59%) ILs.

AB - Environmentally open applications as herbicides or active pharmaceutical ingredients are discussed for ionic liquids (ILs). Since most of the ILs are not readily biodegradable in the environment, they may persist there. To prevent the accumulation of persistent and toxic ILs, both the cation and anion need to be designed to completely mineralise in the environment. Several studies summarised structure-biodegradability relationships (SBRs) and gained rules of thumb for ILs’ biodegradability based on the available literature data. However, no study systematically analysed a dataset using an in silico tool. Therefore, to identify SBRs a dataset on the ready biodegradability of 508 ILs was clustered according to IL similarity by using the software Canvas by Schrödinger. The biodegradability was divided into three classes (biodegradation rates 0-19%, 20-59% and ≥60%). The identified SBRs were compared with the available rules of thumb from the literature. The results show that the cholinium cation and its derivatives acetylcholine, betaine and carnitine are promising candidates for designing environmentally mineralising ILs if a good biodegradable anion is chosen. Imidazolium and phosphonium ILs should be avoided. For pyrrolidinium and quaternary ammonium compounds cations containing ester or carboxyl groups in side chains and alkylsulphate anions should be tested to close gaps in SBRs and possibly design a mineralising IL. Due to the limited data of morpholinium, 1,4-diazabicyclo[2.2.2]octanium (DABCO), piperidinium, prolinium, piperazinium and thiazolium ILs, SBRs could not be clearly identified. Further research is needed on whether structural adjustments according to the findings can increase the biodegradability of not yet fully degrading (20-59%) ILs.

KW - Chemistry

UR - http://www.scopus.com/inward/record.url?scp=85175463584&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/aeb7fc96-0f4d-3695-8827-2cfd069b9b53/

U2 - 10.1039/d3gc02392c

DO - 10.1039/d3gc02392c

M3 - Journal articles

AN - SCOPUS:85175463584

VL - 25

SP - 9226

EP - 9250

JO - Green Chemistry

JF - Green Chemistry

SN - 1463-9262

IS - 22

ER -