Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal-Organic Frameworks

ACS Appl Mater Interfaces. 2021 Jun 23;13(24):28424-28432. doi: 10.1021/acsami.1c08833. Epub 2021 Jun 14.

Abstract

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal-organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {SrIICuII6[(S,S)-methox]1.5[(S,S)-Mecysmox]1.50(OH)2(H2O)}·36H2O (5), featuring narrow functional channels decorated with both -CH2SCH3 and -CH2CH2SCH3 thioalkyl chains-from l-methionine and l-methylcysteine amino acid-derived ligands, respectively-stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions-less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.

Keywords: amino acids; crystal structures; host−guest chemistry; multivariate metal−organic frameworks; neonicotinoid insecticides; water remediation.

MeSH terms

  • Adsorption
  • Cysteine / analogs & derivatives
  • Cysteine / chemistry
  • Insecticides / chemistry
  • Insecticides / isolation & purification*
  • Metal-Organic Frameworks / chemistry*
  • Methionine / chemistry
  • Neonicotinoids / chemistry
  • Neonicotinoids / isolation & purification*
  • Solid Phase Extraction / methods
  • Sulfides / chemistry*
  • Water Pollutants, Chemical / chemistry
  • Water Pollutants, Chemical / isolation & purification*
  • Water Purification / methods

Substances

  • Insecticides
  • Metal-Organic Frameworks
  • Neonicotinoids
  • Sulfides
  • Water Pollutants, Chemical
  • S-methylcysteine
  • Methionine
  • Cysteine