Complexation and enantioselectivity of novel bridge-like uranyl- 2-((1Z,9Z)-9-(2-Hydroxyphenyl)-3,5,6,8-tetrahydrobenzo[h][1,4,7,10] dioxadiazacyclododecin-2-yl)-5-methoxyphenol with chiral organophosphorus pesticide enantiomers of R/S-malathions

Abstract

ABSTRACT Designing new uranyl complexes with enantioselectivity is of great significance for the identification and separation of enantiomers of chiral pesticides. In this paper, a new asymmetric rigid uranyl-2-((1Z,9Z)-9-(2-Hydroxyphenyl)-3,5,6,8-tetrahydrobenzo[h][1,4,7,10] dioxadiaza-cyclododecin-2-yl)-5-methoxyphenol(Uranyl-HTDM) was designed, we used Uranyl-HTDM as a receptor to selectively coordinate with the guests of the chiral organophosphorus pesticide R/S-malathions(R/S-MLTs) to explore the receptor's enatioselectivity recognition of the chiral guests of R/S-MLTs. Density functional theory (DFT) method was used to comprehensively study the complexation mode of the receptor with enantiomers. The results showed that the U of Uranyl-HTDM could coordinate with both the thiophosphoryl sulfur and carbonyl oxygens of R/S-MLTs in different environments, respectively. The thermodynamics calculations further indicated that the receptor could selectively recognize the thiophosphoryl sulfur and carbonyl oxygen atoms of R/S-malathions, and the complexation abilities of Uranyl-HTDM to the R/S-malathions under different solvents were not the same. The smaller the polarity of solvents, the stronger the complexation ability of Uranyl-HTDM with R-malathion, toluene was an ideal solvent with large △G change and enatioselectivity coefficient of 99.55%. The study provides useful references for the design of new uranyl-salophens and for the experimental study on the molecular recognition of chiral organophosphorus pesticides.