Shujing Zhang, Youli Qiu and Yu Li* Pages 1 - 12 ( 12 )
Background: Polybrominated diphenyl ethers (PBDEs) are dangerous for the environment and human health because of their persistent organic pollutant (POP) characteristics, which have attracted extensive research attention. Raman spectroscopy is a simple highly sensitive detection operation. This study was performed to obtain environmentally friendly non-POP PBDE derivatives with simple detection-based molecular design and provide theoretical support for establishing enhanced Raman spectroscopic detection techniques.Methods: A three-dimensional quantitative structure-activity relationship (3DQSAR) pharmacophore model of characteristic PBDE Raman spectral was established using 20 and 10 PBDEs as training and test sets, respectively. Full-factor experimental design was used to modify representative commercial PBDEs, and their flame retardancy and POP characteristics were evaluated. Results: The pharmacophore model (Hypo1) exhibited good predictive ability with the largest correlation coefficient (R2) of 0.88, the smallest root mean square (RMS) value of 0.231, and total cost of 81.488 with a configuration value of 12.56 (˂17).74 monosubstituted and disubstituted PBDE derivatives were obtained based on the Hypo 1 pharmacophore model and full-factor experimental design auxiliary. Twenty PBDE derivatives were screened, and their flame-retardant capabilities were enhanced and their migration and bio-concentration were reduced (log(KOW) <5), with unchanged toxicity and high biodegradability. The Raman spectral intensities increased up to 380%. In addition, interference analysis of the Raman peaks by group frequency indicated that the 20 PBDE derivatives were easily detected with no interference in gaseous environments. Conclusion: Nine pharmacophore models were constructed in this study; Hypo 1 was the most accurate. Twenty PBDE derivatives showed Raman spectral intensities increased up to 380%; these were classified as new non-POP environmentally friendly flame retardants with low toxicity, low migration, good biodegradability, and low bio-concentrations. 2D QSAR analysis showed that the most positive Milliken charge and lowest occupied orbital energy were the main contributors to the PBDE Raman spectral intensities. Raman peak analysis revealed no interference between the derivatives in gaseous environments.
Derivatization, full factor experimental design, molecule modification, pharmacophore model, polybrominated diphenyl ethers, raman characteristic vibration spectrum.
College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206