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Current Analytical Chemistry

Editor-in-Chief

ISSN (Print): 1573-4110
ISSN (Online): 1875-6727

Research Article

Detection Method of Environmentally Friendly Non-POP PBDEs by Derivatization-Enhanced Raman Spectroscopy Using the Pharmacophore Model

Author(s): Shujing Zhang, Youli Qiu and Yu Li*

Volume 15, Issue 6, 2019

Page: [656 - 667] Pages: 12

DOI: 10.2174/1573411014666180829103520

Price: $65

Abstract

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.

Keywords: Derivatization, Full factor experimental design, molecule modification, pharmacophore model, polybrominated diphenyl ethers, raman characteristic vibration spectrum.

Graphical Abstract
[1]
Stiborova, H.; Vrkoslavova, J.; Lovecka, P.; Pulkrabova, J.; Hradkova, P.; Hajslova, J.; Demnerova, K. Aerobic biodegradation of selected Polybrominated Diphenyl Ethers (PBDEs) in wastewater sewage sludge. Chemosphere, 2015, 118(1), 315-321.
[2]
Besis, A.; Samara, C. Polybrominated Diphenyl Ethers (PBDEs) in the indoor and outdoor environments-A review on occurrence and human exposure. Environ. Pollut., 2012, 169(15), 217-229.
[3]
Arellano, L.; Fernández, P.; López, J.F.; Rose, N.L.; Nickus, U. Thies, H.; Stuchlik, E.; Camarero, L.; Catalan, J.; Grimalt, J.O. Atmospheric deposition of polybromodiphenyl ethers in remote mountain regions of Europe. Atmospheric. Chem. Phys., 2013, 13(8), 4441.
[4]
Shaw, S.D.; Berger, M.L.; Brenner, D.; Carpenter, D.O.; Tao, L.; Hong, C.S.; Kannan, K. Polybrominated Diphenyl Ethers (PBDEs) in farmed and wild salmon marketed in the Northeastern United States. Chemosphere, 2008, 71(8), 1422-1431.
[5]
Besis, A.; Samara, C. Polybrominated Diphenyl Ethers (PBDEs) in the indoor and outdoor environments--a review on occurrence and human exposure. Environ. Pollut., 2012, 169(15), 217.
[6]
Darnerud, P.O.; Eriksen, G.S.; Johannesson, T.; Larsen, P.B.; Vi-luksela, M. Polybrominated diphenyl ethers: occurrence, dietary exposure, and toxicology. Environ. Health Persp., 2001, 109(suppl. 1), 49-68.
[7]
Òscar, A.; Aminot, Y.; Vilà-Cano, J.; Köck-Schulmeyer, M.; Readman, J.M.; Marques, A.; Godinho, C.; Botteon, E.; Ferrari, F.; Boti, V.; Albanis, T.; Eljarrat, E.; Barceló, D. Halogenated and organophosphorus flame retardants in European aquaculture samples. Sci. Total Environ., 2018, 612, 492-500.
[8]
Civan, M.Y.; Kara, U.M. Risk assessment of PBDEs and PAHs in house dust in Kocaeli, Turkey: Levels and sources. Environ. Sci. Pollut. R., 2016, 23(23), 1-16.
[9]
Huang, Y.; Zhang, D.; Yang, Y.; Zeng, X.; Ran, Y. Distribution and partitioning of polybrominated diphenyl ethers in sediments from the pearl river delta and guiyu, South China. Environ. Pollut., 2018, 235, 104-112.
[10]
Cowell, W.J.; Sjödin, A.; Jones, R.; Wang, Y.; Wang, S. Determinants of prenatal exposure to polybrominated diphenyl ethers (PBDEs) among urban, minority infants born between 1998 and 2006. Environ. Pollut., 2018, 233, 774-781.
[11]
Jiang, X.; Lai, Y.; Wang, W.; Jiang, W.; Zhan, J. Surface-enhanced Raman spectroscopy detection of polybrominated diphenyl ethers using a portable Raman spectrometer. Talanta, 2013, 116(22), 14-17.
[12]
Allchin, C.R.; Law, R.J.; Morris, S. Polybrominated diphenyl ethers in sediments and biota downstream of potential sources in the UK. Environ. Sci. Pollut. R., 1999, 105(2), 197-207.
[13]
Vecchiato, M.; Zambon, S.; Argiriadis, E.; Barbante, C.; Gambaro, A.; Piazza, R. Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Antarctic ice-free areas: Influence of local sources on lakes and soils. Microchem. J., 2015, 120, 26-33.
[14]
Vilaplana, F.; Karlsson, P.; Ribes-Greus, A.; Lvasson, P.; Karlsson, S. Analysis of brominated flame retardants in styrenic polymers: Comparison of the extraction efficiency of ultrasonication, microwave- assisted extraction and pressurised liquid extraction. J. Chromatogr. A., 2008, s1196-1197(1), 139-146.
[15]
Zeng, Y.L.; Jiang, L.; Cai, X.Y.; Li, Y. Identification of the characteristic vibrations for 16 PAHs based on Raman spectrum. Spectrosc Spect. Anal. 2014, 34(11), 2999-3004.
[16]
Jiang, L.; Li, Y. Study on identification of PBDEs and characteristic information extraction of biological toxicity based on infrared spectrum partition. Spectrosc. Spect. Anal., 2016, 36(11), 3530-3535.
[17]
Alicia, J.A.; Alex, L.G.; Suzanne, G.R.; Disney, M.D. Development of pharmacophore models for small molecules targeting RNA: application to the RNA repeat expansion in myotonic dystrophy type 1. Bioorg. Med. Chem. Lett., 2016, 26(23), 5792-5796.
[18]
Parkes, K.E.; Ermert, P.; Fässler, J.; Ives, J.; Martin, J.A.; Merrett, J.H.; Obrecht, D.; Williams, G.; Klumpp, K. Use of a pharmacophore model to discover a new class of influenza endonuclease inhibitors. J. Med. Chem., 2003, 46(7), 1153-1164.
[19]
Liu, B. Latest research progress on environment-friendly flame retardant polystyrene; Synthetic. Mater. Aging. Appl, 2014.
[20]
Gupta, A.K.; Chakroborty, S.; Srivastava, K.; Puri, S.K.; Saxena, A.K. Pharmacophore modeling of substituted 1,2,4-Trioxanes for quantitative prediction of their antimalarial activity. J. Chem. Inf. Model., 2010, 50(8), 1510-1520.
[21]
Nayana, R.S.; Bommisetty, S.K.; Singh, K.; Bairy, S.K.; Nunna, S.; Pramod, A.; Muttineni, R. Structural analysis of carboline derivatives as inhibitors of MAPKAP K2 using 3D QSAR and docking studies. J. Chem. Inf. Model., 2009, 49(1), 53-67.
[22]
Arooj, M.; Thangapandian, S.; John, S.; Hwang, S.; Park, J.K.; Lee, K.W. 3D QSAR pharmacophore modeling, in silico screening, and density functional theory (DFT) approaches for identification of human chymase inhibitors. Int. J. Mol. Sci., 2011, 12(12), 9236-9264.
[23]
Jiang, L.; Li, Y. How do the substituents affect and regulate the relative retention times of polychlorinated biphenyls during gas chromatography? J. Chemometr., 2016, 29(11), 606-614.
[24]
Li, X.L.; Ye, L.; Wang, X.X.; Wang, X.Z.; Liu, H.L.; Zhu, Y.L.; Yu, H.X. Combined 3D-QSAR, molecular docking and molecular dynamics study on thyroidhormone activity of hydroxylated polybrominated diphenyl ethers to thyroidreceptors β. Toxicol. Appl. Pharm., 2012, 265(3), 300-307.
[25]
Li, W.L.; Si, H.Z.; Li, Y.; Ge, C.Z.; Song, F.C. Ma, X.T.; Duan, Y.B.; Zhai, H.L. 3D-QSAR and molecular docking studies on designing inhibitors of the Hepatitis C virus NS5B polymerase. J. Mol. Struct., 2016, 1117, 227-239.
[26]
Holt, P.A.; Chairs, J.B.; Trent, J.O. Molecular docking of intercalators and groove-binders to nucleic acids using autodock and surflex. J. Chem. Inf. Model., 2008, 39(48), 1602-1615.
[27]
Yang, M.; Zhou, L.; Zuo, Z.L.; Tang, X.Y.; Liu, J. Structure-based virtual screening for glycosyltransferase51. Mol. Simulat., 2008, 34(9), 849-856.
[28]
Chen, G.; Konstantinov, A.D.; Chittinm, B.G.; Joyce, E.M.; Bols, N-C.; Bunce, N.J. Synthesis of polybrominated diphenyl ethers and their capacity to induce CYP1A by the Ah receptor mediated pathway. Environ. Sci. Technol., 2001, 35(18), 3749-3756.
[29]
Thangapandian, S.; John, S.; Sakkiah, S.; Lee, K.W. Pharmacophorebased virtual screening and Bayesian model for the identification of potential human leukotriene A4 hydrolase inhibitors. Eur. J. Med. Chem., 2011, 46(5), 1593-1603.
[30]
Jiang, L.; Li, Y. Modification of PBDEs(BDE-15,BDE-47,BDE-85 and BDE-126)biological toxicity, bioconcentration, persistence and atmospheric long-range transport potential based on the pharmacophore modeling assistant with the full factor experimental design. J. Hazard. Mater., 2016, 307, 202-212.
[31]
Lane, L.A.; Qian, X.; Nie, S. SERS nanoparticles in medicine: from label-free detection to spectroscopic tagging. Chem. Rev., 2015, 115(19), 10489-10529.
[32]
Chu, Z.H.; Li, Y. Designing modified polybrominated diphenyl ether BDE-47, BDE-99, BDE-100, BDE-183, and BDE-209 molecules with decreased estrogenic activities using 3D-QSAR, pharmacophore models coupled with resolution V of the 210-3 fractional factorial design and molecular docking. J. Hazard. Mater., 2018, 364, 151-162.
[33]
Papa, E.; Kovarich, S.; Gramatica, P. QSAR modeling and prediction of the endocrine-disrupting potencies of brominated flame retardants. Chem. Res. Toxicol., 2010, 23(5), 946-954.
[34]
Qiu, Y.L.; Zeng, Y.L.; Jiang, L.; Li, Y. Identification of the Raman characteristic spectrum vibrations for various PAEs based on benzene solvent effect. Chin. J. Lumin., 2015, 36(8), 976-982.

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