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Sorption of hydrophobic organic contaminants on functionalized biochar: protagonist role of π-π electron-donor-acceptor interactions and hydrogen bonds
Journal of Hazardous Materials ( IF 13.6 ) Pub Date : 2018-08-07 , DOI: 10.1016/j.jhazmat.2018.08.005
Mohammad Boshir Ahmed , John L. Zhou , Huu H. Ngo , Md. Abu Hasan Johir , Liying Sun , Mohammad Asadullah , Dalel Belhaj

The sorption of five potent endocrine disruptors as representative hydrophobic organic contaminants (HOCs) namely estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2) and bisphenol A (BPA) on functionalized biochar (fBC) was systematically examined, with a particular focus on the importance of π-electron-donor (phenanthrene: PHEN) and π-electron-acceptors (1,3-dinitrobenzene: DNB, p-amino benzoic acid: PABA) on sorption. Experimental results suggested that hydrogen-bond formation and π-π-electron-donor-acceptor (EDA) interactions were the dominant sorption mechanisms. The sorption of HOCs decreased as E1 > E2 > EE2 > E3 > BPA based on the Freundlich and Polanyi-Mane-models. The comparison of adsorption coefficient (Kd) normalized against hexadecane-water partition coefficient (KHW) between HOCs and PHEN indicated strong π-π-EDA interactions. π-π interactions among DNB, PHEN and HOCs were verified by the observed upfield frequency (Hz) shifts using proton nuclear magnetic resonance (1H NMR) which identified the specific direction of π-π interactions. UV-vis spectra showed charge-transfer bands for π-donors (PHEN and HOCs) with the model π-acceptor (DNB) also demonstrating the role of π-π EDA interactions. The role of π-electron-donor and π-electron-acceptor domains in fBC was identified at different solution pH.



中文翻译:

疏水性有机污染物在功能化生物炭上的吸附:π-π电子-供体-受体相互作用和氢键的主角作用

五个有效的内分泌干扰物为代表的疏水性有机污染物(肝卵圆细胞)即雌酮(E1),图17的吸附β雌二醇(E2),雌三醇(E3),17 α -ethynylestradiol(EE2)和双酚A(BPA)在官能化生物炭(fBC)进行了系统检查,特别关注π电子给体(菲:PHEN)和π电子受体(1,3-二硝基苯:DNB,氨基苯甲酸:PABA)对吸附的重要性。实验结果表明,氢键的形成和π-π-电子-给体-受体(EDA)的相互作用是主要的吸附机理。根据Freundlich和Polanyi-Mane模型,随着E1> E2> EE2> E3> BPA,HOC的吸附降低。吸附系数比较(Kd)对HOC和PHEN之间的十六烷-水分配系数( K HW)进行了归一化,表明存在很强的π-π-EDA相互作用。DNB,PHEN和HOC之间的π-π相互作用通过使用质子核磁共振( 1 H NMR)观察到的高场频率(Hz)位移进行了验证,该位移确定了π-π相互作用的特定方向。紫外-可见光谱显示了π-供体(PHEN和HOC)的电荷转移带,其中模型π-受体(DNB)也证明了π-πEDA相互作用的作用。在不同溶液pH下,fBC中的π电子给体和π电子受体域的作用得到了确认。

更新日期:2018-08-08
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