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pH 和离子强度对含氮多环芳烃化合物与腐殖酸之间结合常数的影响。

pH and ionic strength effects on the binding constant between a nitrogen-containing polycyclic aromatic compound and humic acid.

机构信息

Department of Marine Environment and Engineering, National Sun Yat-sen University, Kaohsiung, 804, Taiwan.

出版信息

Environ Sci Pollut Res Int. 2015 Sep;22(17):13234-42. doi: 10.1007/s11356-015-4392-z. Epub 2015 May 5.

Abstract

Polycyclic aromatic compounds (PACs) are widespread environmental pollutants with a high potential to act as human carcinogens and mutagens. The behavior of PACs is significantly affected by their interactions with dissolved organic matter (DOM), such as their transport, solubility, bioavailability, and bioaccumulation in the aquatic environment. Being a basic PAC, benzo(h)quinoline (BQ) is the dominant species, as the solution's pH value is higher than BQ's pK a (pK a of BQ = 4.2). In contrast, benzo(h)quinolinium (BQH(+)) is the major species, as the solution's pH value is lower than its pK a. The binding constant (K DOC), measured by fluorescence quenching, between BQ/BQH(+) and Leonardite humic acid (LHA) would decrease 70 to 95 % and 20 to 90 % when increasing the ionic strength in acidic and neutral to basic conditions, respectively. The results can be attributed to the added cation (Na(+) and Mg(2+)), which forms a bridge with LHA and enhances the intramolecular reaction among these functional groups, therefore inducing the coiling up within the LHA molecule. In addition, the decrease of the K DOC with added MgCl2/MgSO4 (75-95 %) is higher than that with added NaCl/Na2SO4 (20-75 %), indicating that the K DOC was affected by the charge density of cations. The fluorescence intensity of BQH(+) in the absence of LHA (F 0) was found to decay only in the acidic solution with Cl(-), suggesting that Cl(-) might be a heavy atom serving as a quencher in an acidic solution.

摘要

多环芳烃(PACs)是广泛存在的环境污染物,具有很高的致癌性和致突变性。PACs 的行为受其与溶解有机物(DOM)相互作用的显著影响,如在水环境中的迁移、溶解度、生物利用度和生物积累。苯并(h)喹啉(BQ)作为一种基本的 PAC,是主要存在的物质,因为溶液的 pH 值高于 BQ 的 pKa(BQ 的 pKa=4.2)。相反,当溶液的 pH 值低于其 pKa 时,主要存在的物质是苯并(h)喹啉鎓(BQH(+))。通过荧光猝灭法测量的 BQ/BQH(+)与莱纳德ite 腐殖酸(LHA)之间的结合常数(K DOC),在酸性和中性至碱性条件下分别增加离子强度时,会降低 70%至 95%和 20%至 90%。这一结果可归因于添加的阳离子(Na(+)和 Mg(2+))与 LHA 形成桥接,增强了这些官能团之间的分子内反应,从而导致 LHA 分子内的卷曲。此外,与添加 NaCl/Na2SO4(20%至 75%)相比,添加 MgCl2/MgSO4(75%至 95%)时 K DOC 的降低幅度更高,表明 K DOC 受到阳离子电荷密度的影响。在不存在 LHA 的情况下,BQH(+)的荧光强度(F 0)仅在酸性溶液中与 Cl(-)一起衰减,这表明 Cl(-)可能是酸性溶液中的一种重原子猝灭剂。

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