化学学报 ›› 2007, Vol. 65 ›› Issue (20): 2309-2314. 上一篇    下一篇

研究论文

同步-偏振-导数荧光法同时测定三种苯二酚异构体的研究

杨季冬1,2,张书然1,刘绍璞*,1   

  1. (1西南大学化学化工学院 重庆 400715)
    (2涪陵师范学院化学系 重庆 408003)
  • 投稿日期:2006-11-20 修回日期:2007-03-10 发布日期:2007-10-28
  • 通讯作者: 刘绍璞

Simultaneous Determination of Three Dihydroxybenzene Isomers by Synchronous-Polarization-Derivative Fluorescence Spectrometry

YANG Ji-Dong1,2; ZHANG Shu-Ran1; LIU Shao-Pu*,1   

  1. (1 College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715)
    (2 Department of Chemistry, Fuling Teachers College, Chongqing 408003)
  • Received:2006-11-20 Revised:2007-03-10 Published:2007-10-28
  • Contact: LIU Shao-Pu

苯二酚的三种异构体, 由于其吸收光谱和荧光光谱均重叠严重, 不能用常规分光光度法和荧光法进行同时测定. 而以λ=0 nm进行同步扫描时, 在350~500 nm之间具有相似的荧光光谱特征, 其荧光强度有良好的加和性, 可以对三者进行总量测定. 研究还发现三种苯二酚异构体与Cu2+和异烟肼形成1∶1∶2的配位合物时, 用Δλ=30 nm进行同步扫描并采用偏振和一阶导数法, 间苯二酚的导数荧光峰位于260 nm处, 对苯二酚的导数荧光峰位于320 nm处, 两者能很好分开, 而此时邻苯二酚荧光峰消失, 因此可在三者的混合物中分别测定间、对苯二酚, 然后再从总量中减去间、对苯二酚的含量, 从而测到邻苯二酚的浓度, 因此本工作通过上述方法可对三种苯二酚异构体进行同时测定. 其线性范围均在3×10-6~5×10-4 mol/L之内, 间苯二酚和对苯二酚的检出限分别是2.5×10-7 mol/L和3.1×10-7 mol/L; 其混和物总量的检出限是4.5×10-7 mol/L, RSD均在5%以下. 该方法简便快速, 有良好的准确性和重复性, 用于环境水样中三种苯二酚的同时测定, 获得满意结果.

关键词: 同步-偏振-导数荧光法, 苯二酚异构体, 异烟肼, Cu(II), 同时测定

Three dihydroxybenzene (DHB) isomers could not be simultaneously determined by ordinary spectrophotometry and fluorometric method because the overlaps of their absorption spectra and fluorescence spectra were severe. The total amount of these three isomers could be measured when they were synchronously scanned at Δλ=0 nm because they have homoplastic character of fluorescence spectrum and favourable additivity of fluorescence intensity in 350~500 nm. It was found that when the three DHB isomers were bound with Cu2+ and isoniazide, ternary complexes were formed in a ratio of 1∶1∶2. When such complexes were synchronously scanned at Δλ=30 nm using polarization and first order derivative techniques, the derivative fluorescence peak of m-DHB appeared at 260 nm, that of p-DHB appeared distinguishably at 320 nm, but that of o-DHB did not appear simultaneously at all. Thus the contents of m-DHB and p-DHB can be determined from their mixture respectively, and then the content of o-DHB can be obtained by subtraction of the contents of m-DHB and p-DHB from the total amount of the mixture. Hence these three DHB isomers can be simultaneously determined through the above method in the experiment. The system responds linearly to each of the three isomers concentrations in the range 3×10-6~5×10-4 mol/L with detection limit of 2.5×10-7 mol/L for m-DHB, 3.6×10-7 mol/L for p-DHB, the detection limit of the total amount of the mixture is 4.5×10-7 mol/L, and the RSD of these systems was under 5%. The method is simple, convenient, quick, veracious and repeatable, which has been successfully applied to simultaneous determination of the three dihydroxybenzene isomers in water samples with satisfactory results.

Key words: synchronous-polarization-derivative fluorescence spectrometry, dihydroxybenzene isomer, isoniazide, Cu(II), simultaneous determination