首页 | 本学科首页   官方微博 | 高级检索  
     检索      


Spectrophotometric determination of the dissociation constants of crown ethers with grafted acridone unit in methanol based on Benesi-Hildebrand evaluation
Authors:Kádár Mihály  Biró András  Tóth Klára  Vermes Borbála  Huszthy Péter
Institution:Institute for General and Analytical Chemistry and Research Group for Technical Analytical Chemistry of the Hungarian Academy of Sciences, Budapest University of Technology and Economic, H-1111 Budapest, Szent Gellért tér 4, Hungary.
Abstract:As potential chromo- and fluorophores for optical sensors a number of acridone grafted crown ethers containing NO2 group(s) and/or Br or Cl atom(s) in the aromatic rings (compounds) were studied by spectrophotometric method. In the first step of this work the acid-base and complexing properties of these compounds as well as those of the acridone, thioacridone and 4,5-dinitroacridone were investigated. Compounds proved to be very week acids and therefore the conventional spectrophotometric method based on the measurement of the ratio of the protonated/deprotonated forms of the compounds was not applicable for the determination of the dissociation constants (pKa values). Thus, a new spectrophotometric approach was elaborated for the pKa determination of these compounds, which is based on spectrophotometric titration in methanol with strong base and the titration results were evaluated by the Benesi-Hildebrand method. (In the studies with TEAOH, TMAOH and LiOMe, the complex formation between the ionophores and the cations of the bases could be excluded.) As it was expected, the experimentally determined pKa values depended on the nature of the substituents of the acridone moiety and pKa values ranged between 12.6 and 14.9. The lower pKa value of thioacridone compared to the acridone can be explained by the larger size of the sulfur atom. The outstandingly larger pKa value for 4,5-dinitroacridone can be attributed to the formation of intramolecular hydrogen-bonds between the ortho-position nitro group and the NH proton. As a trend, the strong electron withdrawing nitro substituents decreased considerably the pKa values of compounds and compared to that of the halogen (Cl and Br) atoms (for example compounds and) of weaker withdrawing effect.
Keywords:Acridones  Proton-ionizable crown ethers  Chromoionophores  Fluoroionophores  pKa determination  Spectrophotometric titration  Benesi-Hildebrand evaluation
本文献已被 ScienceDirect PubMed 等数据库收录!
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号