Theoretical and experimental investigations on relationship between Kohlrausch regulating function/inequality and moving reaction boundary in electrophoresis.
ABSTRACT Kohlrausch regulating function (KRF) has been well defined from a moving boundary system for over 50 years. Recently, a series of theoretical and experimental studies were carried out on the concept of moving reaction boundary (MRB), including moving precipitate boundary, moving neutralization boundary and moving chelation boundaries (MCB). However, there has not been any direct evidence to show whether the KRF has validity for a MRB or not. In this paper, the KRF is derived from the equation of MRB under condition of nonzero boundary velocity. The result directly shows the relation between the KRF and a MRB. The relation is verified by some experimental and simulation results on MCB and moving neutralization boundary as well as Svensson's classic IEF. Furthermore, a Kohlrausch inequality was defined from the equation of MRB and was further proved by numerous data. The results show that we can use the KRF for the investigation on a MRB under the condition of nonzero boundary velocity, whereas we ought to notice with great attention that the KRF does possibly have invalidity under some special cases, such as stationary electrolysis and IEF. The findings hold an evident significance to the study of a MRB with the KRF.
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ABSTRACT: A novel separation mode of isotachophoresis (ITP) was advanced for the study on the continuous moving chelation boundary (MCB) formed with EDTA and two metal ions of Co(II) and Cu(II). The experiments were performed systemically. The relevant results indicated that: (1) there were three boundaries in the whole system, viz., a sharp MCB, a wide moving substitution boundary (MSB) and a sharp complex boundary (CB); (2) within the MSB, an ion substitution reaction occurred between [Co-EDTA](2-) and Cu(II), and the reaction resulted in the release of Co(II) and EDTA from [Co-EDTA](2-) and the binding of Cu(II) with the released EDTA due to log K(Cu(II)) (= 18.80) > log K(Co(II)) (= 16.31); (3) because of the novel ITP mode induced by the MSB as well as the merging of the MCB and CB, the original low concentration Co(II) and Cu(II) were chemically separated as two characteristic coloured zones of pink [Co-EDTA](2-) and blue [Cu-EDTA](2-), and the sensitivities for detection of the two metal ions were greatly enhanced. The quantitative analyses of the zone composition by ICP-AES and UV-vis spectrophotometry supported the mechanism of the novel separation mode induced by the MSB. The further theoretical and experimental results indicated that the separation mode was a novel ITP relied on moving reaction boundary (MRB), rather than a classic ITP based on the moving boundary system developed about 60 years ago. These findings provide guidance for the development of the MRB and the MCB-based ITP separation of metal ions in environmental and biological matrices.The Analyst 01/2010; 135(1):140-8. · 4.23 Impact Factor
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ABSTRACT: In this paper, a general mode and theory of moving chelation boundary based isotachophoresis (MCB-based ITP), together with the concept of decisive metal ion (DMI) having the maximum complexation constant (lg Kmax) with the chelator, were developed from a multi-MCB (mMCB) system. The theoretical deductions were: (i) the reaction boundary velocities in the mMCB system at steady state were equal to each other, resulting in a novel MCB-based ITP separation of metal ions; (ii) the boundary directions and velocities in the system were controlled by the fluxes of chelator and DMI, rather than other metal ions; and (iii) a controllable stacking of metal ions could be simultaneously achieved in the developed system. To demonstrate the deductions, a series of experiments were conducted by using model chelator of EDTA and metal ions of Cu(ii) and Co(ii) due to characteristic colors of blue [Cu-EDTA](2-) and pink [Co-EDTA](2-) complexes. The experiments demonstrated the correctness of theoretical deductions, indicating the validity of the developed model and theory of ITP. These findings provide guidance for the development of MRB-based ITP separation and stacking of metal ions in biological sample matrix and heavy metal ions in environmental samples.The Analyst 06/2013; · 4.23 Impact Factor