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The first spectral study of the tautomerism in I has been performed in 1935: Kuhn, R.; Bar, F. Annalen, 1935, 516, 143.
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The word chemometric is exactly suited for the purposes of quantitative analysis of tautomeric mixtures, because it considers the strategies for extracting more information from the existing data sets. However we do not consider the details of the mathematical optimization procedures, assuming that they have been performed in the best possible way. More about these procedures can be found in the following books: Banday, B.D. Basic optimization methods, E. Arnold: London, 1984;
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The word chemometric is exactly suited for the purposes of quantitative analysis of tautomeric mixtures, because it considers the strategies for extracting more information from the existing data sets. However we do not consider the details of the mathematical optimization procedures, assuming that they have been performed in the best possible way. More about these procedures can be found in the following books: Banday, B.D. Basic optimization methods, E. Arnold: London, 1984;
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DATAN MultiD Analyses AB, is a NIPALS based optimization package specially developed for analysis of various equilibria depending on the T, pH or concentration
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DATAN (MultiD Analyses AB), is a NIPALS based optimization package specially developed for analysis of various equilibria depending on the T, pH or concentration.
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Here, we should make a solvent related remark. In the analysis of tautomeric equilibria, especially in azo dyes and Schiff bases, achieving substantial shift in the equilibrium position by changing solvent composition is the most popular and wide-used method. The changes in solution achieved by temperature elevation are more than moderate in the temperature range available for UV-Vis spectroscopy (from 10 to 100°C depending on the solvent) and hence difficult to interpret. However the use of the solvent composition as a factor affecting the equilibrium brings problems in the quantitative processing of the beautiful pictures that are obtained, because the individual spectra of the tautomers are solvent dependent. Their solvent dependence has two aspects: (a) shape - solvent shift of the individual bands composing it; and/or (b) intensity - solvent influence on the corresponding oscillator strengths
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Here, we should make a solvent related remark. In the analysis of tautomeric equilibria, especially in azo dyes and Schiff bases, achieving substantial shift in the equilibrium position by changing solvent composition is the most popular and wide-used method. The changes in solution achieved by temperature elevation are more than moderate in the temperature range available for UV-Vis spectroscopy (from 10 to 100°C depending on the solvent) and hence difficult to interpret. However the use of the solvent composition as a factor affecting the equilibrium brings problems in the quantitative processing of the beautiful pictures that are obtained, because the individual spectra of the tautomers are solvent dependent. Their solvent dependence has two aspects: (a) shape - solvent shift of the individual bands composing it; and/or (b) intensity - solvent influence on the corresponding oscillator strengths [19] and individual band areas. Our experience in the analysis of tautomeric azonaphthols and related Schiff bases [32-34, 21, 39] shows that there is evident solvatochromic shift in the positions of the longwavelength tautomeric bands (stronger for the K-ones) in the former [32-34], while in the latter no solvatochromism was observed in a wide set of solvents [21,39]. This means that at least in the case of Schiff bases it can be assumed that the individual band positions are solvent independent, i.e. the shape problem does not have substantial effect on the results. The intensity problem is not straightward - it is obvious that the probability of the electronic transitions (oscillator strength) depends on the solvent, but the effect is individual for the definite compounds. Hence, it is difficult to estimate the risk of the assumption for solvent independence of the oscillator strength.
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