RESUMO
Nuclear magnetic resonance (NMR) spectroscopy is an analytical technique largely applied in the analysis of discrimination processes involving enantiomeric substrates and chiral agents, which can interact with the analyte either via covalent bonding or via formation of diastereomeric solvates. However, enantiodiscrimination has been observed, in some cases, even in the absence of any additional chiral selector. The reasons behind this phenomenon must be found in the capability of some chiral substrates to interact with themselves by forming diastereomeric solvates in solution that can generate nonequivalences in the NMR spectra of enantiomerically enriched mixtures. As a result, differentiation of enantiomers is observed, thus allowing the quantification of the enantiomeric composition of the mixture under investigation. The tendency of certain substrates to self-aggregate and to generate diastereomeric adducts in solution can be defined as Self-Induced Diastereomeric Anisochrony (SIDA), but other acronyms have been used to refer to this phenomenon. In the present work, an overview of SIDA processes investigated via NMR spectroscopy will be provided, with a particular emphasis on the nature of the substrates involved, on the interaction mechanisms at the basis of the phenomenon, and on theoretical treatments proposed in the literature to explain them.
RESUMO
Background and Purpose: The widely-used and practically insoluble diprotic acidic dye, bromothymol blue (BTB), is a neutral molecule in strongly acidic aqueous solutions. The Schill (1964) extensive solubility-pH measurement of bromothymol blue in 0.1 and 1.0 M NaCl solutions, with pH adjusted with HCl from 0.0 to 5.4, featured several unusual findings. The data suggest that the difference in solubility of the neutral-form molecule in 1M NaCl is more than 0.7 log unit lower than the solubility in pure water. This could be considered as uncharacteristically high for a salting-out effect. Also, the study reported two apparent values of pKa1, 1.48 and 1.00, in 0.1 M and 1.0 M NaCl solutions, respectively. The only other measured value found for pKa1 in the literature is -0.66 (Gupta and Cadwallader, 1968). Experimental Approach: It was reasoned that the there can be only a single pKa1 for BTB. Also, it was hypothesized that salting-out alone might not account for such a large difference in solubility observed at the two levels of salt. A generalized mass action approach incorporating activity corrections for charged species using the Stokes-Robinson hydration equation and for neutral species using the Setschenow equation, was selected to analyze the Schill solubility-pH data to seek a rationalization of these unusual results. Key Results: BTB reveals complex speciation chemistry in saturated aqueous solutions which had been poorly understood for many years. The appearance of two different values of pKa1 at different levels of NaCl and the anomalously high value of the empirical salting-out constant could be rationalized to normal values by invoking the formation of a very stable neutral dimer (log K2 = 10.0 ± 0.1 M-1). A 'normal' salting-out constant, 0.25 M-1 was then derived. It was also possible to estimate the 'self-interaction' constant. The data analysis in the present study critically depended on the pKa1 = -0.66 reported by Gupta and Cadwallader. Conclusion: A more reasonable salting-out constant and a consistent single value for pKa1 have been determined by considering a self-interacting (aggregation) model involving an uncharged form of the molecule, which is likely a zwitterion, as suggested by literature spectrophotometric studies.
RESUMO
The ultraviolet-visible (UV-Vis) spectra of the aqueous solutions of humic acids (HA) Aldrich were obtained within the concentration range 1-20 mg/L (0.1-2c10-6 mol/L). A conclusion on the existence of the self-association (dimer formation) of HA macromolecules is based on the deviation of the concentration dependence of optical density (OD) from the linear one at [HA] > 10 mg/L (>10-6 mol/L). An original, mathematical algorithm is proposed to determine a dimerization constant K and a molar coefficient of dimer absorption ∊ D(λ) The value of K was (2.56 ± 0.07) c 106 L/mol. The calculated molar coefficients of HA macromolecule dimer absorption, ∊ D(λ) , indicate an increase in the dimer extinction coefficient ∊ D(λ) compared to the double value of the molar monomer absorption 2 ∊ M(λ) . It was established that the spectral dependence of the value ß = ∊ D(λ) / ∊ M(λ) exhibits a minimum within a wavelength range of 300-450 nm, which is due to the difference in the efficiency of the interaction of various sites upon HA macromolecule dimerization. Thus, an approach of studying the processes of self-association is proposed using the method of UV-Vis absorption spectroscopy. This method is implemented for molecules that do not have characteristic absorption bands. The proposed method can also be successfully applied to molecules with characteristic absorption bands.