文摘
Dilution enthalpies of two penicillamine enantiomers, namely, d-penicillamine, l-penicillamine, and their racemate d,l-penicillamine, in N,N-dimethylformamide (DMF) + water mixtures of various compositions have been determined at 298.15 K respectively, using an isothermal titration calorimeter (MicroCal ITC200). According to the McMillan鈥揗ayer theory, homochiral enthalpic pairwise interaction coefficients (hXX) of the three penicillamines in DMF + water mixtures of different mass fractions (wDMF = 0 to 0.3) have been calculated regressively. It is found that hXX coefficients of each enantiomer and their racemate change increasingly with wDMF to the maxima at wDMF = 0.20 and then decrease relatively rapidly, which follows the order hLL > hDD 鈮?hRR > 0 (R represents the racemate mixture of penicillamine). The results are discussed from the point of view of competitive equilibrium between hydrophobic and hydrophilic interactions in solutions.