Optical enrichment of a racemic chiral crystal by X-ray irradiation
GENERATION of optical activity in a racemic mixture of enantiomers, a process relevant to the origin of life and of naturally chiral compounds1, requires chirality in the interaction responsible for the transformation or the environment in which it occurs. Without violating this strict requirement, we have found a way in which optical enrichment of a racemic mixture can occur without any chiral specificity in the mechanism. A racemic mixture of (1-cyanoethyl)(piperidine)cobaloxime, which contains the chiral 1-cyanoethyl group, crystallizes in a chiral space group (P212121) in which R and S enantiomers occupy crystallographically distinct (diastereoisomeric) positions in the asymmetric unit cell. We have prepared single crystals of the D configuration. Irradiating the crystal with X-rays at 343 K causes racemization of the S en-antiomer while the R enantiomer remains unaltered. This racemization is thought to be due solely to the different volume constraints on the two enantiomers in their different crystal environments. The result is that the number of R molecules is increased at the expense of S, and so the overall composition of the crystal changes from racemic to enriched in the R enantiomer.
High-pressure and temperature dependence of the spontaneous resolution of 1,1'-binaphthyl enantiomers.
High pressure increases the temperature of the spontaneous resolution of 1,1'-binaphthyl conformational enantiomers in the crystalline state, which confirms that the enantiomers and racemates are stabilized in the molecular environments in compressed structures. The established pressure-temperature (p-T) preference diagram for the racemate-enantiomer spontaneous crystallization corresponds to a boundary between solid phases, as it is consistent with the Clausius-Clapeyron equation, however, the hysteresis of such a solid-state transformation extends to very high pressure, to 3 GPa, at least according to this study. High-pressure X-ray diffraction study on single crystals of 1,1'-binaphthyl racemate and enantiomer reveals their monotonic compression and structural changes up to 3 GPa. It also reveals the increasing role of intermolecular interactions for stabilizing the structures, despite the exceptionally large density difference between the racemate (1.277 g cm-1) and enantiomers (1.183 g cm-1).
Development of new analytical methods for the determination of caffeine content in aqueous solution of green coffee beans
BackgroundThis study was conducted to develop fast and cost effective methods for the determination of caffeine in green coffee beans. In the present work direct determination of caffeine in aqueous solution of green coffee bean was performed using FT-IR-ATR and fluorescence spectrophotometry. Caffeine was also directly determined in dimethylformamide solution using NIR spectroscopy with univariate calibration technique.ResultsThe percentage of caffeine for the same sample of green coffee beans was determined using the three newly developed methods. The caffeine content of the green coffee beans was found to be 1.52 ± 0.09 (% w/w) using FT-IR-ATR, 1.50 ± 0.14 (% w/w) using NIR and 1.50 ± 0.05 (% w/w) using fluorescence spectroscopy. The means of the three methods were compared by applying one way analysis of variance and at p = 0.05 significance level the means were not significantly different. The percentage of caffeine in the same sample of green coffee bean was also determined by using the literature reported UV/Vis spectrophotometric method for comparison and found to be 1.40 ± 0.02 (% w/w).ConclusionNew simple, rapid and inexpensive methods were developed for direct determination of caffeine content in aqueous solution of green coffee beans using FT-IR-ATR and fluorescence spectrophotometries. NIR spectrophotometry can also be used as alternative choice of caffeine determination using reduced amount of organic solvent (dimethylformamide) and univariate calibration technique. These analytical methods may therefore, be recommended for the rapid, simple, safe and cost effective determination of caffeine in green coffee beans.