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-3 % (w/w)), and the planes do not translate themselves. Thus, the X-ray reflections for twinned crystals and pure enantiomeric crystals differ only by an anomalous correction.
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In the case of conglomerate, the solubility of the racemic mixture is approximately double that of the pure enantiomer (in an ideal case, the solubility of one enantiomer is not modified by the presence of the other); therefore, the crystals of the superfluous enantiomer first have to appear from solution enriched by this enantiomer.
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48
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note
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It is without a doubt that W. J. Pope clearly realized the nature of Pasteur's experiments, and he and his colleague F. S. Kipping made a significant contribution to the further understanding of the spontaneous resolution phenomenon. We refer readers to two references: (a) Kipping, F. S.; Pope, W. J. J. Chem. Soc., Trans. 1898, 73, 606.
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(b) Kipping, F. S.; Pope, W. J. J. Chem. Soc., Trans. 1897, 71, 989. The first one is dedicated to an elegant investigation of the crystallization of sodium chlorate. The second one is about their interpretation of the pseudoracemism phenomenon, where there is confirmation that the authors had an idea about twinning between enantiomers; however, they used this concept for the structural description of pseudoracemates, which is not actually correct.
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In ref 7j, the authors proposed the use of the term lamellar epitaxy instead of the term lamellar twinning for the description of cases of twinning of opposite enantiomers of the same chemical compound. They bases this idea on the definition of J. D. Dunitz (Acta Crystallogr., Sect. B 1995, 51, 619) that enantiomeric crystals of a conglomerate and a racemate are three different chemical substances if the enantiomerization rate is low and can be considered to be polymorphs if the enantiomerization rate is high. It is seems that the authors solved the confusion because even the same enantiomer can form lamellar twinned crystals, whereas the crystal growth of one substance on crystals of the other it is accepted as epitaxy. However, the confusion arises again if we take into consideration the fact that under certain conditions the enantiomerization rate can be high (for example, the presence of a catalyst or high temperature, which can increase the enantiomerization rate), whereas under another set of conditions the rate will be low. Therefore, in the first case the term twinning is appropriate, but in the second we should use the term epitaxy. We are inclined to take another point of view. Racemate-conglomerate polymorphism takes place when crystallization occurs from solution or in a melt of racemic composition and molecules or ions can assemble equiprobably into racemic crystals (racemic compound) or mechanical mixture of left- and right-handed crystals (conglomerate). To distinguish the ordinary twinning of crystals of the same enantiomer from the twinning of alternating lamellae of two opposite enantiomers leading to crystals of racemic composition, we suggest that the term lamellar racemic twinning be used. We refer readers also to ref 13a, where the term twinning by inversion for twinning between the two opposite enantiomers is proposed.
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Although ESI MS is widely used for the investigation of self-assembly processes in solution, we think that this technique is of limited use for crystal nucleation studies. Other types of equipment such as cold-spray MS (ref 36) or sonic-spray MS (ref 37) are more promising.
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