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Localized Crystallization of Enantiomeric Organic Compounds on Chiral Micro-patterns from Various Organic Solutions

机译:不同有机溶液在手性微图案上对映体有机化合物的局部结晶

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The controlled crystallization of enantiomers of an organic compound (a cyclic phosphoric acid derivative) on templated micro-patterned functionalised surfaces is demonstrated. Areas where a complementary chiral thiol has been located were effective heterogeneous nucleation centres when a solution of the compound is evaporated slowly. Various organic solvents were employed, which present a challenge with respect to other examples when water is used. The solvent and the crystallization method have an important influence on the crystal growth of these compounds. When chloroform was employed, well-defined crystals grow away from the surface, whereas crystals grow in the plane from solutions in isopropanol. In both cases, nucleation is confined to the polar patterned regions of the surface, and for isopropanol growth is largely limited within the pattern, which shows the importance of surface chemistry for nucleation and growth. The apparent dependence on the enantiomer used in the latter case could imply stereo-differentiation as a result of short-range interactions (the templating monolayer is disordered, even at the nanometre scale). The size of the pattern of chiral monolayer also determines the outcome of the crystallization; 5 mm dots are most effective. Despite the low surface tension of the samples (relative to the high surface tension of water), differential solvation of the polar and hydrophobic layers of the solvents allows crystallization in the polar regions of the monolayer, therefore the polarity of the regions in which heterogeneous nucleation takes place is indeed very important. Despite the complex nature of the crystallization process, these results are an important step towards to the use of patterned surfaces for heterogeneous selective nucleation of enantiomers.
机译:证明了有机化合物(环状磷酸衍生物)的对映异构体在模板化的微图案化功能化表面上的受控结晶。当化合物的溶液缓慢蒸发时,互补的手性硫醇所在的区域是有效的异质成核中心。使用了各种有机溶剂,当使用水时,相对于其他实例提出了挑战。溶剂和结晶方法对这些化合物的晶体生长具有重要影响。当使用氯仿时,轮廓分明的晶体远离表面生长,而晶体则由异丙醇溶液在平面内生长。在这两种情况下,成核作用都局限于表面的极性图案区域,而异丙醇的生长很大程度上受限于图案内,这表明表面化学对于成核和生长的重要性。在后一种情况下,对对映异构体的明显依赖性可能是由于短程相互作用(模板单层是无序的,甚至是纳米级的)导致的立体分化。手性单分子层的图案大小也决定了结晶的结果。 5毫米点最有效。尽管样品的表面张力低(相对于水的表面张力高),但溶剂的极性和疏水层的差异溶剂化仍允许在单层的极性区域中结晶,因此,异质成核区域的极性发生的确非常重要。尽管结晶过程具有复杂的性质,但这些结果仍是朝着将带图案的表面用于对映异构体的异质选择性成核的重要一步。

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