title: Selective growth and distribution of crystalline enantiomers in hydrogels.
abstract: The crystallization of sodium chlorate (NaClO3) is a classic example of spontaneous chirality, since it is achiral in solution but adopts a chiral form in the solid state. While crystal growth of NaClO3 from pure aqueous solutions yields a 50:50 statistical distribution of d- and l-crystals, large enantiomeric excesses of either d- and l-crystals can be achieved by crystal growth in agarose gel, a naturally occurring chiral polysaccharide. The influence of gel density (0.1-0.75 wt %), temperature, and the diffusion of cosolvents on crystal distribution was discerned from statistical data obtained from 752 gel-mediated crystallization experiments yielding 12,384 individual crystals. These studies demonstrate that the magnitude and direction of the bias can be selectively engineered toward either d- or l-forms by changing the gelation conditions. Aqueous agarose gels infused with 48 wt % NaClO3 at 6 degrees C, favored the growth of d-NaClO3 crystals, with ee's reaching 22% at the highest gel concentrations. Crystal growth under methanol diffusion favored deposition of the opposite enantiomorph, l-NaClO3. The bias in the crystal distribution is enhanced at higher temperatures. Aqueous gels at 24 degrees C infused with methanol cosolvent favored l-NaClO3, with ee's reaching 53%. The changing magnitude and direction of the enantiomorph bias can be ascribed to differences in the agarose conformation and intermolecular interactions between the gel and crystal surfaces that inhibit the formation of the two enantiomers to different extents.
authors.affiliation: Department of Chemistry, Georgetown University, 37th and "O" Streets NW, Washington, DC 20057-1227, USA.
authors.forename: Rositza I
authors.initials: RI
authors.lastname: Petrova
authors.forename: Jennifer A
authors.initials: JA
authors.lastname: Swift
mesh_terms: D002704:Chlorates / Q000737:chemistry; D003460:Crystallization / Q000379:methods; D020100:Hydrogels / Q000737:chemistry*; D012685:Sepharose / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D002704:Chlorates; D020100:Hydrogels; D012685:Sepharose; C032706:sodium chlorate