National Centre for the Control and Evaluation of Medicines, Chemical Medicines Unit, Istituto Superiore di Sanità, Viale Regina Elena 299, 00161, Rome, Italy.
National Centre for the Control and Evaluation of Medicines, Chemical Medicines Unit, Istituto Superiore di Sanità, Viale Regina Elena 299, 00161, Rome, Italy; Department of Chemistry and Technology of Drugs, Sapienza University of Rome, 00185, Rome, Italy.
Talanta. 2020 Oct 1;218:121151. doi: 10.1016/j.talanta.2020.121151. Epub 2020 May 11.
Sulforaphane and iberin are promising chemopreventive chiral phytochemicals. The chirality of these organic isothiocyanates is due to the presence of a stereogenic sulfur atom. Investigations of the effectiveness of single enantiomers as chemoprotective agents highlight the key role played by sulfur chirality on biological activity. The predominant native (R)-enantiomer is active whereas the (S)-counterpart is inactive or poorly active. Here, we provide an enantioselective method for the direct and complete resolution of both chiral sulfoxides by high-performance liquid chromatography on immobilized amylose-derived chiral stationary phases. A set of five different columns was investigated utilizing normal-phase, polar organic and aqueous conditions. The effect of the composition of mobile phase on enantioselectivity and retention was carefully evaluated. U-shape retention maps, which are indicative of a double and competitive hydrophilic interaction liquid chromatography and reversed-phase liquid chromatography retention mechanism, were established by recording the retention factors of the enantiomers of sulforaphane on the Chiralpak IA-3 and Chiralpak IG-3 chiral stationary phases varying progressively the water content in the water-acetonitrile mobile phases.
萝卜硫素和异硫氰酸酯是很有前途的化学预防手性植物化学物质。这些有机异硫氰酸盐的手性是由于存在一个手性硫原子。对单一对映异构体作为化学保护剂的有效性的研究强调了硫手性对生物活性的关键作用。主要的天然（R）-对映异构体是活性的，而（S）-对映异构体是无活性或活性差的。在这里，我们提供了一种通过固定化直链淀粉衍生手性固定相的高效液相色谱对两种手性亚砜进行直接和完全拆分的对映选择性方法。利用正相、极性有机和水相条件研究了五套不同的色谱柱。仔细评估了流动相组成对对映选择性和保留的影响。通过记录在 Chiralpak IA-3 和 Chiralpak IG-3 手性固定相上萝卜硫素对映体的保留因子，建立了 U 形保留图，这表明存在双重和竞争性亲水相互作用液相色谱和反相液相色谱保留机制，随着水-乙腈流动相中水含量的逐渐增加。
