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Replacing methanol with azeotropic ethanol as the co-solvent for improved chiral separations with supercritical fluid chromatography (SFC)

机译:用共沸乙醇替换甲醇作为共溶剂,用于改善具有超临界流体色谱(SFC)的手性分离

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Supercritical and near supercritical fluids are considered green solvents of the future because they decrease the need for toxic organic solvents and are easily recyclable. Consequently, supercritical fluid chromatography, SFC, has emerged as an environment-friendly technique especially for analytical and preparative scale enantiomeric separations. In order to separate a wide range of analytes with differing polarities, most SFC systems employ super- or subcritical carbon dioxide mixed with 5-40% organic solvents. More than 40 chlorinated or non-chlorinated co-solvents have been employed in SFC so far. However, methanol is far and away the dominant SFC mobile phase component as it outperforms most of the other solvents. Given the relatively high cost, non-renewable source of manufacture, and toxicity of methanol in humans, we propose elimination of methanol as a component of the SFC mobile phase by replacing with a biomass derived solvent, i.e., minimum boiling azeotropic ethanol. Azeotropic ethanol contains similar to 4.6% water (aka '190 proof'). It is less expensive and easy to recycle as it distills off at constant composition. This work demonstrates, for the first time, that one can obtain better chiral SFC separations by using '190 proof' ethanol instead of methanol. This solvent choice is shown to be favorable and compatible with a wide range of macrocyclic and chiral polysaccharide column chemistries. In chiral analyses, we show efficiency enhancement up to an order of magnitude and reduced retention by using azeotropic ethanol. In general, SFC separations with azeotropic ethanol can provide enhanced separation performance in a more economical and environmentally friendly format and hopefully change the status quo of current analytical and preparative SFC.
机译:超临界和近超临界流体被认为是未来的绿色溶剂,因为它们会降低对有毒有机溶剂的需求,并且很容易可回收。因此,超临界流体色谱法,SFC作为一种环保技术,特别是对于分析和制备规模对映体分离。为了分离具有不同极性的各种分析物,大多数SFC系统采用与5-40%有机溶剂混合的超临界二氧化碳。到目前为止,SFC采用了超过40个氯化或非氯化共溶剂。然而,甲醇远离显性的SFC流动相组分,因为它优于大多数其他溶剂。鉴于人类中甲醇的成本相对较高,不可再生的制造源和甲醇的毒性,我们通过用生物质衍生的溶剂,即最小沸点共沸乙醇来提出作为SFC流动相的组分的甲醇。共沸乙醇含有类似的4.6%水(AKA'190 Proof')。在恒定的组成下蒸馏出蒸馏时,它的昂贵且易于回收。这项工作首次表现出可以通过使用'190验证'乙醇而不是甲醇来获得更好的手性SFC分离。该溶剂选择被证明是有利的并且与各种大环和手性多糖柱化学品相容。在手性分析中,我们通过使用共沸乙醇来显示效率提高和降低的保留减少。通常,具有共沸乙醇的SFC分离可以以更经济和环境友好的形式提供增强的分离性能,并希望改变目前分析和制备SFC的现状。

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