Tandem Use of Optical Sensing and Machine Learning for the Determination of Absolute Configuration, Enantiomeric and Diastereomeric Ratios, and Concentration of Chiral Samples
Tandem Use of Optical Sensing and Machine Learning for the Determination of Absolute Configuration, Enantiomeric and Diastereomeric Ratios, and Concentration of Chiral Samples
复制标题
DOI：
10.1002/anie.201912904
复制
发表时间：
2019-12-19
影响因子：
16.6
通讯作者：
Wolf, Christian
中科院分区：
文献类型：
--
作者：
De los Santos, Zeus A.;MacAvaney, Sean;Wolf, Christian
我们开发了一种基于简单的混合和测量工作流程的氨基醇精确浓度，er和dr分析的光学方法，该方法完全适用于多孔板技术和微尺度分析。用水杨醛将四种氨基茚满醇立体异构体转化为相应的席夫碱允许基于420 nm处的UV最大值的变化分析dr，这对于同手性和异手性非对映异构体非常不同，并且允许使用340 nm附近的另一吸收带的蓝移分析样品的浓度，这与分析物立体化学无关。随后在原位形成的Cu-II组件在碱的存在和不存在下，能够通过CD分析定量每个非对映体对的ER值。应用线性规划方法和参数扫描算法，我们确定的浓度和相对量的四个立体异构体中的每一个在20个样品的立体异构体组合物有很大的不同，平均绝对百分误差为1.7%。
We have developed an optical method for accurate concentration, er, and dr analysis of amino alcohols based on a simple mix-and-measure workflow that is fully adaptable to multiwell plate technology and microscale analysis. The conversion of the four aminoindanol stereoisomers with salicylaldehyde to the corresponding Schiff base allows analysis of the dr based on a change in the UV maximum at 420 nm that is very different for the homo- and heterochiral diastereomers and of the concentration of the sample using a hypsochromic shift of another absorption band around 340 nm that is independent of the analyte stereochemistry. Subsequent in situ formation of Cu-II assemblies in the absence and presence of base enables quantification of the er values for each diastereomeric pair by CD analysis. Applying a linear programming method and a parameter sweep algorithm, we determined the concentration and relative amounts of each of the four stereoisomers in 20 samples of vastly different stereoisomeric compositions with an averaged absolute percent error of 1.7 %.