Cook Daniel W, Oram Kelson G, Rutan Sarah C, Stoll Dwight R
Department of Chemistry, Virginia Commonwealth University, Richmond, VA, 23284, USA.
Department of Chemistry, Gustavus Adolphus College, St. Peter, MN, 56082, USA.
Anal Chim Acta X. 2019 Mar 5;2:100010. doi: 10.1016/j.acax.2019.100010. eCollection 2019 Jul.
Chromatographic characterization and parameterization studies targeting many solutes require the judicious choice of operating conditions to minimize analysis time without compromising the accuracy of the results. To minimize analysis time, solutes are often grouped into a small number of mixtures; however, this increases the risk of peak overlap. While multivariate curve resolution methods are often able to resolve analyte signals based on their spectral qualities, these methods require that the chromatographically overlapped compounds have dissimilar spectra. In this work, a strategy for grouping compounds into sample mixtures containing solutes with distinct spectral and, optionally, with distinct chromatographic properties, in order to ensure successful solute resolution either chromatographically or with curve resolution methods is proposed. We name this strategy rational design of mixtures (RDM). RDM utilizes multivariate selectivity as a metric for making decisions regarding group membership (, whether to add a particular solute to a particular sample). A group of 97 solutes was used to demonstrate this strategy. Utilizing both estimated chromatographic properties and measured spectra to group these 97 analytes, only 12 groups were required to avoid a situation where two or more solutes in the same group could not be resolved either chromatographically , they have significantly different retention times) or spectrally (i.e., spectra are different enough to enable resolution by curve resolution methods). When only spectral properties were utilized (, the chromatographic properties are unknown ahead of time) the number of groups required to avoid unresolvable overlaps increased to 20. The grouping strategy developed here will improve the time and instrument efficiency of studies that aim to obtain retention data for solutes as a function of operating conditions, whether for method development or determination of the chromatographic parameters of solutes of interest (, ).
针对多种溶质的色谱表征和参数化研究需要明智地选择操作条件，以在不影响结果准确性的前提下尽量缩短分析时间。为了尽量缩短分析时间，溶质通常会被归为少量混合物；然而，这会增加峰重叠的风险。虽然多元曲线分辨方法通常能够根据分析物的光谱特性分辨信号，但这些方法要求色谱重叠的化合物具有不同的光谱。在这项工作中，提出了一种将化合物分组为含有具有不同光谱以及（可选）不同色谱特性溶质的样品混合物的策略，以确保通过色谱法或曲线分辨方法成功分离溶质。我们将此策略称为混合物的合理设计（RDM）。RDM利用多元选择性作为决定组分归属（即是否将特定溶质添加到特定样品中）的指标。使用一组97种溶质来证明该策略。利用估计的色谱特性和测量的光谱对这97种分析物进行分组，仅需12组即可避免同一组中的两种或更多种溶质在色谱上无法分离（即它们具有显著不同的保留时间）或在光谱上无法分离（即光谱差异足够大，能够通过曲线分辨方法分离）的情况。当仅利用光谱特性时（即事先不知道色谱特性），为避免无法解决的重叠所需的组数增加到20组。这里开发的分组策略将提高旨在获取溶质保留数据作为操作条件函数的研究的时间和仪器效率，无论是用于方法开发还是确定感兴趣溶质的色谱参数（即 ）。
