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 (i.e., 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 (i.e., 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 (i.e., 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 (e.g., kw).

中文翻译：

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通过多元选择性为色谱峰跟踪应用合理设计混合物

针对许多溶质的色谱表征和参数化研究需要明智地选择操作条件，以最大限度地减少分析时间而不影响结果的准确性。为了最大限度地缩短分析时间，溶质通常被分成少量的混合物；然而，这会增加峰重叠的风险。虽然多变量曲线解析方法通常能够根据其光谱质量解析分析物信号，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到包含具有不同光谱和可选具有不同色谱特性的溶质的样品混合物中的策略，以确保成功地通过色谱或曲线拆分方法进行溶质拆分。我们将此策略命名为混合物的合理设计（RDM）。RDM 利用多变量选择性作为衡量组成员关系（即，是否向特定样本添加特定溶质）的决策指标。一组 97 种溶质用于演示此策略。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，只需要 12 个组即可避免同一组中的两种或多种溶质无法通过色谱法（即它们具有显着不同的保留时间）或光谱法分离的情况（即，光谱差异足以通过曲线分辨率方法实现分辨率）。当仅使用光谱特性时（即，