Chromatographic retention time peak shifts between consecutive analyses is a well-known fact yet not fully understood. Algorithms have been developed to align peaks between runs, but with no specific studies considering the causes of peak shifts. Here, designed experiments reveal chromatographic shift patterns for a complex peptide mixture that are attributable to the temperature and pH of the mobile phase. These results demonstrate that peak shifts are highly structured and are to a high degree explained by underlying differences in physico-chemical parameters of the chromatographic system and also provide experimental support for the alignment algorithm called the generalized fuzzy Hough transform which exploits this fact. It can be expected that the development of alignment algorithms enters a new phase resulting in increasingly accurate alignment by considering the latent structure of the peak shifts.

连续分析之间的色谱保留时间峰位移是众所周知的事实，但尚未完全了解。已经开发了在运行之间对齐峰的算法，但没有针对峰移位的原因进行专门研究。在这里，设计的实验揭示了复杂肽混合物的色谱移动模式，这归因于流动相的温度和pH。这些结果表明，峰移动是高度结构化的，并且在很大程度上可以通过色谱系统的物理化学参数的根本差异来解释，并且还为利用这一事实的称为广义模糊霍夫变换的比对算法提供了实验支持。