0000000000711362
AUTHOR
A. Gisbert-alonso
Testing experimental designs in liquid chromatography (I): Development and validation of a method for the comprehensive inspection of experimental designs.
The basis of interpretive optimisation in liquid chromatography is the prediction of resolution, from appropriate solute retention models. The reliability of the process depends critically on the quality of the experimental design. This work develops, validates and applies a general methodology aimed to evaluate the quality of any training experimental design, which will be applied in Part II to design optimisation. The methodology is based on the systematic evaluation of the uncertainties associated to the prediction of retention times in comprehensive scans of both isocratic and gradient experimental conditions. It is able to evaluate comprehensively experimental designs of arbitrary comp…
Benefits of solvent concentration pulses in retention time modelling of liquid chromatography
The advantages and disadvantages of the use of isocratic experimental designs including transient increments of organic solvent (i.e., pulses) in the mobile phase(s) of lowest elution strength are explored with modelling purposes. For retained solutes, this type of mixed design offers similar or better predictive capability than gradient designs, shorter measurement time than pure isocratic designs, and retention model parameters that agree with those derived from pure isocratic experiments, with similar uncertainties. The predicted retention times are comparable to those offered by models adjusted from pure isocratic designs, and the solvent waste is appreciably lower. Under a practical st…
Global retention models and their application to the prediction of chromatographic fingerprints
Abstract The resolution of samples containing unknown compounds of different nature, or without standards available, as is the case of chromatographic fingerprints, is still a challenge. Possibly, the most problematic aspect that prevents systematic method development is finding models that describe without bias the retention behaviour of the compounds in the samples. In this work, the use of global models (able to describe the whole sample) is proposed as an alternative to the use of individual models for each solute. Global models contain parameters that are specific for each solute, while other parameters ‒related to the column and solvent‒ are common for all solutes. A special regressio…
Testing experimental designs in liquid chromatography (II): Influence of the design geometry on the prediction performance of retention models.
Abstract In liquid chromatography, the reliability of predictions carried out with retention models depends critically on the quality of the training experimental design. The search of the best design is more complex when gradient runs are used instead of isocratic experiments. In Part I of this work (JCA 1624 (2020) 461180), a general methodology based on the error propagation theory was developed and validated for assessing the quality of training designs involving gradients. The treatment relates the mathematical properties of a retention model with the geometry of the training designs and their subsequent predictions. In that work, only five usual designs were considered. Part II invest…