Improving selective channel occlusion of complex hydrocarbons and fatty acid methyl esters in urea crystals by using an expendable 3D-printed microfluidic device for sample preparation in untargeted petroleomics

In this study, we describe a proof-of-concept investigation of the potential and limitations of employing channel occlusion for sample preparation in untargeted analysis in petroleomics. A middle petroleum distillate composed of fatty acid methyl esters (FAME) and a complex mixture of linear, branched, and cyclic hydrocarbons were selected as the model samples for this investigation. A microfluidic device was engineered to overcome the limitations of channel occlusion, resulting in a quick and robust method for sample preparation. The 3D-printed device using fused deposition modelling (FDM) allowed the combination of a 13-h multi-step sample handling protocol into a 2-min single-step procedure, which is also automation-friendly. Such developments were also evaluated using the analytical eco-scale to guide the development of a green analytical method. The relative standard deviation decreased 2-fold with method miniaturization. The efficiency of n-alkane removal was extended from tridecane (n-C13) to heptadecane (n-C17), compared to original method (n-C16 to n-C17). The analytical performance of the method was investigated for untargeted analysis. The tool used to probe the intra- and inter-class variance was multi-way principal component analysis (MPCA). MPCA modelling revealed that both methods generated equivalent chemical information, highlighting the benefits of reliable and reproducible sample preparation methods, especially for untargeted analysis. Such awareness is critical to avoid the generation of misleading results in fields that heavily rely on untargeted analysis and fingerprinting, such as petroleomics. [Display omitted] •Study of channel occlusion in host-guest system for analytical sample preparation.•Selective separation of linear from branched and cyclic hydrocarbons by channel occlusion.•Task-specific microfluidics enabled controlled crystallization, improving the selectivity of sample preparation.•Analytical eco-scale measurements guided the development of a green method.