Chromatography under critical conditions: An analogy between functionalized and partially cyclic polymers

• We propose a new theoretical approach for describing LCCC of complex polymers.
• This approach is based on the analogy between functionalized polymers and PCMs.
• We predict chromatographic behavior of a variety of complex multi-cyclic polymers.
• We present a simplified theory of LCCC of functionalized PCMs.

An analogy is established between functionalized polymers and partially cyclic macromolecules (PCMs) in the liquid chromatography at critical conditions (LCCC). Application of the functionalized chain analogy (FCA) for prediction of the behavior of complex multi-cyclic PCMs in the LCCC mode is demonstrated. By using FCA, we discuss possibilities of LCCC to separate multi-cyclic PCMs by the number of cycles, and with respect to molecular topology. FCA is also extended to describe PCMs with specifically adsorbing groups; this results in a simplified theory of LCCC of functionalized PCMs. By simulating chromatograms of heterogeneous functionalized PCMs at the conditions of LCCC, we show possible dramatic effects of functional groups on the topological separation of PCMs: even the retention order of components may change to opposite.