title: Theory of chromatography of partially cyclic polymers: Tadpole-type and manacle-type macromolecules.
abstract: A theory of chromatography is developed for partially cyclic polymers of tadpole- and manacle-shaped topological structures. We present exact equations for the distribution coefficient K at different adsorption interactions; simpler approximate formulae are also derived, relevant to the conditions of size-exclusion, adsorption, and critical chromatography. Theoretical chromatograms of heterogeneous partially cyclic polymers are simulated, and conditions for good separation by topology are predicted. According to the theory, an effective SEC-radius of tadpoles and manacles is mostly determined by the molar mass M, and by the linear-cyclic composition. In the interactive chromatography, the effect of molecular topology on the retention becomes significant. At the critical interaction point, partial dependences K(Mlin) and K(Mring) are qualitatively different: while being almost independent of Mlin, K increases with Mring. This behavior could be realized in critical chromatography-for separation of partially cyclic polymers by the number and molar mass of cyclic elements.
authors.affiliation: Institute for Highly Pure Biopreparations, 7 Pudozhskaya, 197110 St. Petersburg, Russia.
authors.forename: Andrey V
authors.initials: AV
authors.lastname: Vakhrushev
authors.affiliation: Institute for Highly Pure Biopreparations, 7 Pudozhskaya, 197110 St. Petersburg, Russia. Electronic address: AlexeiGorbunov@hotmail.com.
authors.forename: Alexei A
authors.initials: AA
authors.lastname: Gorbunov
mesh_terms: D000327:Adsorption; D000818:Animals; D002850:Chromatography, Gel / Q000379:methods; D002853:Chromatography, Liquid / Q000379:methods*; D008962:Models, Theoretical; D008970:Molecular Weight; D011108:Polymers / Q000737:chemistry*
chemical_list: D011108:Polymers
keywords: Chromatography; Critical adsorption interaction; Partially cyclic polymers; Separation by topology; Size-exclusion; Theory