title: Hydrodynamic Analysis Resolves the Pharmaceutically-Relevant Absolute Molar Mass and Solution Properties of Synthetic Poly(ethylene glycol)s Created by Varying Initiation Sites.
abstract: The solution behavior originating from molecular characteristics of synthetic macromolecules plays a pivotal role in many areas, in particular the life sciences. This situation necessitates the use of complementary hydrodynamic analytical methods as the only means for a complete structural understanding of any macromolecule in solution. To this end, we present a combined hydrodynamic approach for studying in-house prepared, low dispersity poly(ethylene glycols)s (PEGs), also known as poly(ethylene oxide)s (PEOs) depending on the classification used, synthesized from varying initiation sites by the living anionic ring opening polymerization. The series of linear PEGs in the molar mass range of only a few thousand to 50 000 g mol-1have been studied in detail via viscometry and sedimentation-diffusion analysis by analytical ultracentrifugation. The obtained estimations for intrinsic viscosity, diffusion coefficients, and sedimentation coefficients of the macromolecules in the solution-based analysis clearly showed self-consistency of the followed hydrodynamic approach. This self-consistency is underpinned by appropriate and physically sound values of hydrodynamic invariants, indicating adequate values of derived absolute molar masses. The classical scaling relations of Kuhn-Mark-Houwink-Sakurada of all molar-mass dependent hydrodynamic estimates show linear trends, allowing for interrelation of all parametric macromolecular characteristics. Differences among these are ascribed to the observation of α-end and chain-length dependent solvation of the macromolecules, identified from viscometric studies. This important information allows for analytical tracing of variations of scaling relationships and a physically sound estimation of hydrodynamic characteristics. The demonstrated self-sufficient methodology paves an important way for a complete structural understanding and potential replacement of pharmaceutically relevant PEGs by alternative macromolecules offering a suite of similar or tractably distinct physicochemical properties.
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena , Philosophenweg 7, 07743 Jena, Germany.
authors.forename: Ivo
authors.initials: I
authors.lastname: Nischang
authors.affiliation: Department of Molecular Biophysics and Physics of Polymers, St. Petersburg State University , Universitetskaya nab. 7/9, 199034, Saint Petersburg, Russia.
authors.forename: Igor
authors.initials: I
authors.lastname: Perevyazko
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena , Philosophenweg 7, 07743 Jena, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Majdanski
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena , Philosophenweg 7, 07743 Jena, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Vitz
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena , Philosophenweg 7, 07743 Jena, Germany.
authors.forename: Grit
authors.initials: G
authors.lastname: Festag
authors.affiliation: Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena , Humboldtstraße 10, 07743 Jena, Germany.|Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena , Philosophenweg 7, 07743 Jena, Germany.
authors.forename: Ulrich S
authors.initials: US
authors.lastname: Schubert
mesh_terms: D000838:Anions / Q000737:chemistry; D002850:Chromatography, Gel; D004058:Diffusion; D057446:Hydrodynamics; D008970:Molecular Weight; D011092:Polyethylene Glycols / Q000737:chemistry*; D058105:Polymerization; D012996:Solutions; D014461:Ultracentrifugation; D014783:Viscosity
chemical_list: D000838:Anions; D012996:Solutions; D011092:Polyethylene Glycols