TY - JOUR

T1 - “Hard” Sphere Behavior of “Soft”, Globular-like, Hyperbranched Polyglycerols − Extensive Molecular Hydrodynamic and Light Scattering Studies

AU - Lezov, Alexey

AU - Gubarev, Alexander

AU - Kaiser, Tobias

AU - Tobaschus, Willi

AU - Tsvetkov, Nikolai

AU - Nischang, Ivo

AU - Schubert, Ulrich S.

AU - Frey, Holger

AU - Perevyazko, Igor

N1 - Funding Information: I.P., A.G., and A.L. are grateful for the support by a grant from the Russian Foundation for Basic Research (project no 18-33-20013). Parts of the experiments were performed at the Center for Diagnostics of Functional Materials for Medicine, Pharmacology and Nanoelectronics of Research Park of Saint Petersburg State University. I.N. and U.S.S. gratefully acknowledge support of this study through the DFG-funded Collaborative Research Center PolyTarget (SFB 1278—project number 316213987, projects A06 and Z01). The authors thank U. Kemmer-Jonas for technical assistance. Publisher Copyright: © 2020 American Chemical Society. All rights reserved. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/11/10

Y1 - 2020/11/10

N2 - Whether or not hyperbranched polymers behave like quasi “hard spheres” in solution is the subject of numerous fundamental discussions, also motivated by research on the perfectly branched dendrimer structures. Experimentally targeting this question, a homologous series of hyperbranched polyglycerols (HPGs) was prepared in a wide range of molar masses from ca. 3000 to 700000 g mol−1 and an overall degree of branching (DB) between 0.55 and 0.59. HPG samples have been investigated by a comprehensive set of experimental hydrodynamic and light scattering approaches, i.e., sedimentation velocity studies in analytical ultracentrifugation, dynamic and static light scattering experiments, isothermal diffusion experiments, intrinsic viscosities, and size exclusion chromatography coupled with multiangle laser light scattering. The physical soundness of the obtained average molar masses, evaluated by the different, arguably, absolute approaches to molar mass estimations was verified via the concept of the hydrodynamic invariant (A0). The A0 values for the here studied and literature available/calculated values for all types of branched macromolecular topologies were found to assume an average of A0 = (2.6 ± 0.4) × 10−10 g cm2 s−2 K−1 mol−1/3. The hyperbranched polyglycerols adopt a very compact, globular-like conformation in aqueous solution, which is accompanied by a very high level of hydration, on average 1.7 g of water per 1 g of HPG macromolecules. The correspondingly determined classical scaling relationships return values that are characteristic for a classical hard sphere conformation: s = 2.16 × 10−3M0.67, [S], D = 251 × 10−3M−0.33, [10−7 cm2 s−1], [η] = 5.9M0, [cm3 g−1]. An experimentally high level of molecular compactness is then also reflected by the corresponding contraction factors, which show up to 50 times less molecular volume of HPGs at high molar mass values than their linear analogues.

AB - Whether or not hyperbranched polymers behave like quasi “hard spheres” in solution is the subject of numerous fundamental discussions, also motivated by research on the perfectly branched dendrimer structures. Experimentally targeting this question, a homologous series of hyperbranched polyglycerols (HPGs) was prepared in a wide range of molar masses from ca. 3000 to 700000 g mol−1 and an overall degree of branching (DB) between 0.55 and 0.59. HPG samples have been investigated by a comprehensive set of experimental hydrodynamic and light scattering approaches, i.e., sedimentation velocity studies in analytical ultracentrifugation, dynamic and static light scattering experiments, isothermal diffusion experiments, intrinsic viscosities, and size exclusion chromatography coupled with multiangle laser light scattering. The physical soundness of the obtained average molar masses, evaluated by the different, arguably, absolute approaches to molar mass estimations was verified via the concept of the hydrodynamic invariant (A0). The A0 values for the here studied and literature available/calculated values for all types of branched macromolecular topologies were found to assume an average of A0 = (2.6 ± 0.4) × 10−10 g cm2 s−2 K−1 mol−1/3. The hyperbranched polyglycerols adopt a very compact, globular-like conformation in aqueous solution, which is accompanied by a very high level of hydration, on average 1.7 g of water per 1 g of HPG macromolecules. The correspondingly determined classical scaling relationships return values that are characteristic for a classical hard sphere conformation: s = 2.16 × 10−3M0.67, [S], D = 251 × 10−3M−0.33, [10−7 cm2 s−1], [η] = 5.9M0, [cm3 g−1]. An experimentally high level of molecular compactness is then also reflected by the corresponding contraction factors, which show up to 50 times less molecular volume of HPGs at high molar mass values than their linear analogues.

UR - http://www.scopus.com/inward/record.url?scp=85096197141&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/44a459a8-89e0-3cc6-89e0-b9493c08c6f1/

U2 - 10.1021/acs.macromol.0c01340

DO - 10.1021/acs.macromol.0c01340

M3 - Article

AN - SCOPUS:85096197141

VL - 53

SP - 9220

EP - 9233

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 21

ER -