Incentives of Using the Hydrodynamic Invariant and Sedimentation Parameter for the Study of Naturally- and Synthetically-Based Macromolecules in Solution

Abstract

The interrelation of experimental rotational and translational hydrodynamic friction data as a basis for the study of macromolecules in solution represents a useful attempt for the verification of hydrodynamic information. Such interrelation originates from the basic development of colloid and macromolecular science and has proven to be a powerful tool for the study of naturally- and synthetically-based, i.e., artificial, macromolecules. In this tutorial review, we introduce this very basic concept with a brief historical background, the governing physical principles, and guidelines for anyone making use of it. This is because very often data to determine such an interrelation are available and it only takes a set of simple equations for it to be established. We exemplify this with data collected over recent years, focused primarily on water-based macromolecular systems and with relevance for pharmaceutical applications. We conclude with future incentives and opportunities for verifying an advanced design and tailored properties of natural/synthetic macromolecular materials in a dispersed or dissolved manner, i.e., in solution. Particular importance for the here outlined concept emanates from the situation that the classical scaling relationships of Kuhn–Mark–Houwink–Sakurada, most frequently applied in macromolecular science, are fulfilled, once the hydrodynamic invariant and/or sedimentation parameter are established. However, the hydrodynamic invariant and sedimentation parameter concept do not require a series of molar masses for their establishment and can help in the verification of a sound estimation of molar mass values of macromolecules.

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

“…In the literature, distinct characteristic values of A 0 , in [g cm 2 s −2 K −1 mol −1/3 ] for all basic macromolecular systems in solution are available. 35,41,54 In general, for linear flexible polymer chains, the average value of A 0 = (3.2 ± 0.2) × 10 −10 was found, while for rigid chain macromolecules, the average value of A 0 is (3.7 ± 0.4) × 10 19 on high-molar-mass HPGs with up to ≈ 9 × 10 6 g mol −1 molar mass, the calculated average values of A 0 are (2.5 ± 0.3) × 10 −10 . The experimental values averaged around A 0 = 2.5 are very peculiar since those are notably lower than the theoretical minimum limit predicted for a solid impermeable sphere, i.e., A 0 = 2.914 .…”

“…In the literature, distinct characteristic values of A 0 , in [g cm 2 s –2 K –1 mol –1/3 ] for all basic macromolecular systems in solution are available. ,, In general, for linear flexible polymer chains, the average value of A 0 = (3.2 ± 0.2) × 10 –10 was found, while for rigid chain macromolecules, the average value of A 0 is (3.7 ± 0.4) × 10 –10 . However, for branched and hyperbranched polymer systems, systematic studies of the A 0 values are scarce and practically absent in the literature.…”

Reincarnation of the Analytical Ultracentrifuge: Emerging Opportunities for Nanomedicine

“…The AUC enables characterization of solution components covering the entire colloidal size range by widely adjustable rotor speeds and, therefore, centrifugal forces. From its beginnings, it has been primarily used for the characterization of particles, proteins, and macromolecules of natural origin. ,− Much efforts have also been devoted into the characterization of natural and synthetic (man-made) polymer systems. ,,,− Translation to nanomedicines concerns EMA and FDA approved drug formulations utilizing stealth polymers such as the “gold standard” poly­(ethylene glycol) (PEG) and recently discussed alternatives such as, e.g., poly­(2-alkyl-2-oxazoline)­s (POx)­s , and linear polyglycerols (LPG)­s . The determination of the buoyancy factor, (1 – υϱ 0 ), in eqs and is common for studies with polymer systems by density increment measurements utilizing a densimeter, allowing the assessment of υ. ,,,− …”

“…The study of the above-mentioned polymer systems is oftentimes performed in concert with the concept of intrinsic viscosities finding its origin with Staudinger (vide supra). ,− , Therefore, we mainly focus our attention on this new field of characterization research and systems making use of an AUC.…”

“Polymer Analysis” Section, in Journal Polymers

“…A selection of cutting-edge “Hot Papers” published in the Polymer Analysis section of Polymers is presented at the end of this Editorial [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ].…”