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.
Highlights
The rise of the macromolecular hypothesis [1] and, the conceptual existence of macromolecules can be traced back to Hermann Staudinger, who can be associated with the very initial studies of macromolecules at the beginning of the last century [2,3,4]
We attempted the contextualization of the results with the concept of the hydrodynamic invariant and sedimentation parameter
We found that average values for the hydrodynamic invariant and sedimentation parameter, when compared to the first cumulative literature data, are in fundamental agreement
Summary
The rise of the macromolecular hypothesis [1] and, the conceptual existence of macromolecules can be traced back to Hermann Staudinger, who can be associated with the very initial studies of macromolecules at the beginning of the last century [2,3,4]. The measurement of sedimentation coefficients by sedimentation velocity experiments making use of analytical ultracentrifugation as well as diffusion coefficients decoupled from sedimentation, found their inception at this period of time as well [10] With these selected major pioneering contributions to the field of research of macromolecular hydrodynamics, important for this review, began the study of basic hydrodynamic characteristics of macromolecules and colloids in solution, the intrinsic viscosity, the (intrinsic) diffusion coefficient, and the (intrinsic) sedimentation coefficient. This concerns the absolute molar mass, inaccessible by calibrated standard procedures, such as size-exclusion chromatography It is exactly this advancement in synthetic concepts and opportunities that requires a retro-synthetic analysis of macromolecular structures in solution, reconciled by their fundamental molecular hydrodynamic properties. Their establishment is based on the very prime hydrodynamic characteristics, i.e., (intrinsic) viscosity/concentration sedimentation coefficient, (intrinsic) sedimentation coefficient, and (intrinsic) diffusion coefficient of a particular macromolecular sample
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