Conformational Parameters and Hydrodynamic Behavior of Poly(2-Methyl-2-Oxazoline) in a Broad Molar Mass Range

In this work, we report our results on the hydrodynamic behavior of poly(2-methyl-2-oxazoline) (PMeOx). PMeOx is gaining significant attention for use as hydrophilic polymer in pharmaceutical carriers as an alternative for the commonly used poly(ethylene glycol) (PEG), for which antibodies are found in a significant fraction of the human population. The main focus of the current study is to determine the hydrodynamic characteristics of PMeOx under physiological conditions, which serves as basis for better understanding of the use of PMeOx in pharmaceutical applications. This goal was achieved by studying PMeOx solutions in phosphate-buffered saline (PBS) as a solvent at 37 °C. This study was performed based on two series of PMeOx samples; one series is synthesized by conventional living cationic ring-opening polymerization, which is limited by the maximum chain length that can be achieved, and a second series is obtained by an alternative synthesis strategy based on acetylation of well-defined linear poly(ethylene imine) (PEI) prepared by controlled side-chain hydrolysis of a defined high molar mass of poly(2-ethyl-2-oxazoline). The combination of these two series of PMeOx allowed the determination of the Kuhn–Mark–Houwink–Sakurada equations in a broad molar mass range. For intrinsic viscosity, sedimentation and diffusion coefficients, the following expressions were obtained: η=0.015M0.77, s0=0.019M0.42 and D0=2600M−0.58, respectively. As a result, it can be concluded that the phosphate-buffered saline buffer at 37 °C represents a thermodynamically good solvent for PMeOx, based on the scaling indices of the equations. The conformational parameters for PMeOx chains were also determined, revealing an equilibrium rigidity or Kuhn segment length, (A) of 1.7 nm and a polymer chain diameter (d) of 0.4 nm. The obtained value for the equilibrium rigidity is very similar to the reported values for other hydrophilic polymers, such as PEG, poly(vinylpyrrolidone) and poly(2-ethyl-2-oxazoline), making PMeOx a relevant alternative to PEG

Hydrodynamic Characteristics and Conformational Parameters of Ferrocene-Terpyridine-Based Polymers

Nowadays, the study of metallopolymers is one of the fastest growing areas of polymer science. Metallopolymers have great potential for application in multiple technological and various biomedical processes. The macromolecules with the possibility of varying the number and type of metal ions along the entire length of the polymer chain are of particular interest. In this regard, this study presents results on two successfully synthesized homopolymers, random and block copolymers based on PMMA, containing ferrocene and terpyridine moieties in the side chain. Different architectures of copolymers may attribute interesting properties when creating complexes with various metal ions. A detailed hydrodynamic study of these structures was carried out, the consistency of hydrodynamic data was established using the concept of a hydrodynamic invariant, the absolute values of the molar masses of the studied objects were calculated, and the conformational parameters of macromolecules were determined. Using the Fixman–Stockmayer theory, the equilibrium rigidities of the studied systems were calculated and the relationship between the chemical structure and conformational characteristics was established. The studied copolymers can be attributed to the class of flexible-chain macromolecules. An increase in the equilibrium rigidity value with an increase of the side chain, which is characteristic of comb-shaped polymers, was determined

Temperature-responsive star-shaped poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) with central thiacalix[4]arene fragments: structure and properties in solutions

Temperature-responsive star-shaped poly(2-ethyl-2-oxazoline) (star-PETOX) and poly(2-isopropyl-2-oxazoline) (star-PIPOX) with arms grafted to the lower rim of thiacalix[4]arene were studied in solutions by viscometry, sedimentation velocity, light scattering, and small-angle neutron scattering. The experiments were carried out in water and tetrahydrofuran solutions. It was revealed that in tetrahydrofuran, the studied polymers were present only as individual molecules, while in aqueous solutions, in addition to individual molecules, large polymer aggregates were found. Molecular characteristics of the star-PETOX and star-PIPOX samples were estimated; their behavior in tetrahydrofuran and water was studied over a wide temperature range. It was established that a cloud point of the aqueous solution of star-PETOX (67 °C) is higher than that of a solution of star-PIPOX (35 °C). Comparison of the data obtained by dynamic light scattering and small-angle neutron scattering turned out to be fruitful in revealing all the structural levels of the organization of star-PETOX and star-PIPOX in aqueous solutions. They include the level of the individual macromolecules and the level of supramolecular organization with a star-like architecture