Conducting polymers demonstrate low solubility in organic solvents. Introducing aliphatic substituents into polymer chains improves their solubility, but may also lead to changes in conformational characteristics of macromolecules. In the present work, the studies of hydrodynamic properties and conformational characteristics of comb-shaped poly(3-hexylthiophene) with aliphatic side substituents were carried out in chloroform solutions. Conformational analysis of the studied macromolecules was performed for the first time using homologous series with a wide range of molecular weights of the polymers in dilute solutions. The hydrodynamic properties of these macromolecules were interpreted using the worm-like spherocylinder model and the straight spherocylinder model. The projection of the monomer unit in the direction of the main polymer chain k 5 0.37 nm was determined experimentally. The following parameters of poly(3-hexylthiophene) were characterized and quantified: equilibrium rigidity (Kuhn segment length) ff 5 6.7 nm and hydrodynamic diameter of a polymer chain d 5 0.6 nm.
a b s t r a c tThe samples of poly(12-acryloylaminododecanoic acid) were synthesized in micellar solutions of the monomer. The possibility of obtaining polymeric ionogenic surfactants of different molecular masses by varying concentration of monomeric surfactant was demonstrated. Detailed studies of the obtained polymer were performed using macromolecular hydrodynamic methods, dynamic light scattering, scanning probe microscopy and flow birefringence. The parameter of equilibrium rigidity of macromolecules (the Kuhn segment length A ¼ 62 Â 10 À8 cm) and their effective hydrodynamic diameter were determined in mixed solvent (dioxane-cyclohexanol). Contributions made by optical microform and macroform effects to the observed dynamic birefringence were analyzed in detail. The intrinsic optical anisotropy of the monomer unit was estimated; it correlates well with the corresponding values for comb-shaped polymers of similar structure.
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.
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