POS8-0025

The impact of topology and chain length of polyvinylpyrrolidone macromolecules on the crystallization of naproxen

Topic

S8. Frontiers of Functional Polymers in Biology and Medicine

When and Where

Oct 1, 2026 08:30 - 09:30

Room 301 (Grand Ballroom)

Session Chairs

Jinkee HONG

Ki Su KIM

Presenter(s)

Ewa Ozimina Kaminska (Department of Pharmacognosy and Phytochemistry, Faculty of Pharmaceutical Sciences in Sosnowiec, Medical University of Silesia in Katowice, Jagiellonska 4, 41-200 Sosnowiec, Poland)

Co-Author(s)

Luiza Orszulak (Institute of Chemistry, Faculty of Science and Technology, University of Silesia in Katowice, Szkolna 9, 40-007 Katowice, Poland), Karolina Jurkiewicz (Institute of Physics, Faculty of Science and Technology, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland), Magdalena Tarnacka (Institute of Physics, Faculty of Science and Technology, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland), Barbara Hachuła (Institute of Chemistry, Faculty of Science and Technology, University of Silesia in Katowice, Szkolna 9, 40-007 Katowice, Poland), Kamil Kaminski (Institute of Physics, Faculty of Science and Technology, University of Silesia in Katowice, 75 Pulku Piechoty 1A, 41-500 Chorzow, Poland), Patryk Włodarczyk (Institute of Non Ferrous Metals, Sowinskiego 5, 44-100 Gliwice, Poland)

Abstract

This study explores the application of self-synthesized polyvinylpyrrolidone (PVP) homopolymers with diverse architectures as inhibitory matrices for the crystallization of naproxen (NAP), a poor glass-forming compound. Amorphous binary mixtures composed of NAP and (i) linear PVP (linPVP38k), (ii) three-arm star-shaped PVP (starPVP), (iii) linear PVP matching the molecular mass (M_n) of one star arm (linPVP14k), and (iv) commercial PVP K30, were examined. Using differential scanning calorimetry (DSC), X-ray diffraction (XRD), infrared spectroscopy (IR), and molecular dynamics (MD) simulations, we investigated the impact of polymer topology, chain length, and dispersity (Ð) on NAP crystallization kinetics and intermolecular interactions in NAP-PVP systems. Isothermal DSC studies revealed that linPVP38k with a higher M_n (~40,000) and low Ð is the most effective stabilizer, surpassing both the star-shaped architecture and the commercial reference. Interestingly, near the T_g, NAP crystallization proceeds at a similar rate for the mixtures with starPVP and linPVP14k (matching the M_n of one star arm). XRD investigations showed that, regardless of the polymer topology or M_n, NAP crystallizes into the same polymorphic form. IR and MD simulations demonstrated that the greatest long-term stability (up to four months) of the 60:40 w/w NAP-PVP systems, confirmed by XRD, is mainly due to H-bonds between NAP and PVP molecules. The high polymer content prevents the self-association of NAP molecules, thus significantly affecting crystallization kinetics. Moreover, MD analysis indicated the greatest homogeneity in the NAP-linPVP38k mixture, explaining the effective crystallization inhibition by the polymer with an M_n similar to PVP K30 but with relatively uniform chain lengths (low Ð). These findings are of particular importance for the design of new pharmaceutical formulations containing polymers with well-defined macromolecular parameters and architectures.

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