Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Roka, Nikoletta; Kokkorogianni, Olga; Kontoes-Georgoudakis, Philippos; Choinopoulos, Ιoannis; Pitsikalis, Marinos

doi:10.3390/polym14040701

Cited by 15 publications

(10 citation statements)

References 185 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A promising technique for producing complex macromolecular structures appears to be Reversible Addition–Fragmentation Chain Transfer (RAFT) polymerization, where a crucial role is played by a suitably selected Chain Transfer Agent (CTA) for a specific type of monomer [ 51 ]. As indicated in the literature, suitable CTAs for N -vinyl monomers (including VP) are compounds from the xanthate and dithiocarbamate groups [ 52 , 53 ]. It should also be emphasized that a significant majority of commercially available CTAs are single-functional compounds, allowing for the formation of linear macromolecules.…”

Section: Resultsmentioning

confidence: 99%

The Impact of Various Poly(vinylpyrrolidone) Polymers on the Crystallization Process of Metronidazole

Orszulak,

Lamrani,

Tarnacka

et al. 2024

Pharmaceutics

View full text Add to dashboard Cite

In this paper, we propose one-step synthetic strategies for obtaining well-defined linear and star-shaped polyvinylpyrrolidone (linPVP and starPVP). The produced macromolecules and a commercial PVP K30 with linear topology were investigated as potential matrices for suppressing metronidazole (MTZ) crystallization. Interestingly, during the formation of binary mixtures (BMs) containing different polymers and MTZ, we found that linear PVPs exhibit maximum miscibility with the drug at a 50:50 weight ratio (w/w), while the star-shaped polymer mixes with MTZ even at a 30:70 w/w. To explain these observations, comprehensive studies of MTZ-PVP formulations with various contents of both components were performed using Fourier-transform infrared spectroscopy, differential scanning calorimetry, and X-ray diffraction. The obtained results clearly showed that the polymer’s topology plays a significant role in the type of interactions occurring between the matrix and MTZ. Additionally, we established that for MTZ-PVP 50:50 and 75:25 w/w BMs, linear polymers have the most substantial impact on inhibiting the crystallization of API. The star-shaped macromolecule turned out to be the least effective in stabilizing amorphous MTZ at these polymer concentrations. Nevertheless, long-term structural investigations of the MTZ-starPVP 30:70 w/w system (which is not achievable for linear PVPs) demonstrated its complete amorphousness for over one month.

show abstract

Section: Resultsmentioning

confidence: 99%

The Impact of Various Poly(vinylpyrrolidone) Polymers on the Crystallization Process of Metronidazole

Orszulak,

Lamrani,

Tarnacka

et al. 2024

Pharmaceutics

View full text Add to dashboard Cite

show abstract

“…For many years, PVP has been widely used in the medical, cosmetic, and food industries due to its unique chemical and biological properties: it is nontoxic to humans, biocompatible, and highly water-soluble . Other properties, such as film-forming ability, chemical and thermal resistance, and its amorphous character, are also desirable and widely utilized in the above-mentioned industrial sectors. , Hence, there are numerous works in the literature where the influence of this macromolecule on improving the solubility of APIs by forming ASDs is considered. Unfortunately, despite the great importance of this polymer, scientists still only examine the role of molecular weights ( M n ) of commercially available PVP, − while the impact of other factors, such as polymer topology or dispersity ( Đ ) on the pharmacokinetic properties of numerous pharmaceuticals, is not described at all.…”

Section: Resultsmentioning

confidence: 99%

The Influence of PVP Polymer Topology on the Liquid Crystalline Order of Itraconazole in Binary Systems

Orszulak,

Lamrani,

Bernat

et al. 2024

Mol. Pharmaceutics

View full text Add to dashboard Cite

This study presents a novel approach by utilizing poly-(vinylpyrrolidone)s (PVPs) with various topologies as potential matrices for the liquid crystalline (LC) active pharmaceutical ingredient itraconazole (ITZ). We examined amorphous solid dispersions (ASDs) composed of ITZ and (i) self-synthesized linear PVP, (ii) self-synthesized star-shaped PVP, and (iii) commercial linear PVP K30. Differential scanning calorimetry, X-ray diffraction, and broad-band dielectric spectroscopy were employed to get a comprehensive insight into the thermal and structural properties, as well as global and local molecular dynamics of ITZ−PVP systems. The primary objective was to assess the influence of PVPs' topology and the composition of ASD on the LC ordering, changes in the temperature of transitions between mesophases, the rate of their restoration, and finally the solubility of ITZ in the prepared ASDs. Our research clearly showed that regardless of the PVP type, both LC transitions, from smectic (Sm) to nematic (N) and from N to isotropic (I) phases, are effectively suppressed. Moreover, a significant difference in the miscibility of different PVPs with the investigated API was found. This phenomenon also affected the solubility of API, which was the greatest, up to 100 μg/mL in the case of starPVP 85:15 w/w mixture in comparison to neat crystalline API (5 μg/mL). Obtained data emphasize the crucial role of the polymer's topology in designing new pharmaceutical formulations.

show abstract

“…One of these methods is the reversible addition-fragmentation chain transfer polymerization or, in short, RAFT, which was developed in the late 1990s . Many different types of block copolymers were successfully synthesized by applying RAFT techniques. − However, these polymers are synthesized primarily in laboratory scales yielding only small amounts of polymers (in the lower gram scale). Apart from a couple of studies utilizing continuous flow processes as a way to enhance the scale of these reactions, − the scale-up of RAFT polymerization has not been the focus.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of the Synthesis of Poly(4-vinylpyridine) Macro-Reversible Addition-Fragmentation Chain Transfer Agents for the Preparation of Block Copolymers

Kandelhard

Pashayev

Schymura

et al. 2023

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most common controlled polymerization techniques to prepare well-defined, rather narrow dispersed polymers due to reduced demands in reactant preparation. Despite these advantages, RAFT polymerization was so far primarily utilized on small laboratory scales. This study presents a first step to a scaled-up RAFT polymerization by developing and experimentally validating a kinetic model on the example of the polymerization of 4-vinylpyridine (4VP), which to date is not described in the literature. With the implementation of the results from modeling, the synthesis process was extended to a medium scale (from 6 to 36 g), while the same high conversions, molar mass, and low dispersity as in the smaller scale were achieved. The process is also optimized regarding the high degree of livingness necessary for using the 4VP polymers as a macro-RAFT agent in the subsequent reaction step for the synthesis of poly(4-vinylpyridine)-b-polystyrene diblock copolymers by RAFT dispersion polymerization.

show abstract

Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

Cited by 15 publications

References 185 publications

The Impact of Various Poly(vinylpyrrolidone) Polymers on the Crystallization Process of Metronidazole

The Impact of Various Poly(vinylpyrrolidone) Polymers on the Crystallization Process of Metronidazole

The Influence of PVP Polymer Topology on the Liquid Crystalline Order of Itraconazole in Binary Systems

Kinetic Modeling of the Synthesis of Poly(4-vinylpyridine) Macro-Reversible Addition-Fragmentation Chain Transfer Agents for the Preparation of Block Copolymers

Contact Info

Product

Resources

About