Cryostructuring of Polymeric Systems: 67 Properties and Microstructure of Poly(Vinyl Alcohol) Cryogels Formed in the Presence of Phenol or Bis-Phenols Introduced into the Aqueous Polymeric Solutions Prior to Their Freeze-Thaw Processing.

Poly(vinyl alcohol) (PVA) physical cryogels that contained the additives of o-, m-, and p-bis-phenols or phenol were prepared, and their physico-chemical characteristics and macroporous morphology and the solute release dynamics were evaluated. These phenolic additives caused changes in the viscosity of initial PVA solutions before their freeze-thaw processing and facilitated the growth in the rigidity of the resultant cryogels, while their heat endurance decreased. The magnitude of the effects depended on the interposition of phenolic hydroxyls in the molecules of the used additives and was stipulated by their H-bonding with PVA OH-groups. Subsequent rinsing of such "primary" cryogels with pure water led to the lowering of their rigidity. The average size of macropores inside these heterophase gels also depended on the additive type. It was found also that the release of phenolic substances from the additive-containing cryogels occurred via virtually a free diffusion mechanism; therefore, drug delivery systems such as PVA cryogels loaded with either pyrocatechol, resorcinol, hydroquinone, or phenol, upon the in vitro agar diffusion tests, exhibited antibacterial activity typical of these phenols. The promising biomedical potential of the studied nanocomposite gel materials is supposed.

Cryostructuring of Polymeric Systems: 64. Preparation and Properties of Poly(vinyl alcohol)-Based Cryogels Loaded with Antimicrobial Drugs and Assessment of the Potential of Such Gel Materials to Perform as Gel Implants for the Treatment of Infected Wounds.

Physical macroporous poly(vinyl alcohol)-based cryogels formed by the freeze-thaw technique without the use of any foreign cross-linkers are of significant interests for biomedical applications. In the present study, such gel materials loaded with the antimicrobial substances were prepared and their physicochemical properties were evaluated followed by an assessment of their potential to serve as drug carriers that can be used as implants for the treatment of infected wounds. The antibiotic Ceftriaxone and the antimycotic Fluconazole were used as antimicrobial agents. It was shown that the Ceftriaxone additives caused the up-swelling effects with respect to the cryogel matrix and some decrease in its heat endurance but did not result in a substantial change in the gel strength. With that, the drug release from the cryogel vehicle occurred without any diffusion restrictions, which was demonstrated by both the spectrophotometric recording and the microbiological agar diffusion technique. In turn, the in vivo biotesting of such drug-loaded cryogels also showed that these materials were able to function as rather efficient antimicrobial implants injected in the artificially infected model wounds of laboratory rabbits. These results confirmed the promising biomedical potential of similar implants.

Cryostructuring of Polymeric Systems †: Application of Deep Neural Networks for the Classification of Structural Features Peculiar to Macroporous Poly(vinyl alcohol) Cryogels Prepared without and with the Additives of Chaotropes or Kosmotropes.

Macroporous poly(vinyl alcohol) cryogels (PVACGs) are physical gels formed via cryogenic processing of polymer solutions. The properties of PVACGs depend on many factors: the characteristics and concentration of PVA, the absence or presence of foreign solutes, and the freezing-thawing conditions. These factors also affect the macroporous morphology of PVACGs, their total porosity, pore size and size distribution, etc. In this respect, there is the problem with developing a scientifically-grounded classification of the morphological features inherent in various PVACGs. In this study PVA cryogels have been prepared at different temperatures when the initial polymer solutions contained chaotropic or kosmotropic additives. After the completion of gelation, the rigidity and heat endurance of the resultant PVACGs were evaluated, and their macroporous structure was investigated using optical microscopy. The images obtained were treated mathematically, and deep neural networks were used for the classification of these images. Training and test sets were used for their classification. The results of this classification for the specific deep neural network architecture are presented, and the morphometric parameters of the macroporous structure are discussed. It was found that deep neural networks allow us to reliably classify the type of additive or its absence when using a combined dataset.

Cryostructuring of Polymeric Systems. 49. Unexpected "Kosmotropic-Like" Impact of Organic Chaotropes on Freeze⁻Thaw-Induced Gelation of PVA in DMSO.

Urea (URE) and guanidine hydrochloride (GHC) possessing strong chaotropic properties in aqueous media were added to DMSO solutions of poly(vinyl alcohol) (PVA) to be gelled via freeze⁻thaw processing. Unexpectedly, it turned out that in the case of the PVA cryotropic gel formation in DMSO medium, the URE and GHC additives caused the opposite effects to those observed in water, i.e., the formation of the PVA cryogels (PVACGs) was strengthened rather than inhibited. Our studies of this phenomenon showed that such "kosmotropic-like" effects were more pronounced for the PVACGs that were formed in DMSO in the presence of URE additives, with the effects being concentration-dependent. The additives also caused significant changes in the macroporous morphology of the cryogels; the commonly observed trend was a decrease in the structural regularity of the additive-containing samples compared to the additive-free gel sample. The viscosity measurements revealed consistent changes in the intrinsic viscosity, Huggins constant, and the excess activation heat of the viscosity caused by the additives. The results obtained evidently point to the urea-induced decrease in the solvation ability of DMSO with respect to PVA. As a result, this effect can be the key factor that is responsible for strengthening the structure formation upon the freeze⁻thaw gelation of this polymer in DMSO additionally containing additives such as urea, which is capable of competing with PVA for the solvent.