Porous polymer monoliths with thicknesses of 2 and 4 mm were obtained via polymerization of ethylene glycol dimethacrylate (EGDMA) under the influence visible-light irradiation in the presence of a 70 wt% 1-butanol porogenic agent and o-quinone photoinitiators. The o-quinones used were: 3,5-di-tret-butyl-benzoquinone-1,2 (35Q), 3,6-di-tret-butyl-benzoquinone-1,2 (36Q), camphorquinone (CQ), and 9,10-phenanthrenequinone (PQ). Porous monoliths were also synthesized from the same mixture but using 2,2′-azo-bis(iso-butyronitrile) (AIBN) at 100 °C instead o-quinones. According to the results of scanning electron microscopy, all the resulting samples were conglomerates of spherical, polymeric particles with pores between them. Use of mercury porometry showed that the interconnected pore systems of all the polymers were open. The average pore size, D_mod, in such polymers strongly depended on both the nature of the initiator and the method of initiation of polymerization. For polymers obtained in the presence of AIBN, the D_mod value was as low as 0.8 μm. For polymers obtained via photoinitiation in the presence of 36Q, 35Q, CQ, and PQ, the D_mod values were significantly greater, i.e., 9.9, 6.4, 3.6, and 3.7 μm, respectively. The compressive strength and Young’s modulus of the porous monoliths increased symbatically in the series PQ < CQ < 36Q < 35Q < AIBN with decreasing proportions of large pores (over 12 μm) in their polymer structures. The photopolymerization rate of the EGDMA and 1-butanol, 30:70 wt% mixture was maximal for PQ and minimal for 35Q. All polymers tested were non-cytotoxic. Based on the data from MTT testing, it can be noted that the polymers obtained via photoinitiation were characterized by their positive effect on the proliferative activity of human dermal fibroblasts. This makes them promising osteoplastic materials for clinical trials.

Porous polymer monolith materials of 2-mm thickness were obtained by visible light-induced radical polymerization of oligocarbonate dimethacrylate (OCM-2) in the presence of 1-butanol (10 to 70 wt %) as a porogenic additive. The pore characteristics and morphology of polymers were studied by mercury intrusion porosimetry and scanning electron microscopy. Monolithic polymers with both open and closed pores up to 100 nm in size are formed when the alcohol content in the initial composition is up to 20 wt %. The pore structure in such materials is a system of holes in the bulk of the polymer (hole-type pores). Open interconnected pores with a specific volume up to 2.22 cm³/g and modal pore size up to 10 microns are formed in the volume of the polymer with 1-butanol content of more than 30 wt %. Such porous monoliths are a structure of covalently bonded polymer globules (interparticle-type pores). The free space between the globules represents a system of open interconnected pores. In the transition region of 1-butanol concentrations (from 20 to 30 wt %), areas with both structures and intermediate frameworks, as well as honeycomb structures of polymer globules connected by bridges, are fixed on the polymer surface. It was found that the transition from one type of pore system to another is accompanied by a sharp change in the strength characteristics of the polymer. Approximation of experimental data using the sigmoid function made it possible to determine the concentration of the porogenic agent in the vicinity of which the percolation threshold is observed.

Hybrid porous polymers based on poly-EGDMA and polylactide containing vancomycin, the concentration of which in the polymer varied by two orders of magnitude, were synthesized. The processes of polymer biodegradation and vancomycin release were studied in the following model media: phosphate-buffered saline (PBS), trypsin-Versene solution, and trypsin-PBS solution. The maximum antibiotic release was recorded during the first 3 h of extraction. The duration of antibiotic escape from the polymer samples in trypsin-containing media varied from 3 to 22 days, depending on the antibiotic content of the polymer. Keeping samples of the hybrid polymer in trypsin-containing model media resulted in acidification of the solutions—after 45 days, up to a pH of 1.84 in the trypsin-Versene solution and up to pH 1.65 in the trypsin-PBS solution. Here, the time dependences of the vancomycin release from the polymer into the medium and the decrease in pH of the medium correlated. These data are also consistent with the results of a study of the dynamics of sample weight loss during extraction in the examined model media. However, while the polymer porosity increased from ~53 to ~60% the pore size changed insignificantly, over only 10 μm. The polymer samples were characterized by their antibacterial activity against Staphylococcus aureus, and this activity persisted for up to 21 days during biodegradation of the material, regardless of the medium type used in model. Surface-dependent human cells (dermal fibroblasts) adhere well, spread out, and maintain high viability on samples of the functionalized hybrid polymer, thus demonstrating its biocompatibility in vitro.

This paper provides a study of two bone substitutes: a hybrid porous polymer and an osteoplastic matrix based on a bovine-derived xenograft. Both materials are porous, but their pore characteristics are different. The osteoplastic matrix has pores of 300–600 µm and the hybrid polymer has smaller pores, generally of 6–20 µm, but with some pores up to 100 µm across. SEM data confirmed the porometry results and demonstrated the different structures of the materials. Therefore, both materials were characterized by an interconnected porous structure and provided conditions for the adhesion and vital activity of human ASCs in vitro. In an experimental model of rabbit shin bone defect, it was shown that, during the 6-month observation period, neither of the materials caused negative reactions in the experimental animals. By the end of the observation period, restoration of the defects in animals in both groups was completed, and elements of both materials were preserved in the defect areas. Data from morphological examinations and CT data demonstrated that the rate of rabbit bone tissue regeneration with the hybrid polymer was comparable to that with the osteoplastic matrix. Therefore, the hybrid polymer has good potential for use in further research and improvement in biomedical applications.

Recent decades have been characterized by increasing numbers of bone tissue injuries and diseases resulting in the formation of bone defects. The number of such bone defects has also grown due to active surgical approaches implemented after surgical interventions for oncological, infectious, and dystrophic bone lesions. To repair such bone defects requires the use of bone tissue substitutes. Nowadays, constructs based on matrices of various compositions and structures, supplemented with the addition of biologically active components (including growth factors and cells), are the most promising approaches used in bone tissue engineering. The properties of the matrices are of the utmost importance in construct formation. This work presents the results of a comprehensive study of matrices of various natures intended for the formation of complex constructs for bone tissue engineering. Using a set of methods for studying the physical, mechanical, and biological characteristics, the total and associated porosity of the studied matrices, the structure, the mechanical parameters, and the level of cytotoxicity and cytocompatibility were determined. It was shown that all the studied materials were not cytotoxic (cytotoxicity rank of all matrices = 0–1). All matrices were porous, but samples of materials of biological origin had large pores ranging in size from 100 to 1000 μm, and pores of the hybrid polymer were sized from 0.1 to 100 μm. Total and open porosity ranged from 89% and 79% for the allogeneic matrix up to 67% and 48% for the hybrid polymer, respectively, while the σ values (compressive stress at break) of samples of all studied materials were close to each other. When human test culture MSCs interact with samples of these materials, it was shown that the cells adhere to the surface and structure of all materials and retain typical morphology, while also demonstrating the ability to proliferate and migrate along the surface and into the matrix structure, i.e., all materials are cytocompatible. Based on the data obtained, it can be assumed that all the studied matrices can be used for model biomedical studies and as a basis for constructs for bone tissue engineering. An adequate choice of research method at the earliest stages of the development of each material will ensure the most effective approaches for further work and subsequent use of this product.