Gelatin-modified polyurethanes for soft tissue scaffold.

Recently, in the field of biomaterials for soft tissue scaffolds, the interest of their modification with natural polymersis growing. Synthetic polymers are often tough, and many of them do not possess fine biocompatibility. On the other hand, natural polymers are biocompatible but weak when used alone. The combination of natural and synthetic polymers gives the suitable properties for tissue engineering requirements. In our study, we modified gelatin synthetic polyurethanes prepared from polyester poly(ethylene-butylene adipate) (PEBA), aliphatic 1,6-hexamethylene diisocyanate (HDI), and two different chain extenders 1,4-butanediol (BDO) or 1-ethoxy-2-(2-hydroxyethoxy)ethanol (EHEE). From a chemical point of view, we replaced expensive components for building PU, such as 2,6-diisocyanato methyl caproate (LDI) and 1,4-diisocyanatobutane (BDI), with cost-effective HDI. The gelatin was added in situ (in the first step of synthesis) to polyurethane to increase biocompatibility and biodegradability of the obtained material. It appeared that the obtained gelatin-modified PU foams, in which chain extender was BDO, had enhanced interactions with media and their hydrolytic degradation profile was also improved for tissue engineering application. Furthermore, the gelatin introduction had positive impact on gelatin-modified PU foams by increasing their hemocompatibility.

Medical-Grade PCL Based Polyurethane System for FDM 3D Printing-Characterization and Fabrication.

The widespread use of three-dimensional (3D) printing technologies in medicine has contributed to the increased demand for 3D printing materials. In addition, new printing materials that are appearing in the industry do not provide a detailed material characterization. In this paper, we present the synthesis and characterization of polycaprolactone (PCL) based medical-grade thermoplastic polyurethanes, which are suitable for forming in a filament that is dedicated to Fused Deposition Modeling 3D (FDM 3D)printers. For this purpose, we synthesized polyurethane that is based on PCL and 1,6-hexamethylene diisocyanate (HDI) with a different isocyanate index NCO:OH (0.9:1, 1.1:1). Particular characteristics of synthesized materials included, structural properties (FTIR, Raman), thermal (differential scanning calorimetry (DSC), thermogravimetric analysis (TGA)), mechanical and surfaces (contact angle) properties. Moreover, pre-biological tests in vitro and degradation studies were also performed. On the basis of the conducted tests, a material with more desirable properties S-TPU(PCL)0.9 was selected and the optimization of filament forming via melt-extrusion process was described. The initial biological test showed the biocompatibility of synthesized S-TPU(PCL)0.9 with respect to C2C12 cells. It was noticed that the process of thermoplastic polyurethanes (TPU) filaments forming by extrusion was significantly influenced by the appropriate ratio between the temperature profile, rotation speed, and dosage ratio.

Fabrication and Characterization of Flexible Medical-Grade TPU Filament for Fused Deposition Modeling 3DP Technology.

The possibility of using additive manufacturing (AM) in the medicine area has created new opportunities in health care. This has contributed to a sharp increase in demand for 3D printers, their systems and materials that are adapted to strict medical requirements. We described herein a medical-grade thermoplastic polyurethane (S-TPU) which was developed and then formed into a filament for Fused Deposition Modeling (FDM) 3D printers during a melt-extrusion process. S-TPU consisting of aliphatic hexamethylene 1,6-diisocyanate (HDI), amorphous α,ω-dihydroxy(ethylene-butylene adipate) (PEBA) and 1,4 butandiol (BDO) as a chain extender, was synthesized without the use of a catalyst. The filament (F-TPU) properties were characterized by rheological, mechanical, physico-chemical and in vitro biological properties. The tests showed biocompatibility of the obtained filament as well as revealed no significant effect of the filament formation process on its properties. This study may contribute to expanding the range of medical-grade flexible filaments for standard low-budget FDM printers.

Microporous Polyurethane Thin Layer as a Promising Scaffold for Tissue Engineering.

The literature describes that the most efficient cell penetration takes place at 200⁻500 µm depth of the scaffold. Many different scaffold fabrication techniques were described to reach these guidelines. One such technique is solvent casting particulate leaching (SC/PL). The main advantage of this technique is its simplicity and cost efficiency, while its main disadvantage is the scaffold thickness, which is usually not less than 3000 µm. Thus, the scaffold thickness is usually far from the requirements for functional tissue reconstruction. In this paper, we report a successful fabrication of the microporous polyurethane thin layer (MPTL) of 1 mm thick, which was produced using SC/PL technique combined with phase separation (PS). The obtained MPTL was highly porous (82%), had pore size in the range of 65⁻426 µm and scaffold average pore size was equal to 154 ± 3 µm. Thus, it can be considered a suitable scaffold for tissue engineering purpose, according to the morphology criterion. Polyurethane (PUR) processing into MPTL scaffold caused significant decrease of contact angle from 78 ± 4° to 56 ± 6° and obtained MPTL had suitable hydrophilic characteristic for mammalian cells growth and tissue regeneration. Mechanical properties of MPTL were comparable to the properties of native tissues. As evidenced by biotechnological examination the MPTL were highly biocompatible with no observed apparent toxicity on mouse embryonic NIH 3T3 fibroblast cells. Performed studies indicated that obtained MPTL may be suitable scaffold candidate for soft TE purposes such as blood vessels.

The Influence of Calcium Glycerophosphate (GPCa) Modifier on Physicochemical, Mechanical, and Biological Performance of Polyurethanes Applicable as Biomaterials for Bone Tissue Scaffolds Fabrication.

In this paper we describe the synthesis of poly(ester ether urethane)s (PEEURs) by using selected raw materials to reach a biocompatible polyurethane (PU) for biomedical applications. PEEURs were synthesized by using aliphatic 1,6-hexamethylene diisocyanate (HDI), poly(ethylene glycol) (PEG), α,ω-dihydroxy(ethylene-butylene adipate) (Polios), 1,4-butanediol (BDO) as a chain extender and calcium glycerolphosphate salt (GPCa) as a modifier used to stimulate bone tissue regeneration. The obtained unmodified (PURs) and modified with GPCa (PURs-M) PEEURs were studied by various techniques. It was confirmed that urethane prepolymer reacts with GPCa modifier. Further analysis of the obtained PURs and PURs-M by Fourier transform infrared (FTIR) and Raman spectroscopy revealed the chemical composition typical for PUs by the confirmed presence of urethane bonds. Moreover, the FTIR and Raman spectra indicated that GPCa was incorporated into the main PU chain at least at one-side. The scanning electron microscopy (SEM) analysis of the PURs-M surface was in good agreement with the FTIR and Raman analysis due to the fact that inclusions were observed only at 20% of its surface, which were related to the non-reacted GPCa enclosed in the PUR matrix as filler. Further studies of hydrophilicity, mechanical properties, biocompatibility, short term-interactions, and calcification study lead to the final conclusion that the obtained PURs-M may by suitable candidate material for further scaffold fabrication. Scaffolds were prepared by the solvent casting/particulate leaching technique (SC/PL) combined with thermally-induced phase separation (TIPS). Such porous scaffolds had satisfactory pore sizes (36⁻100 µm) and porosity (77⁻82%) so as to be considered as suitable templates for bone tissue regeneration.

Application of bladder acellular matrix in urinary bladder regeneration: the state of the art and future directions.

Construction of the urinary bladder de novo using tissue engineering technologies is the "holy grail" of reconstructive urology. The search for the ideal biomaterial for urinary bladder reconstruction has been ongoing for decades. One of the most promising biomaterials for this purpose seems to be bladder acellular matrix (BAM). In this review we determine the most important factors, which may affect biological and physical properties of BAM and its regeneration potential in tissue engineered urinary bladder. We also point out the directions in modification of BAM, which include incorporation of exogenous growth factors into the BAM structure. Finally, we discuss the results of the urinary bladder regeneration with cell seeded BAM.