[Research Progress in Organocatalysts Used in the Synthesis of Medical Polyurethanes and Their Biotoxicity]. / åŒ»ç”¨èšæ°¨é ¯åˆæˆæ‰€ç”¨æœ‰æœºå‚¬åŒ–å‰‚åŠå ¶ç”Ÿç‰©æ¯’æ€§ç ”ç©¶è¿›å±•.

Medical polyurethanes have emerged as a leading choice for biomedical applications owing to their exceptional biocompatibility and good physical and mechanical properties. Catalysts play a crucial role as additives in the synthesis of medical polyurethanes, enhancing synthesis efficiency and material properties. However, the catalysts used may affect the biocompatibility of polyurethanes and pose potential harm to human health. This review encapsulates the latest findings regarding the catalysts employed in the synthesis of medical polyurethane materials and their biotoxicity. Initially, we reviewed the prevalent types of catalysts used in the synthesis of medical polyurethane materials and described their distinctive characteristics. Subsequently, our focus shifted to exploring the potential biotoxicity associated with these catalysts. Finally, we provided a forward-looking perspective and recommendations for the future trajectory of catalyst selection in the synthesis of medical polyurethane materials. By acquiring a more profound understanding of the properties and biotoxicity of catalysts used in the synthesis of medical polyurethane materials, and by uncovering existing issues and challenges, we can better guide the design of medical polyurethane materials. This, in turn, enables us to chart the course for future development and ultimately enhance the biocompatibility and safety profiles of medical polyurethane materials. Such advancements will promote the continued development and application of medical polyurethane materials in clinical settings.

Improved in vivo stability of silicon-containing polyurethane by fluorocarbon side chain modulation of the surface structure.

As a class of widely used biomedical materials, polyurethanes suffer from their insufficient stability in vivo. Although the commercialized silicone-polyetherurethanes (SiPEUs) have demonstrated excellent biostability compared with polyetherurethanes (PEUs) for long-term implantation, the usage of polydimethylsiloxane (PDMS) inevitably decreased the mechanical properties and unexpected breaches were observed. In this study, we introduced a fluorinated diol (FDO) into SiPEU to modulate the molecular interactions and micro-separated morphology. The fluorinated silicon-containing polyurethane (FSiPEU) was achieved with desirable silicone- and fluorine-enriched surfaces and mechanical properties at a low silicon content. As evidenced by in vitro culture of macrophages and in vivo hematoxylin-eosin (H&E) staining, FSiPEU demonstrated a minimized inflammatory response. After implantation in mice for 6 months, the material was devoid of significant surface degradation and had the least chain cleavage of soft segments. The results indicate that FSiPEU could be promising candidates for long-term implantation considering the combination of biostability, biocompatibility and mechanical performances.

Bioactive 3D porous cobalt-doped alginate/waterborne polyurethane scaffolds with a coral reef-like rough surface for nerve tissue engineering application.

Nerve injuries in the central or peripheral nervous system threaten human health and hinder social development, and effectively repairing or regenerating nerve tissues remains a huge challenge. The rise of tissue engineering strategies has brought new light for this. Similar to the extracellular matrix, biomimetic three-dimensional (3D) porous scaffolds can provide biophysical and biochemical cues to guide cell behaviors and support tissue growth. Here, we prepared a hybrid cobalt-doped alginate/waterborne polyurethane 3D porous scaffold with nano-topology of a "coral reef-like" rough surface via two-step freeze-drying. The experimental results demonstrated that the "coral reef-like" rugged surface topology and bioactive cobalt dopant synergistically promote the neurite outgrowth and up-regulate the synaptophysin expression of neuron-like cells PC12 on the scaffold. Furthermore, the scaffold notably relieved the inflammatory response of microglial cells BV2 with the transformation from pro-inflammatory (M1) to anti-inflammatory (M2) phenotype. We believe that this 3D porous scaffold offers bright design inspiration for neural tissue engineering scaffolds and holds potential applications in nerve repair.

Mechanically robust enzymatically degradable shape memory polyurethane urea with a rapid recovery response induced by NIR.

Biodegradable shape memory polymers have great potential for use in minimally invasive surgical procedures. Herein, a series of shape memory polyurethanes (SMPUs) containing a chymotrypsin-inspired chain extender with adjustable mechanical properties and excellent shape memory effect (SME) was prepared successfully. The chemical structure, mechanical properties, SME and in vitro degradation of the PUs were systematically characterized by proton nuclear magnetic resonance spectroscopy, tensile testing, dynamic mechanical analysis under controlled force mode, and scanning electronic microscopy. By increasing the molecular weight of poly(ε-caprolactone) (PCL) and hard segment content, a PCL4000-based SMPU with a modulus value of 115 MPa was obtained, which is three times that of a PCL2000-based sample. Further, the modulus of the PCL4000-based SMPU was increased by 50% while that of the PCL2000-based SMPU was significantly reduced when temperature increased from 23 °C to 37 °C. In addition, the PCL4000-based SMPU exhibited excellent SME with the shape fixity ratio and recovery ratio almost reaching 100%. Gold nanorods were further incorporated into the PU matrix, endowing the materials with a fast near-infrared (NIR) response in 23 s for shape recovery (NIR wavelength of 808 nm, 1.5 W). Combined with enzymatic degradability, these PU/gold-nanorod composites exhibit great potential to be used in biodegradable shape memory expanding stents.

Aligned 3D porous polyurethane scaffolds for biological anisotropic tissue regeneration.

A green fabrication process (organic solvent-free) of artificial scaffolds is required in tissue engineering field. In this work, a series of aligned three-dimensional (3D) scaffolds are made from biodegradable waterborne polyurethane (PU) emulsion via directional freeze-drying method to ensure no organic byproducts. After optimizing the concentration of polymer in the emulsion and investigating different freezing temperatures, an aligned PUs scaffold (PU14) generated from 14 wt% polymer content and processed at -196°C was selected based on the desired oriented porous structure (pore size of 32.5 ± 9.3 µm, porosity of 92%) and balanced mechanical properties both in the horizontal direction (strength of 41.3 kPa, modulus of 72.3 kPa) and in the vertical direction (strength of 45.5 kPa, modulus of 139.3 kPa). The response of L929 cells and the regeneration of muscle tissue demonstrated that such pure material-based aligned 3D scaffold can facilitate the development of orientated cells and anisotropic tissue regeneration both in vitro and in vivo. Thus, these pure material-based scaffolds with ordered architecture have great potentials in tissue engineering for biological anisotropic tissue regeneration, such as muscle, nerve, spinal cord and so on.

A waterborne polyurethane 3D scaffold containing PLGA with a controllable degradation rate and an anti-inflammatory effect for potential applications in neural tissue repair.

Currently, implanting tissue engineering scaffolds is one of the treatment methods for the regeneration of damaged tissues. The matching of the degradation rate of the scaffolds with the regeneration rate of the damaged zone is a big challenge in tissue engineering. Here, we have synthesized a series of biodegradable waterborne polyurethane emulsions and fabricated three-dimensional (3D) connected porous polyurethane scaffolds by freeze-drying. The degradation rate of the scaffolds was controlled by adjusting the relative ratio of poly-ε-caprolactone (PCL) and poly(lactic-co-glycolic acid) (PLGA) in the soft segment. The degradation rate of the scaffolds gradually accelerated with the increase of the relative proportion of PLGA. By co-culture with BV2 microglia, the scaffolds promoted the differentiation of BV2 into an anti-inflammatory M2 phenotype rather than a pro-inflammatory M1 phenotype as the proportion of PLGA increases. When the BV2 cells were stimulated with lipopolysaccharide (LPS), the scaffolds with a higher PLGA ratio showed a much stronger anti-inflammatory effect. Then, we demonstrated that the scaffolds could promote the PC12 neurons to differentiate into neurites. Therefore, we believe that the polyurethane scaffolds have a promising potential application in neural tissue repair.