Microstructure Evolution of Reactive Polyurethane Films During In Situ Polyaddition and Film-Formation Processes.

Due to the advantages of low energy consumption, no air and water pollutions, the reactive polyurethane films (RPUFs) are replacing the solvated and waterborne PUFs nowadays, which significantly promotes the green and low-carbon production of PU films. However, the microstructure evolution and in situ film-formation mechanism of RPUFs in solvent-free media are still unclear. Herein, according to time-temperature equivalence principle, the in situ polyaddition and film-formation processes of RPUFs generated by the typical polyaddition of diisocyanate terminated prepolymer (component B) and polyether glycol (component A) are thoroughly investigated at 25 °C. According to the temporal change of viscosity, the RPUFs gradually transfer from liquid to gel and finally to solid state. Further characterizing the molecular weight, hydrogen bonds, crystallinity, gel content, and phase images, the polyaddition and film-formation processes can be divided into three stages as 1) chain extension and microcrystallization; 2) gelation and demicrocrystallization; 3) microphase separation and film-formation. This work promotes the understanding of the microstructure evolution and film-formation mechanism of RPUFs, which can be used as the theoretical guidance for the controllable preparation of high-performance products based on RPUFs.

Development of Thermoplastic Polyurethane Films for the Replacement of Corneal Endothelial Function of Transparency Maintenance.

Endothelial keratoplasty is the main surgical procedure for treating corneal endothelial dysfunction (CED), which is limited by the global shortage of donor corneas. Herein, we developed and evaluated the modified thermoplastic polyurethane (M-TPU) films with gelatin-glycidyl methacrylate to replace the corneal endothelial function and maintain corneal transparency. The films displayed comparable light transmission characteristics with normal corneas and clinically favorable mechanical properties for surgical manipulation. After surface modification, the hydrophilicity and biocompatibility of M-TPU films were significantly improved. In the rabbit CED model, the M-TPU implants exhibited firm adhesion to the exposed stromal surface. The rabbit corneal transparency and thickness could be restored completely within 1 week of M-TPU film implantation. There was no significant inflammatory reaction and immune rejection during the follow-up of 1 month. Proteomic analysis suggested that the complement inhibition, the increase of mineral absorption, and the decrease of P53 apoptosis signaling pathway and lysine degradation might be beneficial in maintaining the corneal transparency. Overall, our study demonstrated the potential of M-TPU films as artificial implants for the replacement of corneal endothelial function to restore corneal thickness and transparency.

Encapsulation of AgNPs in a Lignin Isocyanate Film: Characterization and Antimicrobial Properties.

Lignin isolated from agricultural residues is a promising alternative for petroleum-based polymers as feedstocks in development of antimicrobial materials. A polymer blend based on silver nanoparticles and lignin-toluene diisocyanate film (AgNPs-Lg-TDIs) was generated from organosolv lignin and silver nanoparticles (AgNPs). Lignin was isolated from Parthenium hysterophorus using acidified methanol and used to synthesize lignin capped silver nanoparticles. Lignin-toluene diisocyanate film (Lg-TDI) was prepared by treating lignin (Lg) with toluene diisocyanate (TDI) followed by solvent casting to form films. Functional groups present and thermal properties of the films were evaluated using Fourier-transform infrared spectrophotometry (FT-IR), thermal gravimetry (TGA), and differential scanning calorimetry (DSC). Scanning electron microscopy (SEM), UV-visible spectrophotometry (UV-Vis), and Powder X-ray diffractometry (XRD) were used to assess the morphology, optical properties, and crystallinity of the films. Embedding AgNPs in the Lg-TDI films increased the thermal stability and the residual ash during thermal analysis, and the presence of powder diffraction peaks at 2θ = 20, 38, 44, 55, and 58° in the films correspond to lignin and silver crystal planes (111). SEM micrographs of the films revealed the presence of AgNPs in the TDI matrix with variable sizes of between 50 to 250 nm. The doped films had a UV radiation cut-off at 400 nm as compared to that of undoped films, but they did not exhibit significant antimicrobial activity against selected microorganisms.

Fabrication of litchi-like lignin/zinc oxide composites with enhanced antibacterial activity and their application in polyurethane films.

Lignin has been demonstrated to be green and effective for the modification of ZnO-based materials. In this work, quaternized lignin/zinc oxide nanostructured hybrid composites (QLS/ZnO NCs) were synthesized with good dispersion and uniform particle size via a facile hydrothermal method. Sodium lignosulfonate (LS) was modified by quaternization to endow the positive charges, which effectively captured bacteria due to the electrostatic interactions. Interestingly, QLS/ZnO NCs show a litchi-like morphology consisting of nanorods with diameters of 5-10 nm, which further resulted in damage to the bacterial cell membrane. Owing to the surface charge and rough surface topology for bacterial capture, QLS/ZnO NCs exhibited greatly enhanced antibacterial activity compared with bare ZnO. After being treated with QLS/ZnO NCs for 90 min, the sterilization rates of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) reached 97.54% and 99.55%, respectively. Due to the reactive oxygen species (ROS) produced by ZnO under light irradiation, the antibacterial activity of QLS/ZnO NCs could be further enhanced. In addition, the minimal inhibition concentrations (MICs) of QLS/ZnO NCs towards E. coli and S. aureus were both 100 µg/mL, and the minimum bactericidal concentrations (MBCs) were 100 µg/mL and 200 µg/mL, respectively. Moreover, with the incorporation of QLS/ZnO NCs into polyurethane films, the composite films showed excellent antibacterial activity, strong tensile strength and enhanced ultraviolet light blocking performance.

Mitigation of monocyte driven thrombosis on cobalt chrome surfaces in contact with whole blood by thin film polar/hydrophobic/ionic polyurethane coatings.

Monocytes are active at the crossroads between inflammation and coagulation processes since they can secrete pro-inflammatory cytokines and express tissue factor (TF), a major initiator of coagulation. Cobalt-chrome (CoCr), a metal alloy, used as a biomaterial for vascular stents, has been shown to be potentially pro-thrombotic and pro-inflammatory. Research work with a polymer from a family of degradable-polar hydrophobic ionic polyurethanes (D-PHI), called HHHI, has been shown to exhibit anti-inflammatory responses from human monocytes. We have generated multifunctional polyurethane thin films (MPTF) based on the HHHI chemistry, as a thin coating for CoCr and have evaluated the reactivity of blood with MPTF-coated CoCr. The results showed that the coating of CoCr with MPTF derived from HHHI prevents thrombin generation, reduces coagulation activation, and suppresses fibrin formation in whole blood. Activation of monocytes was also suppressed at the surface of MPTF-coated CoCr and specifically the decrease in thrombin generation was accompanied by a significant decrease in TF and pro-inflammatory cytokine levels. Mass spectroscopy of the adsorbed proteins showed lower levels of fibrinogen, fibronectin and complement C3, C4, and C8 when compared to CoCr. We can conclude that MPTFs reduce the pro-thrombotic and pro-inflammatory phenotype of monocytes and macrophages on CoCr, and prevent clotting in whole blood.

Study of chemical, physico-mechanical and biological properties of 4,4'-methylenebis(cyclohexyl isocyanate)-based polyurethane films.

Polyurethane films were obtained in the solvent-free cycloaliphatic polyaddition process of 4,4'-methylenebis(cyclohexyl isocyanate), poly(ε-caprolactone) diol or poly(oxytetramethylene) glycol and 1,4-butanediol. Chemical structures of the polymers were confirmed by FTIR, NMR and GPC methods. Their surface, thermal and mechanical properties have been evaluated. Results of biological studies with polyurethane films as potential biomaterials for medical applications revealed their mild cytotoxicity against normal human fibroblasts (BJ) and immortalized keratinocytes (HaCaT). STATEMENT OF SIGNIFICANCE: The research is relevant for the potential uses of polyurethane films made from commercial raw materials as general medical supplies.

Composites prepared from the waterborne polyurethane cationomers-modified graphene. Part I. Synthesis, structure, and physicochemical properties.

In the reaction of 4,4'-methylenebis(phenyl isocyanate), polycaprolactone diol, and N-methyldiethanolamine, they were synthesized aqueous dispersions of polyurethane cationomers, from which films were prepared after adding 0-2 wt% graphene. In order to obtain nanocomposites, graphene was previously noncovalent functionalized in tetrahydrofurane in the field of ultrasound. The chemical structure and the morphology of obtained nanocomposites were analyzed by IR spectroscopy, atomic force microscopy (AFM), and differential scanning calorimetry (DSC) microcalorimetry methods. It was found that the presence of graphene results in increased thermal and mechanical strength of received polymer films and contributes to the increase in hydrophobicity of generally hydrophilic coatings prepared from waterborne polyurethane cationomers. Based on received results, possible interactions between graphene and phase structure of polyurethane cationomers were discussed. Relating to the so far described applications of graphene for the modification of polyurethanes, the novelty of this work is the concept of incorporation of graphene particles to polyurethane cationomer chains exclusively through a simple noncovalent functionalization and to investigate the effect of graphene on the properties obtained in this way of thin polyurethane film.