Physicochemical and Mechanical Properties of Non-Isocyanate Polyhydroxyurethanes (NIPHUs) from Epoxidized Soybean Oil: Candidates for Wound Dressing Applications.

Only 0.1% of polyurethanes available on the market are from renewable sources. With increasing concern about climate change, the substitution of monomers derived from petrochemical sources and the application of eco-friendly synthesis processes is crucial for the development of biomaterials. Therefore, polyhydroxyurethanes have been utilized, as their synthesis route allows for the carbonation of vegetable oils with carbon dioxide and the substitution of isocyanates known for their high toxicity, carcinogenicity, and petrochemical origin. In this study, polyhydroxyurethanes were obtained from carbonated soybean oil in combination with two diamines, one that is aliphatic (1,4-butadiamine (putrescine)) and another that is cycloaliphatic (1,3-cyclohexanobis(methylamine)). Four polyhydroxyurethanes were obtained, showing stability in hydrolytic and oxidative media, thermal stability above 200 °C, tensile strength between 0.9 and 1.1 MPa, an elongation at break between 81 and 222%, a water absorption rate up 102%, and contact angles between 63.70 and 101.39. New formulations of bio-based NIPHUs can be developed with the inclusion of a cycloaliphatic diamine (CHM) for the improvement of mechanical properties, which represents a more sustainable process for obtaining NIPHUs with the physicochemical, mechanical, and thermal properties required for the preparation of wound dressings.

Obtention and Study of Polyurethane-Based Active Packaging with Curcumin and/or Chitosan Additives for Fruits and Vegetables-Part I: Analysis of Morphological, Mechanical, Barrier, and Migration Properties.

Several polyurethane-formulated films with curcumin and/or chitosan additives for food packaging have been previously obtained. The study examines the effect of the additives on the film's morphological, mechanical, barrier, and migration properties. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), water contact angle, thermogravimetric and differential thermal analysis (TGA and DTGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), oxygen transmission rate (OTR), water vapor transmission rate (WVTR), and the overall and specific migration tests were conducted. The results show that the presence of chitosan significantly increased the overall migration and mechanical properties, such as the elongation at break, tensile strength, and Young's modulus of most polyurethane formulations, while curcumin had a minor influence on the mechanical performance. Based on the results, formulations with curcumin but without chitosan are suitable for food packaging.

Incorporation of Chitosan in Polyurethanes Based on Modified Castor Oil for Cardiovascular Applications.

The increased demand for vascular grafts for the treatment of cardiovascular diseases has led to the search for novel biomaterials that can achieve the properties of the tissue. According to this, the investigation of polyurethanes has been a promising approach to overcome the present limitations. However, some biological properties remain to be overcome, such as thrombogenicity and hemocompatibility, among others. This paper aims to synthesize polyurethanes based on castor oil and castor oil transesterified with triethanolamine (TEA) and pentaerythritol (PE) and with the incorporation of 1% chitosan. Analysis of the wettability, enzymatic degradation, mechanical properties (tensile strength and elongation at break), and thermal stability was performed. Along with the evaluation of the cytotoxicity against mouse fibroblast (L929) and human dermal fibroblast (HDFa) cells, the hemolysis rate and platelet adhesion were determined. The castor-oil-based polyurethanes with and without 1% chitosan posed hydrophobic surfaces and water absorptions of less than 2% and enzymatic degradation below 0.5%. Also, they were thermally stable until 300 °C, with tensile strength like cardiovascular tissues. The synthesized castor oil/chitosan polyurethanes are non-cytotoxic (cell viabilities above 80%) to L929 and HDFa cells and non-thrombogenic and non-hemolytic (less than 2%); therefore, they are suitable for cardiovascular applications.

Assessment of the Anti-Thrombogenic Activity of Polyurethane Starch Composites.

The increasing morbidity and mortality of patients due to post-surgery complications of coronary artery bypass grafts (CABPG) are related to blood-material interactions. Thus, the characterization of the thrombogenicity of the biomaterial for cardiovascular devices is of particular interest. This research evaluated the anti-thrombogenic activity of polyurethanes-starch composites. We previously synthesized polyurethane matrices that were obtained from polycaprolactone diol (PCL), polyethylene glycol (PEG), pentaerythritol (PE), and isophorone diisocyanate (IPDI). In addition, potato starch (AL-N) and zwitterionic starch (AL-Z) were added as fillers. The anti-thrombogenic property was characterized by the clot formation time, platelet adhesion, protein absorption, TAT complex levels, and hemolysis. Additionally, we evaluated the cell viability of the endothelial and smooth muscle cells. Statically significant differences among the polyurethane matrices (P1, P2, and P3) were found for protein absorption and the blood clotting time without fillers. The polyurethanes composites with AL-Z presented an improvement in the anti-thrombogenic property. On the other hand, the composites with AL-Z reduced the viability of the endothelial cells and did not significantly affect the AoSCM (except for P1, which increased). These results classify these biomaterials as inert; therefore, they can be used for cardiovascular applications.

Influence of Starch on the Structure-Properties Relationship in Polyethylene Glycol/Polycaprolactone Diol Polyurethanes.

Improvements in the antithrombogenicity activity of biomaterials for cardiovascular applications are necessary to meet the demand for vascular grafts in the world. Zwitterionic compounds tend to be used due to their anti-fouling properties, which reduce platelet adhesions and protein absorptions. Therefore, in this research, potato starch (AL-N) and zwitterionic starch (AL-Z) (obtained by Williamson etherification) were included as fillers in polyurethane (PU) matrices from polycaprolactone diol (PCL), polyethylene glycol (PEG), pentaerythritol (PE) and isophorone diisocyanate (IPDI) in order to study their effect in terms of their physicochemical, mechanical and thermal properties. We conducted our evaluation using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), contact angle analysis, swelling behavior, thermogravimetric analysis (TGA), tensile/strain analysis, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDS), dynamic mechanic analysis (DMA), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The results showed that AL-N and AL-Z modified these properties, where AL-N improved tensile strength, and AL-Z increased the hydrophilicity of polyurethanes matrices; additionally, AL-N had interactions with the soft segments, and AL-Z had interactions with the hard segments. Finally, both fillers reduced the degree of crystallinity and did not affect the thermal stability of polyurethanes.

Insights into the Design of Polyurethane Dressings Suitable for the Stages of Skin Wound-Healing: A Systematic Review.

Dressings made with polyurethanes have been found to exhibit good and varied biological properties that make them good candidates for this application. However, as has been seen, the wound-healing process is complex, which includes four different stages. So far, the design and evaluation of polyurethane for wound dressing has focused on achieving good properties (mechanical, physicochemical, and biological), but each of them separates from the others or even directed at only one of the stages of skin wound-healing. Therefore, the aim of this systematic review is to explore the applications of polyurethanes in wound dressings and to determine whether could be designed to cover more than one stage of skin wound-healing. The PRISMA guidelines were followed. The current research in this field does not consider each stage separately, and the design of polyurethane dressings is focused on covering all the stages of wound healing with a single material but is necessary to replace polyurethanes in short periods of time. Additionally, little emphasis is placed on the hemostasis stage and further characterization of polyurethanes is still needed to correlate mechanical and physicochemical properties with biological properties at each stage of the wound-healing. Current research demonstrates an effort to characterize the materials physiochemically and mechanically, but in terms of their biological properties, most of the literature is based on the performance of histological tests of explants morphologically probing the compromised tissues, which give an indication of the potential use of polyurethanes in the generation of wound-healing dressings.

Why Polyurethanes Have Been Used in the Manufacture and Design of Cardiovascular Devices: A Systematic Review.

We conducted a systematic review in accordance with the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) statement to ascertain why polyurethanes (PUs) have been used in the manufacture and design of cardiovascular devices. A complete database search was performed with PubMed, Scopus, and Web of Science as the information sources. The search period ranged from 1 January 2005 to 31 December 2019. We recovered 1552 articles in the first stage. After the duplicate selection and extraction procedures, a total of 21 papers were included in the analysis. We concluded that polyurethanes are being applied in medical devices because they have the capability to tolerate contractile forces that originate during the cardiac cycle without undergoing plastic deformation or failure, and the capability to imitate the behaviors of different tissues. Studies have reported that polyurethanes cause severe problems when applied in blood-contacting devices that are implanted for long periods. However, the chemical compositions and surface characteristics of polyurethanes can be modified to improve their mechanical properties, blood compatibility, and endothelial cell adhesion, and to reduce their protein adhesion. These modifications enable the use of polyurethanes in the manufacture and design of cardiovascular devices.

Influence of Polyol/Crosslinker Blend Composition on Phase Separation and Thermo-Mechanical Properties of Polyurethane Thin Films.

Polyurethanes (PUs) from Polyethylene glycol (PEG) and polycaprolactone diol (PCL) and a crosslinker, Pentaerythritol (PE), were synthetized with isophorone diisocyanate (IPDI). In this study, we investigated the effect of polyol and crosslinker composition on phase separation and thermo-mechanical properties. The properties were studied through dynamic mechanical analysis, X-ray scattering, atomic force microscopy (AFM), and thermogravimetric analysis (TGA). The results showed changes in PUs properties, microphase structure, and separation due to the composition of polyol/crosslinker blend. So, the largest concentration of PE produced multimodal loss factor patterns, indicating segment segregation while PUs with a PEG/PCL = 1 displayed a monomodal loss factor pattern, indicating a homogeneously distributed microphase separation. Additionally, the increase of the PEG concentration enhanced the damping capacity. On the other hand, agglomeration and thread-like structures of hard segments (HS) were observed through AFM. Finally, the thermal behavior of PUs was affected by chemical composition. Lower concentration of PE reduced the crosslinking; hence, the temperature with the maximum degradation rate.

Candidate Polyurethanes Based on Castor Oil (Ricinus communis), with Polycaprolactone Diol and Chitosan Additions, for Use in Biomedical Applications.

Polyurethanes are widely used in the development of medical devices due to their biocompatibility, degradability, non-toxicity and chemical versatility. Polyurethanes were obtained from polyols derived from castor oil, and isophorone diisocyanate, with the incorporation of polycaprolactone-diol (15% w/w) and chitosan (3% w/w). The objective of this research was to evaluate the effect of the type of polyol and the incorporation of polycaprolactone-diol and chitosan on the mechanical and biological properties of the polyurethanes to identify the optimal ones for applications such as wound dressings or tissue engineering. Polyurethanes were characterized by stress-strain, contact angle by sessile drop method, thermogravimetric analysis, differential scanning calorimetry, water uptake and in vitro degradation by enzymatic processes. In vitro biological properties were evaluated by a 24 h cytotoxicity test using the colorimetric assay MTT and the LIVE/DEAD kit with cell line L-929 (mouse embryonic fibroblasts). In vitro evaluation of the possible inflammatory effect of polyurethane-based materials was evaluated by means of the expression of anti-inflammatory and proinflammatory cytokines expressed in a cellular model such as THP-1 cells by means of the MILLIPLEX® MAP kit. The modification of polyols derived from castor oil increases the mechanical properties of interest for a wide range of applications. The polyurethanes evaluated did not generate a cytotoxic effect on the evaluated cell line. The assessed polyurethanes are suggested as possible candidate biomaterials for wound dressings due to their improved mechanical properties and biocompatibility.

Surface Response Methodology-Based Mixture Design to Study the Influence of Polyol Blend Composition on Polyurethanes' Properties.

Polyurethanes are materials with a strong structure-property relationship. The goal of this research was to study the effect of a polyol blend composition of polyurethanes on its properties using a mixture design and setting mathematic models for each property. Water absorption, hydrolytic degradation, contact angle, tensile strength hardness and modulus were studied. Additionally, thermal stability was studied by thermogravimetric analysis. Area under the curve was used to evaluate the effect of polyol blend composition on thermal stability and kinetics of water absorption and hydrolytic degradation. Least squares were used to calculate the regression coefficients. Models for the properties were significant, and lack of fit was not (p < 0.05). Fit statistics suggest both good fitting and prediction. Water absorption, hydrolytic degradation and contact angle were mediated by the hydrophilic nature of the polyols. Tensile strength, modulus and hardness could be regulated by the PE content and the characteristics of polyols. Regression of DTG curves from thermal analysis showed improvement of thermal stability with the increase of PCL and PE. An ANOVA test of the model terms demonstrated that three component influences on bulk properties like water absorption, hydrolytic degradation, hardness, tensile strength and modulus. The PEG*PCL interaction influences on the contact angle, which is a surface property. Mixture design application allowed for an understanding of the structure-property relationship through mathematic models.

Effect of the incorporation of chitosan on the physico-chemical, mechanical properties and biological activity on a mixture of polycaprolactone and polyurethanes obtained from castor oil.

In the present study, polyurethane materials were obtained from castor oil, polycaprolactone and isophorone diisocyanate by incorporating different concentrations of chitosan (0.5, 1.0 and 2.0% w/w) as an additive to improve the mechanical properties and the biological activity of polyurethanes. The polyurethanes were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, stress/strain fracture tests and swelling analysis, and the hydrophilic character of the surface was determined by contact angle trials. The objectives of the study were to evaluate the effect of the incorporation of chitosan on the changes of the physico-chemical and mechanical properties and the in vitro biological activity of the polyurethanes. It was found that the incorporation of chitosan enhances the ultimate tensile strength of the polyurethanes and does not affect the strain at fracture in polyurethanes with 5% w/w of polycaprolactone and concentrations of chitosan ranging from 0 to 2% w/w. In addition, PCL5-Q-PU formulations and their degradation products did not affect cell viability of L929 mouse fibroblast and 3T3, respectively. Polyurethane formulations showed antibacterial activities against Staphylococcus aureus and Escherichia coli bacteria. The results of this study have highlighted the potential biomedical application of this polyurethanes related to soft and cardiovascular tissues.

Microbial degradation, cytotoxicity and antibacterial activity of polyurethanes based on modified castor oil and polycaprolactone.

The objective of this study was to assess the effects of type of polyol and concentration of polycaprolactone (PCL) in polyurethanes (PUs) on microbial degradability, cytotoxicity, biological properties and antibacterial activity to establish whether these materials may have biomedical applications. Chemically modified and unmodified castor oil, PCL and isophorone diisocyanate in a 1:1 ratio of NCO/OH were used. PUs were characterized by stress/strain fracture tests and hardness (ASTM D 676-59). Hydrophilic character was determined by contact angle trials and morphology was evaluated by scanning electron microscopy. Degradability with Escherichia coli and Pseudomonas aeruginosa was evaluated by measuring variations in the weight of the polymers. Cytotoxicity was evaluated using the ISO 10993-5 (MTT) method with mouse embryonic fibroblasts L-929 (ATCC® CCL-1) in direct contact with the PUs and with NIH/3T3 cells (ATCC® CRL-1658) in indirect contact with the PUs. Antimicrobial activity against E. coli and P. aeruginosa was determined. PUs derived from castor oil modified (P0 and P1) have higher mechanical properties than PUs obtained from castor oil unmodified (CO). The viability of L-929 mouse fibroblasts in contact with polymers was greater than 70%. An assessment of NIH/3T3 cells in indirect contact with PUs revealed no-toxic degradation products. Finally, the antibacterial effect of the PUs decreased by 77% for E. coli and 56% for P. aeruginosa after 24 h. These results indicate that PUs synthesized with PCL have biocidal activity against Gram-negative bacteria and do not induce cytotoxic responses, indicating the potential use of these materials in the biomedical field.