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Biodegradable segmented polyurethanes were prepared with poly(caprolactone) diol as a soft segment, 4,4′-methylene bis(cyclohexyl isocyanate) (HMDI) and either butanediol or dithioerythritol as chain extenders. Platelet adhesion was similar in all segmented polyurethanes studied and not different from Tecoflex® although an early stage of activation was observed on biodegradable segmented polyurethane prepared with dithioerythritol. Relative viability was higher than 80% on human umbilical vein endothelial cells in contact with biodegradable segmented polyurethane extracts after 1, 2 and 7 days. Furthermore, both biodegradable segmented polyurethane materials supported human umbilical vein endothelial cell adhesion, spreading, and viability similar to Tecoflex® medical-grade polyurethane. These biodegradable segmented polyurethanes represent promising materials for cardiovascular applications. [ABSTRACT FROM AUTHOR]

Diabetic foot ulcers are a common complication of diabetes mellitus and can lead to severe infections and delayed wound healing. The development of effective wound dressings is crucial to promoting faster healing and preventing infections. This investigation aims to fabricate and characterize electrospun meshes composed of poly(ε-caprolactone) and collagen, extracted from tilapia skin. Additionally, tetracycline and chloramphenicol were incorporated into the dressings to explore their potential to combat wound infections. A comprehensive characterization was carried out, covering the physical structure, chemical composition, and potential application-related properties of the materials by the combination of scanning electron microscopy, Fourier transform infrared (FTIR), mechanical analysis, cell viability, live/dead staining, and microbiological analysis. Changes in mechanical properties were observed, related to the morphology of the membranes; the presence of the active molecules is evidenced by FTIR analysis; cell viability above control was observed for all the prepared membranes, and they were active in antimicrobial tests, suggesting that the developed materials have the potential to be further explored as wound dressings or scaffolds for diabetic foot ulcers., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Background: Polymeric electrospun mats have been used as scaffolds in tissue engineering for the development of novel materials due to its characteristics. The usage of synthetic materials has gone in decline due to environmental problems associated with their synthesis and waste disposal. Biomaterials such as biopolymers have been used recently due to good compatibility on biological applications and sustainability., Objective: The purpose of this work is to obtain novel materials based on synthetic and natural polymers for applications on tissue engineering., Methods: Aloe vera mucilage was obtained, chemically characterized, and used as an active compound contained in electrospun mats. Polymeric scaffolds were obtained in single, coaxial and tri-layer structures, characterized and evaluated in cell culture., Results: Mucilage loaded electrospun fibers showed good compatibility due to formation of hydrogen bonds between polymers and biomolecules from its structure, evidenced by FTIR spectra and thermal properties. Cell viability test showed that most of the obtained mats result on viability higher than 75%, resulting in nontoxic materials, ready to be used on scaffolding applications., Conclusion: Mucilage containing fibers resulted on materials with potential use on scaffolding applications due to their mechanical performance and cell viability results.

The preparation method of hydrogels has a significant effect on their structural and physicochemical properties. In this report, physically and chemically cross-linked poly(vinyl alcohol) (PVA) networks containing humic acid (HA) were alternatively prepared by autoclaving (AC) and through glutaraldehyde (GA) addition, respectively, for agricultural purposes. PVA/HA hydrogels were comparatively characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, mechanical assays, scanning electron microscopy, swelling kinetics measurements, and water retention tests in soil. AC hydrogels showed a more homogeneous porous microstructure, higher swelling levels, and a better capacity to preserve the humidity of soil than those obtained by adding GA. Both PVA/HA hydrogels exhibited no phytotoxicity on cultivation trials of Sorghum sp. , but the plant growth was promoted with the GA-cross-linked network as compared to the effect of the AC sample. The release behavior of urea was modified according to the preparation method of the PVA/HA hydrogels. After 3 days of sustained urea release, 91% of the fertilizer was delivered from the AC hydrogel, whereas a lower amount of 56% was released for the GA-cross-linked hydrogel. Beyond the advantages of applying PVA/HA hydrogels in the agricultural field, an appropriate method of preparing these materials endows them with specific properties according to the requirements of the target crop., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Segmented polyurethanes based on polycaprolactone, 4,4 (metylene-bis-cyclohexyl) isocyanate, and l-lysine were synthesized, manufactured as small vascular grafts and characterized according to ISO 7198 standard for cardiovascular implants-tubular vascular prosthesis. In terms of mechanical properties, the newly synthesized polyurethane films exhibited lower secant modulus than Tecoflex™ SG 80A, a well-known medical grade polyurethane. Similarly, when tested as grafts, the l-lysine-based polyurethane exhibited lower longitudinal failure load (11.5 N vs. 116 N), lower circumferential failure load per unit length (5.67 N/mm vs. 14.0 N/mm) and lower suture forces for both nylon (13.3 N vs. 24.0 N) and silk (14.0 N vs. 19.3 N) when compared to Tecoflex™ SG 80A grafts. l-Lysine-based graft exhibited a burst strength of 3620 mmHg (482.6 kPa) and a compliance of 0.16%/mmHg. The cell adhesion was demonstrated with NIH/3T3 fibroblasts where cell adhesion was observed on both films and grafts, while cell alignment was observed only on the grafts. The mechanical properties of this polyurethane and the possibility of strain-induced PCL crystals as the switching phase for shape memory materials, allowed a strain recovery ratio and a strain fixity ratio with values higher than 95% and 90%, respectively, with a repeatability of the shape-memory properties up to 4 thermo-mechanical cycles. Overall, the properties of lysine-based polyurethanes are suitable for large diameter vascular grafts where cell alignment can be controlled by their shape memory potential., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Segmented polyurethanes were prepared with polycaprolactone diol as soft segment and various amounts of 4,4´-Methylenebis(cyclohexyl isocyanate) and atorvastatin, a statin used for lowering cholesterol, in order to obtain SPU with different content of rigid segments. Polyurethanes with 35% or 50% of rigid segment content were physicochemically characterized and their biocompatibility assessed with L929 fibroblasts. High concentrations of atorvastatin were incorporated by increasing the content of rigid segments as shown by FTIR, Raman, NMR, XPS and EDX. Thermal and mechanical characterization showed that polyurethanes containing atorvastatin and 35% of rigid segments were low modulus (13 MPa) semicrystalline polymers as they exhibited a glass transition temperature (T g ) at -38 °C, melting temperature (T m ) at 46 °C and crystallinity close to 35.9% as determined by DSC. In agreement with this, X-ray diffraction showed reflections at 21.3° and 23.6° for PCL without reflections for atorvastatin suggesting its presence in amorphous form with higher potential bioavailability. Low content of rigid segments led to highly degradable polymer in acidic, alkaline and oxidative media with an acceptable fibroblast cytotoxicity up to 7 days possibly due to low atorvastatin content.

The development of elastomeric, bioresorbable and biocompatible segmented polyurethanes (SPUs) for use in tissue-engineering applications has attracted considerable interest because of the existing need of mechanically tunable scaffolds for regeneration of different tissues, but the incorporation of osteoinductive molecules into SPUs has been limited. In this study, SPUs were synthesized from poly (ε-caprolactone)diol, 4,4'-methylene bis(cyclohexyl isocyanate) using biologically active compounds such as ascorbic acid, L-glutamine, β-glycerol phosphate, and dexamethasone as chain extenders. Fourier transform infrared spectroscopy (FTIR) revealed the formation of both urethanes and urea linkages while differential scanning calorimetry, dynamic mechanical analysis, X-ray diffraction and mechanical testing showed that these polyurethanes were semi-crystalline polymers exhibiting high deformations. Cytocompatibility studies showed that only SPUs containing β-glycerol phosphate supported human mesenchymal stem cell adhesion, growth, and osteogenic differentiation, rendering them potentially suitable for bone tissue regeneration, whereas other SPUs failed to support either cell growth or osteogenic differentiation, or both. This study demonstrates that modification of SPUs with osteogenic compounds can lead to new cytocompatible polymers for regenerative medicine applications.

The development of elastomeric, bioresorbable, and biocompatible segmented polyurethanes (SPUs) for use in tissue-engineering applications has attracted considerable interest in recent years because of the existing need for mechanically tunable scaffolds for regeneration of different tissues. In this study segmented polyurethanes were synthesized from poly(ε-caprolactone)diol, 4,4'-methylene bis(cyclohexyl isocyanate) (HMDI) using osteogenic compounds such as ascorbic acid (AA) and l-glutamine (GL) as chain extenders, which are known to play a role in osteoblast proliferation and collagen synthesis. Fourier transform infrared spectroscopy (FTIR) revealed the formation of urethane linkages at 3373, 1729, and 1522 cm -1 (N-H stretching, C[double bond, length as m-dash]O stretching and N-H bending + C-N stretching vibrations, respectively) while urea formation was confirmed by the appearance of a peak at 1632 cm -1 . Differential scanning calorimetry, dynamic mechanical analysis, X-ray diffraction and mechanical testing of the polyurethanes showed that these polyurethanes were semi-crystalline polymers (T g = -25 °C; T m = 51.4-53.8 °C; 2θ = 21.3° and 23.4°) exhibiting elastomeric behavior (ε > 1000%) only for those prepared by HA incorporation during prepolymer formation. Dense and porous composite matrices of the segmented polyurethanes were prepared by the addition of hydroxyapatite (HA) via either mechanical mixing or in situ polymerization and supercritical fluid processing, respectively. The addition of HA by physical mixing decreased the crystallinity (from 38% to 31%) of the composites prepared with ascorbic acid as the chain extender. Both T g of the composites and the strain were also lowered to -38 or 36 °C and 27-39% for ascorbic acid and glutamine containing polyurethanes respectively. Composites prepared with ascorbic acid as the chain extender yielded higher Young's modulus and tensile strength than composites prepared with glutamine when HA was incorporated during prepolymer formation. Composites obtained by incorporation of HA by physical mixing revealed a poor dispersion in comparison to composites obtained via HA inclusion during prepolymer formation. In contrast, good dispersion of HA and porosity were achieved at 60 °C, 400 bar and holding times between 0.5 h and 2 h with a downtime between 15 min and 60 min in the CO 2 reactor. Biocompatibility studies showed that SPUs containing ascorbic acid allowed the increase of alveolar osteoblast proliferation; hence, they are potentially suitable for bone tissue regeneration.

Polyurethanes are very often used in the cardiovascular field due to their tunable physicochemical properties and acceptable hemocompatibility although they suffer from poor endothelialization. With this in mind, we proposed the synthesis of a family of degradable segmented poly(urea)urethanes (SPUUs) using amino acids (L-arginine, glycine and L-aspartic acid) as chain extenders. These polymers degraded slowly in PBS (pH 7.4) after 24 weeks via a gradual decrease in molecular weight. In contrast, accelerated degradation showed higher mass loss under acidic, alkaline and oxidative media. MTT tests on polyurethanes with L-arginine as chain extenders showed no adverse effect on the metabolism of human umbilical vein endothelial cells (HUVECs) indicating the leachables did not provoke any toxic responses. In addition, SPUUs containing L-arginine promoted higher levels of HUVECs adhesion, spreading and viability after 7 days compared to the commonly used Tecoflex(®) polyurethane. The biodegradability and HUVEC proliferation on L-arginine-based SPUUs suggests that they can be used in the design of vascular grafts for tissue engineering.

Novel biodegradable segmented polyurethanes (SPUs) were synthesized with polycaprolactone diol, 4,4'-methylen bis (cyclohexyl isocyanate) (HMDI), and either L-glutathione or its constituent amino acids (L-glutamic acid, L-cysteine and glycine) as chain extenders. Fourier transform infrared spectroscopy analysis revealed the feasibility of obtaining polyurethanes through the presence of NH (Amide II), C-N, C-O, and C=O bands and the absence of NCO band. Differential scanning calorimetry and X-ray diffraction revealed that a semicrystalline polymer (T m = 42-52 °C; 2θ = 21.3° and 23°) was obtained in all cases, while dynamic mechanical analysis (DMA) revealed an amorphous phase (T g = -30 to -36 (o)C). These properties, in addition to their high molecular weight, led to high moduli and higher extensibilities when glycine and glutamic acid were used as chain extenders. Clotting times (Lee-White test) and activated partial thromboplastin time determined on these polyurethanes were longer than with glass. In addition, all synthesized SPU exhibited platelet activation indexes below the collagen type I positive control. Human umbilical vein endothelial cells viability was higher in SPUs containing either glycine or cysteine. The obtained results indicate that SPUs that use cysteine as chain extender are promising candidates for cardiovascular applications.

Biodegradable segmented polyurethanes (BSPUs) were prepared with poly(caprolactone) as a soft segment, 4,4'-methylene bis (cyclohexyl isocyanate) and either butanediol (BSPU1) or dithioerythritol (BSPU2) as a chain extender. BSPU samples were characterized in terms of their physicochemical properties and their hemocompatibility. Polymers were then degraded in acidic (HCl 2N), alkaline (NaOH 5M) and oxidative (H(2)O(2) 30wt.%) media and characterized by their mass loss, Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Undegraded BSPU1 and BSPU2 exhibited different properties, such as the glass transition temperature T(g) of the soft segment (-25 vs. 4 degrees C), mechanical properties (600% vs. 900% strain to break) and blood coagulating properties (clotting time=11.46 vs. 8.13min). After acidic and alkaline degradation, the disappearance of the 1728cm(-1) band of polycaprolactone (PCL) on both types of BSPU was detected by FTIR. However, the oxidative environment did not affect the soft segment severely as the presence of PCL crystalline domains were observed both by DSC (melting temperature T(m)=52.8 degrees C) and XRD (2theta=21.3 degrees and 23.7 degrees ). By TGA three decomposition temperatures were recorded for both BSPU samples, but the higher decomposition temperature was enhanced after acidic and alkaline degradation. The formation of the porous structure on BSPU1 was observed by SEM, while a granular surface was observed on BSPU2 after alkaline degradation., (Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)