Poly Ester Urethane Research Articles

Assessing Aquatic Baseline Toxicity of Plastic-Associated Chemicals: Development and Validation of the Target Plastic Model.

We developed a Target Plastic Model (TPM) to estimate the critical plastic burden of organic toxicants in five types of plastics, namely, polydimethylsiloxane (PDMS), polyoxymethylene (POM), polyacrylate (PA), low-density polyethylene (LDPE), and polyurethane ester (PU), following the Target Lipid Model (TLM) framework. By substituting the lipid-water partition coefficient in the TLM with plastic-water partition coefficients to create TPM, we demonstrated that the biomimetic nature of these plastic phases allows for the calculation of critical plastic burdens of toxicants, similar to the notion of critical lipid burdens in TLM. Following this approach, the critical plastic burdens of baseline (n = 115), less-inert (n = 73), and reactive (n = 75) toxicants ranged from 0.17 to 51.33, 0.04 to 26.62, and 1.00 × 10-6 to 6.78 × 10-4 mmol/kg of plastic, respectively. Our study showed that PDMS, PA, POM, PE, and PU are similar to biomembranes in mimicking the passive exchange of chemicals with the water phase. Using the TPM, median lethal concentration (LC50) values for fish exposed to baseline toxicants were predicted, and the results agreed with experimental values, with RMSE ranging from 0.311 to 0.538 log unit. Similarly, for the same data set of baseline toxicants, other widely used models, including the TLM (RMSE: 0.32-0.34), ECOSAR (RMSE: 0.35), and the Abraham Solvation Model (ASM; RMSE: 0.31), demonstrated comparable agreement between experimental and predicted values. For less inert chemicals, predictions were within a factor of 5 of experimental values. Comparatively, ASM and ECOSAR showed predictions within a factor of 2 and 3, respectively. The TLM based on phospholipid had predictions within a factor of 3 and octanol within a factor of 4, indicating that the TPM's performance for less inert chemicals is comparable to these established models. Unlike these methods, the TPM requires only the knowledge of plastic bound concentration for a given plastic phase to calculate baseline toxic units, bypassing the need for extensive LC50 and plastic-water partition coefficient data, which are often limited for emerging chemicals. Taken together, the TPM can provide valuable insights into the toxicities of chemicals associated with environmental plastic phases, assisting in selecting the best polymeric phase for passive sampling and designing better passive dosing techniques for toxicity experiments.

4D-Printed Tool for Compressing a Shape Memory Polyurethane Foam during Programming.

Although several force application concepts are known that can be used to deform shape memory polymers (SMPs) within the scope of programming, controlled deformation is challenging in the case of samples with a cylinder-like shape, which need to be homogeneously compressed starting from the lateral surface. To solve this problem, this contribution follows a material approach that takes advantage of four-dimensional (4D) printing. Fused filament fabrication (FFF) was used as an additive manufacturing (AM) technique to produce a thermoresponsive tool in a cylindrical shape from a polyether urethane (PEU) having a glass transition temperature (Tg) close to 55 °C, as determined by differential scanning calorimetry (DSC). Once it was 4D-printed, a sample of laser cut polyester urethane urea (PEUU) foam with a cylindrical wall was placed inside of it. Subsequent heating to 75 °C and keeping that temperature constant for 15 min resulted in the compression of the foam, because the internal stresses of the PEU were transferred to the PEUU, whose soft segments were completely molten at 65 °C as verified by DSC. Upon cooling to -15 °C and thus below the offset temperature of the soft segment crystallization transition of the PEUU, the foam was fixed in its new shape. After 900 days of storage at temperatures close to 23 °C, the foam recovered its original shape upon reheating to 75 °C. In another experiment, a 4D-printed cylinder was put into hibernation for 900 days before its thermoresponsiveness was investigated. In the future, 4D-printed tools may be produced in many geometries, which fit well to the shapes of the SMPs to be programmed. Beyond programming SMP foams, transferring the forces released by 4D-printed tools to other programmable materials can further expand technical possibilities.

Nerve Wrap for Local Delivery of FK506/Tacrolimus Accelerates Nerve Regeneration.

Peripheral nerve injuries (PNIs) occur frequently and can lead to devastating and permanent sensory and motor function disabilities. Systemic tacrolimus (FK506) administration has been shown to hasten recovery and improve functional outcomes after PNI repair. Unfortunately, high systemic levels of FK506 can result in adverse side effects. The localized administration of FK506 could provide the neuroregenerative benefits of FK506 while avoiding systemic, off-target side effects. This study investigates the utility of a novel FK506-impregnated polyester urethane urea (PEUU) nerve wrap to treat PNI in a previously validated rat infraorbital nerve (ION) transection and repair model. ION function was assessed by microelectrode recordings of trigeminal ganglion cells responding to controlled vibrissae deflections in ION-transected and -repaired animals, with and without the nerve wrap. Peristimulus time histograms (PSTHs) having 1 ms bins were constructed from spike times of individual single units. Responses to stimulus onsets (ON responses) were calculated during a 20 ms period beginning 1 ms after deflection onset; this epoch captures the initial, transient phase of the whisker-evoked response. Compared to no-wrap controls, rats with PEUU-FK506 wraps functionally recovered earlier, displaying larger response magnitudes. With nerve wrap treatment, FK506 blood levels up to six weeks were measured nearly at the limit of quantification (LOQ ≥ 2.0 ng/mL); whereas the drug concentrations within the ION and muscle were much higher, demonstrating the local delivery of FK506 to treat PNI. An immunohistological assessment of ION showed increased myelin expression for animals assigned to neurorrhaphy with PEUU-FK506 treatment compared to untreated or systemic-FK506-treated animals, suggesting that improved PNI outcomes using PEUU-FK506 is mediated by the modulation of Schwann cell activity.

Degree of cure of orthodontic composite attachments underneath aligners.

The aim of this study was to assess the percentage degree of cure (DC%) of 2-mm-thick resin composite attachments used for aligner treatment. Three types of aligner - two thermoformed aligners (Clear Aligner [CLA], polyethylene terephthalate glycol modified; and Invisalign [INV], polyester urethane) and a three-dimensional-printed aligner (Graphy TC-85DAC [GRP], an acrylate-methacrylate copolymer) - were selected, along with two universal resin composites (3M Filtek Universal [FTU] and Charisma Topaz ONE [CTO]). Samples of each composite were placed under each aligner, and the degree of cure of each composite was evaluated on the top (facing the aligner) and the bottom (facing the substrate) attachment surfaces after curing. Five specimens were used per combination of aligner and composite, and an additional group of composites irradiated without aligners served as the control. The DC% measurements were performed using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The DC% across the aligners were (median values) 33.8%-44.8% for CLA, 33.6%-40.8% for INV, 32.8%-40.6% for GRP, and 40.0%-51.7% for the control group. The DC% values of the attachments cured under any aligner were significantly lower than that of the corresponding control, with the values recorded on the top surfaces being 6% higher than those on the bottom surfaces after adjusting for aligner group and composite type.

Rheological, Ballistic, and Mechanical Properties of 3D Printed, Photocured Composite Propellants

This study explores the rheological, mechanical, and ballistic properties of printed ammonium perchlorate composite propellant at 82.5% solids loading with binders curable with ultraviolet light of wavelength from 215 to 400 nm (UV). A polybutadiene urethane acrylate and two polyester urethane acrylate propellants are printed by an in-house-fabricated fused deposition molding printer. Propellants are all shear-thinning and have significantly lower viscosity than similar hydroxyl-terminated polybutadiene (HTPB) propellants. Uniaxial stress–strain measurements indicate that ultimate tensile strength and ultimate tensile strain of all photocurable propellants are found to be greater than HTPB propellant. In particular, the ultimate tensile strain of polyester urethane acrylate propellant is six times that of HTPB propellant, demonstrating high compliance. Ballistic properties are measured from combustion of printed propellant articles in a windowed Crawford combustion bomb at inert gas pressures of up to 12.1 MPa. The burning characteristics were found to be relatively planar, though strong burning rate anisotropy, expected as a result of print layer inhomogeneities, was observed in two of the three formulations. Overall, pressure exponents of the propellants were mild and ranged from 0.17 to 0.33. These results are compared and contrasted to those of other printed propellants. These results provide valuable insight into the selection of a safe binder system for printing of photocurable composite propellants.

Polyester urethane urea (PEUU) functionalization for enhanced anti-thrombotic performance: advancing regenerative cardiovascular devices through innovative surface modifications.

Introduction: Thrombogenesis, a major cause of implantable cardiovascular device failure, can be addressed through the use of biodegradable polymers modified with anticoagulating moieties. This study introduces a novel polyester urethane urea (PEUU) functionalized with various anti-platelet deposition molecules for enhanced antiplatelet performance in regenerative cardiovascular devices. Methods: PEUU, synthesized from poly-caprolactone, 1,4-diisocyanatobutane, and putrescine, was chemically oxidized to introduce carboxyl groups, creating PEUU-COOH. This polymer was functionalized in situ with polyethyleneimine, 4-arm polyethylene glycol, seleno-L-cystine, heparin sodium, and fondaparinux. Functionalization was confirmed using Fourier-transformed infrared spectroscopy and X-ray photoelectron spectroscopy. Bio-compatibility and hemocompatibility were validated through metabolic activity and hemolysis assays. The anti-thrombotic activity was assessed using platelet aggregation, lactate dehydrogenase activation assays, and scanning electron microscopy surface imaging. The whole-blood clotting time quantification assay was employed to evaluate anticoagulation properties. Results: Results demonstrated high biocompatibility and hemocompatibility, with the most potent anti-thrombotic activity observed on pegylated surfaces. However, seleno-L-cystine and fondaparinux exhibited no anti-platelet activity. Discussion: The findings highlight the importance of balancing various factors and addressing challenges associated with different approaches when developing innovative surface modifications for cardiovascular devices.

BIO26: Engineering Anti-platelet polymers for regenerative cardiovascular applications

Thrombogenesis is the main failure cause of implantable cardiovascular devices. Thrombus formation not only occludes devices but exacerbates immune responses responsible for foreign body reaction. Biodegradable polymers modified with anticoagulating moieties represent a strategy to overcome these limitations. Herein, we propose the use of a novel polyester urethane urea (PEUU) with pendant carboxyl groups for functionalization with different anti-platelet deposition molecules. PEUU was synthesized from PCL (Polycaprolactone), 1,4-diisocyanatobutane and putrescine, and then chemically oxidized to introduce carboxyl groups in the polymer backbone (PEUU-COOH). PEUU-COOH was functionalized in-situ with Polyethyleneimine mW 400 (PEI), 4 arm Polyethylene Glycol (PEG-4-Arm-NH2), seleno-L-cystine, heparin sodium and fondaporinux as anti-platelet deposition molecules. After solvent casting, functionalization was confirmed via Fourier-transformed infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Metabolic activity (MTT) and hemolysis assays were performed to validate biocompatibility. Anti-platelet activity of PRP exposed films was examined via a platelet aggregation assay, through an activation assay via lactate dehydrogenase (LDH), and by surface imaging with scanning electron microscopy (SEM). Whole-blood clotting time quantification assay was carried out to evaluate anticogulating properties. Upon oxidation, PEUU exhibited COOH pendant groups that were successfully employed to conjugate the anti-platelet molecules, obtaining homogeneous films. Overall cytotoxicity was below 20% and the hemolysis was below 5%, suggesting high biocompatibility and hemocompatibility. The most potent anticoagulant activity was obtained for heparin-functionalized materials followed by PEG-4-Arm-NH2 and PEI. Surprisingly, Seleno-L-cystine and Fondaporinux showed no anti-platelet activity. Results indicate that the polymers introduced here are a promising strategy to avoid thrombogenesis in vascular grafts.

Comparative biodeterioration at air interfaces of adipate-based polyester polyurethane coatings by fungal microcolonies of Aureobasidium sp. W12

Understanding conditions that enable environmentally common microbes to aggressively deteriorate polymer materials are important for predicting and controlling the environmental fates of these materials. For protective paints and coatings in terrestrial environments, processes at air interfaces are among important factors to understand. Here, we track fungal biodeterioration at air/solid polymer interfaces under nutrient limitation and high humidity, using polymer compositions common in commercial polyester polyurethanes. A fungal isolate, Aureobasidium sp. W12, was collected from an aircraft and identified as a polyester degrader through screening assays. Two polyadipate-based materials were then used for W12 coating deterioration analysis: a commercial polyester polyurethane, Irogran® PS455–203, and a model polyester urethane, PEA-HM. Single and micro-aggregated cell clusters distributed within ∼1.5 mm diameter regions were prepared on the polymer surfaces and incubated with no supplemental nutrients at >95% relative humidity for up to 13 days. Coating deterioration was semi-quantitatively monitored through ester carbonyl loss by transmission FTIR spectroscopy and both materials were rapidly deteriorated, although at different rates. With ∼0.5 monolayer cell surface coverage, PEA-HM showed about 6 × greater molar ester deterioration versus Irogran® over the first 24 h. By 13 days, the polyester fractions of Irogran coatings were deteriorated to an average depth of about 0.1 µm, while PEA-HM coatings about 1 µm thick were completely deteriorated in 5 days within and beyond cell covered regions. Localized analysis of non-uniform PEA-HM deterioration showed that quantities on the order of 10 individual Aureobasidium yeast cells could locally deteriorate through 1–2 µm of PEA-HM coating within 12 days (with deterioration rates up to about 2 × 10−6 µmol ester / (cell × day)). These results correlate conditions and polymer properties that promote high deterioration potentials of Aureobasidium W12 microcolonies at air / coating interfaces.

4D Printing of Electroactive Triple-Shape Composites.

Triple-shape polymers can memorize two independent shapes during a controlled recovery process. This work reports the 4D printing of electro-active triple-shape composites based on thermoplastic blends. Composite blends comprising polyester urethane (PEU), polylactic acid (PLA), and multiwall carbon nanotubes (MWCNTs) as conductive fillers were prepared by conventional melt processing methods. Morphological analysis of the composites revealed a phase separated morphology with aggregates of MWCNTs uniformly dispersed in the blend. Thermal analysis showed two different transition temperatures based on the melting point of the crystallizable switching domain of the PEU (Tm~50 ± 1 °C) and the glass transition temperature of amorphous PLA (Tg~61 ± 1 °C). The composites were suitable for 3D printing by fused filament fabrication (FFF). 3D models based on single or multiple materials were printed to demonstrate and quantify the triple-shape effect. The resulting parts were subjected to resistive heating by passing electric current at different voltages. The printed demonstrators were programmed by a thermo-mechanical programming procedure and the triple-shape effect was realized by increasing the voltage in a stepwise fashion. The 3D printing of such electroactive composites paves the way for more complex shapes with defined geometries and novel methods for triggering shape memory, with potential applications in space, robotics, and actuation technologies.

Harnessing length and height changes in thermoresponsive programmable materials

Abstract Shape-memory polymers can be used to develop thermoresponsive programmable materials that can take on sensory and actuator tasks as their ambient temperature changes. In this contribution, a self-synthesised poly(1,10-decylene adipate) diol-based polyester urethane (PEU) was used for their fabrication. After processing the PEU into filaments, programmable materials, including a gear-like object, the teeth of a ‘bevel gear’ and a unit cell, were additively manufactured by fused filament fabrication. In any case, a thermomechanical treatment was conducted that involved the deformation of the polymer at 75°C. After cooling to 15°C, the programmable materials were unloaded and the thermoresponsiveness between 23°C and 58°C was investigated. A maximum thermoreversible change in height of about 39% was detected for the ‘gear’. With regard to the ‘bevel gear’, proof of feasibility was provided for use as overheating protection, so that a force transmission could be switched off when heated and switched on when cooled down. The unit cell actuated under a weak external load of 0.01 N, thus exhibiting thermoreversible length changes of about 45%.

Εffect of cleansers on the composition and mechanical properties of orthodontic aligners in vitro

BackgroundThe aim of the study was to investigate the effect of three aligner cleaners on the composition and mechanical properties of two types of orthodontic aligners.Materials and methodsThe cleaners tested were two alkaline peroxide solutions (Retainer Brite—RB; Retainer Cleaner—RC) and one peroxide-free (Steraligner—ST) and the aligners Clear Aligner (C, polyester) and Invisalign (I, polyester–urethane). The aligners were immersed in the cleaner solutions as instructed every day (15 min for RB, RC; 5 min for ST) for a two-week period. The acidity of the solutions was tested with a pH meter. The changes in the chemical composition of the aligners were studied by attenuated total-reflection Fourier transform infrared spectrometry (ATR-FTIR), while Instrumented Indentation Testing (IIT) was used for assessment of changes in Martens Hardness (HM), modulus (EIT), elastic index (nIT) and relaxation (RIT).ResultsRB and RC were weakly acidic (pH = 6.3), whereas ST was mildly acidic (pH = 4.8). The ATR-FTIR analysis demonstrated evidence of acidic hydrolysis of C in ST and I in RB. The IIT-derived properties of I were not affected by the cleaners. However, for C a significant change was found in HM (all cleaners), nIT (all cleaners) and RIT (RB, ST). Although the chemical changes support a hydrolytic material deterioration, the results of mechanical properties may interfere with the material residual stresses during fabrication.ConclusionsCaution should be exerted in the selection of aligner cleaners. The mild acidic cleanser was more aggressive to the polyester, whereas an alkaline peroxide to the polyester–urethane aligner.

Synthesis and characterization of thermoplastic poly(piperazine succinate) metallopolymers coordinated to ruthenium(III) or iron(III)

AbstractMetal‐containing polymers represent an ever‐expanding frontier of material science. Of the numerous biocompatible ligands used to create a metallopolymer, piperazine‐containing polymers are still in their early development, even though piperazine is a common functional group in drug design and bioengineering scaffolding elements. We report the first synthesis and characterization (with NMR, IR, GPC, UV–vis spectroscopy, and thermal analysis) of two thermoplastic poly(alkyl piperazine succinate) diols with either propyl or hexyl alkane chains bridging the piperazines. These polyester diols were then chain extended with hexamethylene diisocyanate to create highly amorphous polyester urethane thermoplastic polymers. Ru(III) or Fe(III) was then successfully coordinated with these polymers, with approximately 30% of the bulk metallopolymer product becoming 250x the molecular weight of the non‐metal containing polymers. However, coordination of Fe(III), and to a lesser extent Ru(III), to these polypiperazines accelerated the hydrolysis of the polyester linkage in water over 15 days. Thus, these novel polymers are highly biodegradable with Fe(III) metallopolymers hydrolyzing faster than Ru(III) metallopolymers and poly(propyl piperazine succinate) polymers hydrolyzing faster than poly(hexyl piperazine succinate) polymers.

Organometallic complexation phenomenon observed during the natural aging of polyester urethane in the presence of iron corrosion

Shoes with polyester urethane soles have been stored for 3 decades in a museum environment after several months of mining use. Upon observation of sole material ageing under natural conditions, the shoes were laboratory stored since 2017 in order to evidence and follow signs of polyester urethane degradation. This study aims at characterizing a complex degradation material found on several shoes of the museum’s collection. Combining chemical composition analysis (EDX), mass spectroscopy (EGA-MS, py-GCMS) and vibrational spectroscopy (Raman and IR), results evidence the presence of iron carboxylates in different coordination modes. This study highlights the formation of a hitherto unknown degradation material of polyester urethane: an organometallic complex with iron ions coordinated with carboxylic rests of polyester polyol chains. The compound arises from the interaction between iron ions from the corrosion of structural metallic elements of the sole, and the polyester polyol fragments from the hydrolysis of the polyester urethane.

Effectiveness of different epidural coverage materials for preventing postoperative scar hyperplasia and dural adhesion in spine

Objective: To analyze the effects and mechanisms of three commonly used epidural coverings, gelatin sponge, bovine Achilles tendon extract collagen and polyester urethane fiber, in preventing epidural scar adhesions after laminectomy in rats. Methods: Forty-eight adult Wistar rats were excised from L2 to L5 lamina to establish laminectomy models, and were divided into four groups with random number table according to different covering materials (12 rats in each group): blank group (group A), gelatin sponge group (absorbable, group B), polyester urethane fiber group (non-absorbable, group C) and bovine Achilles tendon extract collagen group (absorbable, group D). At 4 and 12 weeks postoperatively, the spinal tissues of the operated area were taken for gross observation (Rydell scar adhesion rating criteria) and histological observation (Nussbaum criteria); and the expression of three scar proliferation-related cytokines, basic fibroblast growth factor (bFGF), growth transforming factor β1 (TGF-β1) and vascular endothelial growth factor (VEGF), were measured in the peridural tissues. The differences between the indices in each group were analyzed and compared. Results: All 48 rats survived, and gross and histological findings at 4 and 12 weeks showed no dural adhesions in the gelatin sponge and bovine Achilles tendon extract collagen groups, adhesions in the polyester urethane fiber group, and heavy adhesions and spinal cord compression in the blank control group. There were significant differences in the Rydell grade and Nussbaum histological score between the absorbable material group and the non-absorbable group (both P<0.05). Western protein blotting at 4 and 12 weeks confirmed that the expression levels of three cytokines, including bFGF, TGF-β1, and VEGF, were lower in the absorbable material group than those in the non-absorbable group (all P<0.01). Immunofluorescence tests at 12 weeks confirmed that the expression of bFGF, TGF-β1 and VEGF were all lower in the gelatin sponge group (9.81±0.81, 12.42±2.35, 8.63±1.76) and the bovine Achilles tendon extract collagen group (12.70±2.02, 8.23±1.03, 10.19±2.67) than those in the polyester urethane fiber group (33.94±2.03, 30.29±2.76, 25.79±1.21) (all P<0.01). Conclusions: Bovine achilles tendon extract collagen and gelatin sponge can effectively reduce the hyperplasia of scar and dural adhesions after spinal surgery.

Structural Strength Analyses for Low Brass Filler Biomaterial with Anti-Trauma Effects in Articular Cartilage Scaffold Design.

The existing harder biomaterial does not protect the tissue cells with blunt-force trauma effects, making it a poor choice for the articular cartilage scaffold design. Despite the traditional mechanical strengths, this study aims to discover alternative structural strengths for the scaffold supports. The metallic filler polymer reinforced method was used to fabricate the test specimen, either low brass (Cu80Zn20) or titanium dioxide filler, with composition weight percentages (wt.%) of 0, 2, 5, 15, and 30 in polyester urethane adhesive. The specimens were investigated for tensile, flexural, field emission scanning electron microscopy (FESEM), and X-ray diffraction (XRD) tests. The tensile and flexural test results increased with wt.%, but there were higher values for low brass filler specimens. The tensile strength curves were extended to discover an additional tensile strength occurring before 83% wt.%. The higher flexural stress was because of the Cu solvent and Zn solute substituting each other randomly. The FESEM micrograph showed a cubo-octahedron shaped structure that was similar to the AuCu3 structure class. The XRD pattern showed two prominent peaks of 2θ of 42.6° (110) and 49.7° (200) with d-spacings of 1.138 Å and 1.010 Å, respectively, that indicated the typical face-centred cubic superlattice structure with Cu and Zn atoms. Compared to the copper, zinc, and cart brass, the low brass indicated these superlattice structures had ordered–disordered transitional states. As a result, this additional strength was created by the superlattice structure and ordered–disordered transitional states. This innovative strength has the potential to develop into an anti-trauma biomaterial for osteoarthritic patients.

Biodegradation of Polyester Polyurethane by Embarria clematidis.

Polyester urethanes (PUR) are widely used in industries and have led to a worldwide plastic waste problem. Thus, novel solutions for PUR degradation are required to reduce environmental pollution. This work investigates the PUR biodegradation efficiency of 33 fungal species using a polyester-polyurethane colloid branded Impranil DLN (Impranil) compared to Aspergillus niger, which served as the positive control. The biodegradation is evaluated based on its ability to clear Impranil in media. Eleven fungi can clear Impranil in both solid- and liquid-medium assays. The highest degradation was attributed to Embarria clematidis cultured with Impranil as a carbon source. The degradation was confirmed by the Sturm test, Fourier-transform infrared (FTIR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS). From the Sturm test, CO2 at a concentration of 0.85 g/L was found in E. clematidis cultured with 150 mL of Impranil solution after a 2-week incubation period while the CO2 at a concentration of 0.53 g/L was detected from A. niger in the same conditions. The biodegradation was further confirmed by evaluating the clearance percentage of supernatant of E. clematidis and A. niger culturing with Impranil from the Sturm test. The clearance percentage of E. clematidis and A. niger supernatant was 88.84 and 48.97%, respectively. Moreover, the degradation of soft segment and breakdown of ester linkages were observed, as evidenced by the decrease of the carbonyl (1,715 cm–1) and N-H stretching (1,340 cm–1 and 1,020 cm–1) FTIR spectral peaks, respectively. GC-MS detected 3Z-heptenol, 5Z-octenol, 2E,4E-hexadienol acetate, and 3E,6Z-nonadienol as degradation products from the E. clematidis culture supernatant. This fungus was screened for its ability to produce extracellular esterase, protease, and urease enzymes. Extracellular esterase, very low urease, and no protease activities were detected in the culture supernatant of E. clematidis in the presence of Impranil. E. clematidis can degrade Impranil partially via hydrolysis of ester linkages by cell-bound esterases at a considerable rate without any prior treatment. This fungus not only degraded Impranil but also mineralized them into CO2 and H2O. E. clematidis can be applied in the process of biochemical depolymerization of PUR for the pure monomers recycling.

Susceptibility to Degradation in Soil of Branched Polyesterurethane Blends with Polylactide and Starch.

A very important method of reducing the amount of polymer waste in the environment is the introduction to the market of polymers susceptible to degradation under the influence of environmental factors. This paper presents the results of testing the susceptibility to degradation in soil of branched polyesterurethane (PUR) based on poly([R,S]-3-hydroxybutyrate) (R,S-PHB), modified with poly([D,L]-lactide) (PLA) and starch (St). Weight losses of samples and changes in surface morphology (SEM, OM and contact angle system) with simultaneously only slight changes in molecular weight (GPC), chemical structure (FTIR and 1HNMR) and thermal properties (DSC) indicate that these materials are subject to enzymatic degradation caused by the presence of microorganisms in the soil. Chemical modification of branched polyesterurethanes with R,S-PHB and their physical blending with small amounts of PLA and St resulted in a slow but progressive degradation of the samples.

Structural Characterization Analyses of Low Brass Filler Biomaterial for Hard Tissue Implanted Scaffold Applications.

A biomaterial was created for hard tissue implanted scaffolds as a translational therapeutic approach. The existing biomaterials containing titanium dioxide filler posed a risk of oxygen gas vacancy. This will block the canaliculars, leading to a limit on the nutrient fluid supply. To overcome this problem, low brass was used as an alternative filler to eliminate the gas vacancy. Low brass with composition percentages of 0%, 2%, 5%, 15%, and 30% was filled into the polyester urethane liquidusing the metallic filler polymer reinforced method. The structural characterizations of the low brass filler biomaterial were investigated by Field Emission Scanning Electron Microscopy. The results showed the surface membrane strength was higher than the side and cross-section. The composition shapes found were hexagon for polyester urethane and peanut for low brass. Low brass stabilised polyester urethane in biomaterials by the formation of two 5-ringed tetrahedral crystal structures. The average pore diameter was 308.9 nm, which is suitable for articular cartilage cells. The pore distribution was quite dispersed, and its curve had a linear relationship between area and diameter, suggestive of the sphere-shaped pores. The average porosities were different between using FESEM results of 6.04% and the calculated result of 3.28%. In conclusion, this biomaterial had a higher surface membrane strength and rather homogeneous dispersed pore structures.

Low volatile monofunctional reactive diluents for radiation curable formulations

AbstractIn the last decades the importance of UV curable formulations has increased continuously. Their fast curing speed, solvent‐free polymerization conditions, and the formation of hard and highly crosslinked photopolymer networks represent major benefits. Commercial UV resins generally consist of multi‐functional vinyl oligomers, photoinitiators, additives, and reactive diluents. Mono‐ and multi‐functional reactive diluents serve as thinners to lower the overall resin viscosity and to improve processability. However, many monofunctional reactive diluents like isobornyl (meth)acrylate or benzyl (meth)acrylate exhibit high volatility, often already at room temperature. This causes adverse effects such as unpleasant odor, potential health risks, and changing resin composition during processing. A new group of monomers that show high potential for replacing traditional highly volatile reactive diluents are salicylate (meth)acrylates. In this work, salicylate‐based thinners are synthesized, polymerized, and characterized with respect to their viscosity, volatility, thermal stability, photoreactivity, and thermomechanical properties of their homopolymers. Additionally, a first example of their diluting effect in a highly viscous difunctional polyester urethane methacrylate is demonstrated with 30 wt% of a cycloaliphatically and an aromatically substituted salicylate methacrylate. The polymers of the diluted resin exhibit similarly high glass transition temperatures of 110 and 126 °C, which are in the range of the polymers of the undiluted resin.

Fabrication of biodegradable polyurethane electrospun webs of fibers modified with biocompatible graphene oxide nanofiller

A successful optimization of the electrospinning parameters for obtainment of biodegradable polyester urethane (DP) webs of fibers, neat and graphene oxide (GO) modified, was performed. The effect of the processing parameters (distance between the needle tip and the collector, applied voltage, and flowing rate), solution type and polymer concentration, on the fiber-forming process and the obtained fibers’ morphology was examined. The best homogeneity of the fibers was achieved for 12 wt% DP dissolved in 80:20 wt% mixture of chloroform and ethanol, applying similar processing parameters for the neat and modified samples (0.5 ml/h pumping rate, 15 kV applied voltage, and 150 mm distance to the collector, for the neat sample, and 0.4 ml/h, 18 kV, and 110 mm, for the GO modified samples). The main novelty of this work is the modification of DP with low quantities (0.5, 1.0 and 2.0 wt%) of GO – the “next generation” nanomaterial for stem cell control. The morphological characterization revealed a fibrous microstructure consisting of randomly oriented fibers with a diameters ranging from hundreds nanometers to couple micrometers, representing a feasible imitation of the structure of extracellular matrix (ECM). The XRD studies showed high dispersion of GO in DP matrix and even exfoliation for the sample that contains 2 wt% GO. Raman studies neatly complemented the highest filler/matrix interactions and the superior levels of dispersion for this sample. TGA was used to analyze the thermo-oxidative degradation and also to determine the actual content of GO present in the samples.