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Polymeric blends are employed in the production of filaments for additive manufacturing to balance mechanical and processability properties. The mechanical and thermal properties of polymeric filaments made of poly (lactic acid) (PLA), polyhydroxyalkanoates (PHA), and its blend (PLA-PHA) are investigated herein and correlated to their measured structural and physicochemical properties. PLA exhibits the highest stiffness and tensile strength, but lower toughness. The mechanical properties of the PLA-PHA blend were similar to those of PLA, but with a significantly higher toughness. Despite the lower mechanical properties of neat PHA, incorporating a small amount (12 wt.%) of PHA into PLA significantly enhances toughness (approximately 50%) compared to pure PLA. The synergistic effect is attributed to the spherulitic morphology of blended PHA in PLA, promoting interactions between the amorphous regions of both polymers. Thermal stability is notably improved in the PLA-PHA blend, as determined by thermogravimetric analysis. The blend also exhibits lower cold crystallization and glass transition temperatures as compared to PLA, which is beneficial for additive manufacturing. Following additive manufacturing, X-ray photoelectron spectroscopic showed that the three filaments present an increase in C-C and C=O bonds associated with the loss of C-O bonds. The thermal process induces a slight increase in crystallinity in PHA due to chain reorganization. The study provides insights into the thermal and structural changes occurring during the melting process of additive manufacturing.

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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.

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The design and analysis of a device to measure the burst strength (strength under a state of pure radial internal pressure) and compliance of vascular grafts and flexible pressurized tubes is presented. The device comprises three main sections, viz., a clean air-dry pressure controller, a test specimen holder, and automated software for control and data collection. Air pressure is controlled by means of a valve and a dedicated mechanism allowing reaching up to 120 psi in increments of 1 psi, and recording pressure changes with 0.04 psi resolution. The circumferential strain is determined by measuring the radial displacement of the vascular graft using an optical arrangement capable of determining a maximum radial displacement of 10 mm with 0.02 mm resolution. The instrument provides a low uncertainty in compliance (±0.32%/100 mm Hg-1) and burst strength measurements. Due to its simplicity, the device can easily be reproduced in other laboratories contributing to a dedicated instrument with high resolution at low cost. The reliability of the apparatus is further confirmed by conducting finite element analysis, elasticity solutions for pressurized cylinders, and testing of small diameter vascular grafts made of a commercial aliphatic polyurethane tested under radial internal pressure.

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The circumferential compliance and burst strength of vascular grafts are predicted through the conically modified von Mises and elasticity theories, providing an analytical closed form solution for both parameters. Besides the graft's radii, the model for circumferential compliance depends solely on the elastic modulus and Poisson's ratio of the polymer material, and its accuracy was verified by finite element analysis and measurements. The analytical expression of the burst strength requires accurate determination of the material's tensile and compressive yield stress, which were carefully obtained by using digital image correlation measurements in uniaxial tensile and compressive tests of the constitutive material. The average measured circumferential compliance and burst strength of an 8mm graft made of a commonly used biomaterial, Tecoflex® SG-80A, are 1.05%/100mmHg-1 and 34.1psi (1763mmHg) and the proposed analytical predictions fall within the experimental scattering. Thus, it is shown that the circumferential compliance and burst strength of vascular grafts can be analytically predicted by knowing the elastic and yield material properties accurately, without needing to actually test the graft under radial pressure. This is a major advantage which can aid in the design and tailoring of vascular grafts.

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Conventional approaches to bone regeneration rarely use multiwall carbon nanotubes (MWCNTs) but instead use polymeric matrices filled with hydroxyapatite, calcium phosphates and bioactive glasses. In this study, we prepared composites of MWCNTs/polycaprolactone (PCL) for bone regeneration as follows: (a) MWCNTs randomly dispersed on PCL, (b) MWCNTs aligned with an electrical field to determine if the orientation favors the growing of human dental pulp stem cells (HDPSCs), and (c) MWCNTs modified with ß-glycerol phosphate (BGP) to analyze its osteogenic potential. Raman spectroscopy confirmed the presence of MWCNTs and BGP on PCL, whereas the increase in crystallinity by the addition of MWCNTs to PCL was confirmed by X-ray diffraction and differential scanning calorimetry. A higher elastic modulus (608 ± 4.3 MPa), maximum stress (42 ± 6.1 MPa) and electrical conductivity (1.67 × 10(-7) S/m) were observed in non-aligned MWCNTs compared with the pristine PCL. Cell viability at 14 days was similar in all samples according to the live/dead assay, but the 21 day cell proliferation, measured by MTT was higher in MWCNTs aligned with BGP. Von Kossa and Alizarin red showed larger amounts of mineral deposits on MWCNTs aligned with BGP, indicating that at 21 days, this scaffold promotes osteogenic differentiation of HDPSCs.

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In this work, the effect of the incorporation of core-shell particles on the fracture mechanisms of the acrylic bone cements by using acoustic emission (AE) technique during the quasi-static compression mechanical test was investigated. Core-shell particles were composed of a poly(butyl acrylate) (PBA) rubbery core and a methyl methacrylate/styrene copolymer (P(MMA-co-St)) outer glassy shell. Nanoparticles were prepared with different core-shell ratio (20/80, 30/70, 40/60 and 50/50) and were incorporated into the solid phase of bone cement at several percentages (5, 10 and 15 wt%). It was observed that the particles exhibited a spherical morphology averaging ca. 125 nm in diameter, and the dynamic mechanical analysis (DMA) thermograms revealed the desired structuring pattern of phases associated with core-shell structures. A fracture mechanism was proposed taking into account the detected AE signals and the scanning electron microscopy (SEM) micrographs. In this regard, core-shell nanoparticles can act as both additional nucleation sites for microcracks (and crazes) and to hinder the microcrack propagation acting as a barrier to its growth; this behavior was presented by all formulations. Cement samples containing 15 wt% of core-shell nanoparticles, either 40/60 or 50/50, were fractured at 40% deformation. This fact seems related to the coalescence of microcracks after they surround the agglomerates of core-shell nanoparticles to continue growing up. This work also demonstrated the potential of the AE technique to be used as an accurate and reliable detection tool for quasi-static compression test in acrylic bone cements.

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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 (Tg = -25 °C; Tm = 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 Tg 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 CO2 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.

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Core-shell nanoparticles consisting of polybutyl acrylate (PBA) rubbery core and a polymethyl methacrylate (PMMA) shell, with different core-shell ratios, were synthesized in order to enhance the fracture toughness of the acrylic bone cements prepared with them. It was observed by TEM and SEM that the core-shell nanoparticles exhibited a spherical morphology with ca. 120 nm in diameter and that both modulus and tensile strength decreased by increasing the PBA content; the desired structuring pattern in the synthesized particles was confirmed by DMA. Also, experimental bone cements were prepared with variable amounts (0, 5, 10 and 20 wt.%) of nanoparticles with a core-shell ratio of 30/70 in order to study the influence of these nanostructured particles on the physicochemical, mechanical and fracture properties of bone cements. It was found that the addition of nanostructured particles to bone cements caused a significant reduction in the peak temperature and setting time while the glass transition temperature (Tg) of cements increased with increasing particles content. On the other hand, modulus and strength of bone cements decreased when particles were incorporated but fracture toughness was increased.

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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.

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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.

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In this work, we report the preparation of bone cements by using methyl methacrylate (MMA) as a base monomer and either hydroxyapatite (HA), alpha tricalcium phosphate (α-TCP) or bovine bone particles as bioactive fillers. In general, it was observed that curing times increased by the addition of any of these fillers (from 4 to 6.7 min). Maximum temperatures decrease slightly by the addition of 20 wt.% of either α-TCP or bovine bone (80.3°C and 73.2°C respectively) but it did not change by the addition of HA (84.3°C) with respect to PMMA only bone cement used as control. Residual monomer content was lower than 4% in the bioactive bone cements. By using α-TCP or bovine bone compressive strength increased with respect to the unfilled bone cement but it was reduced when HA was used. However, all these formulations fulfill the 70 MPa required for bone cement use. Flexural strength was increased by using either a-TCP o bovine bone but the addition of HA decreased this properties compared to the base bone cement. However, the minimum flexural strength (50 MPa) was fulfilled only in those experimental formulations containing low amounts of α-TCP. The minimum tensile strength (30 MPa) was satisfied by all formulations but it was always lower than the exhibited by the unfilled bone cement.

Este trabajo reporta la preparación de cementos óseos utilizando metacrilato de metilo (MMA) como monómero base y rellenos bioactivos tales como hidroxiapatita (HA), fosfato tricálcico alfa (α-TCP) o hueso bovino. En general, los tiempos de curado aumentaron con la inclusión de estos refuerzos (de 4 hasta 6.7 min). La temperatura máxima alcanzada durante la polimerización del cemento disminuyó ligeramente al adicionar 20% de α-TCP o hueso bovino (80.3°C y 73.2°C respectivamente) y se mantuvo sin cambio en las formulaciones con HA (84.3°C) con respecto al control de solo PMMA. El contenido de monómero residual en los cementos bioactivos fue menor al 4%. La presencia de α-TCP o hueso bovino aumentó la resistencia a la compresión del cemento base y la adición de HA la disminuyó, cumpliendo en todos los casos con la resistencia mínima a la compresión (70 MPa) sugerida para su uso como cemento óseo. La adición de α-TCP o hueso bovino aumentó la resistencia a la flexión del cemento base pero la adición de HA la redujo aunque el requerimiento mínimo de resistencia a la flexión (50 MPa) fue cumplido solamente al usar concentraciones bajas de α-TCP. La resistencia tensil mínima (30 MPa) fue satisfecha por todas las formulaciones aunque siempre fue menor que la exhibida por el cemento base.

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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.

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Bone cements prepared with methyl methacrylate and either methacrylic acid or diethyl amino ethyl methacrylate as comonomers were characterized by infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, dynamic mechanical thermal analysis, and mechanical testing. Selected formulations containing these functionalized methacrylates were filled with hydroxyapatite and studied in terms of their properties in tension, compression and bending, and X-ray diffraction. It was found that residual monomer was not greatly affected by the presence of either acid or basic comonomers in the unfilled bone cements. In contrast, molecular weight, curing times, and glass transition temperature were composition dependent. For samples with acidic comonomer, a faster curing time, higher molecular weight, and higher glass transition temperatures were observed with respect to those with the basic comonomer. X-ray diffraction revealed that the crystalline structure was not affected by the nature of comonomer in the bone cement while scanning electron microscopy showed that hydroxyapatite remained as clusters in the bone cement. The mechanical properties of filled bone cements depended mainly on composition and type of testing. Hydroxyapatite-filled bone cements fullfilled the minimum compressive strength (70 MPa) required for bone cement use. However, the minimum tensile strength (30 MPa) was only fullfilled by cements prepared without comonomer and those containing methacrylic acid. The minimum bending strength requirement (50 MPa) was not satisfied by any of the formulations studied.

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