Biological evaluation of poly-l-lactic acid composite containing bioactive glass

Biodegradable and biocompatible materials are the basis for medical application. As an initial step for developing bone internal fixation materials, the biological evaluation of poly-l-lactic acid/bioactive glass (PLLA/BG) composite in vitro and in vivo, including the hemolysis test, pyrogen test, acute systemic toxicity test, genetic toxicity test, anaphylaxis test, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test, direct cell culture and in vivo implant experiment, was performed. The results indicated that PLLA/BG composite showed no acute systemic toxicity, genetic toxicity, anaphylaxis reaction, and pyrogen reaction, and the hemolysis ratio was 0.39%. MTT assay indicated that no cytotoxic effect was observed for the PLLA/BG composite, and in addition, a significant increase in cellular activity compared to the negative control group was found. Excellent adhesion between fibroblast and PLLA/BG material was observed, the fibroblasts cultured on the PLLA/BG composite substrates revealed a higher proliferation and differentiation rate than those on the pure PLLA substrates. In vivo implant experiment showed that the PLLA/BG composite could maintain the mechanical properties during the course of fracture therapy, and the malleolar fracture of rabbits was healed in 8 weeks on the whole. Therefore, PLLA/BG composites have a promising biological response as a potential implant material.     

In vitro degradation of poly(l-lactide)/poly(ε-caprolactone) blend reinforced with MWCNTs

The physical and mechanical properties of poly(l-lactide)/poly(??-caprolactone) (PLLA/PCL) blends reinforced with multiwalled carbon nanotubes (MWCNTs) before and after in vitro degradation were investigated. Because of brittleness, PLLA needs to be plasticized by PCL as a soft polymer. The MWCNTs are used to balance the stiffness and the flexibility of PLLA/PCL blends. The results showed that with incremental increase in concentration of MWCNTs in composites, the agglomerate points of MWCNTs were increased. The physical and mechanical properties of prepared PLLA/PCL blends and MWCNT/PLLA/PCL nanocomposites were characterized. The X-ray diffraction analysis of the prepared blends and composites showed that MWCNTs, as heterogeneous nucleation points, increased the lamella size and therefore the crystallinity of PLLA/PCL. The mechanical strength of blends was decreased with incremental increase in PCL weight ratio. The mechanical behavior of composites showed large strain after yielding and high elastic strain characteristics. The tensile tests results showed that the tensile modulus and tensile strength are significantly increased with increasing the concentration of MWCNTs in composites, while, the elongation-at-break was decreased. The in vitro degradation rate of polymer blends in phosphate buffer solution (PBS) increased with higher weight ratio of PCL in the blend. The in vitro degradation rate of nanocomposites in PBS increased about 65% when the concentration of MWCNTs increased up to 3% (by weight). The results showed that the degradation kinetics of nanocomposites for scaffolds can be engineered by varying the contents of MWCNTs.     

Porous hydroxyapatite‐bioactive glass hybrid scaffolds fabricated via ceramic honeycomb extrusion

The successful fabrication of hydroxyapatite‐bioactive glass scaffolds using honeycomb extrusion is presented herein. Hydroxyapatite was combined with either 10 wt% stoichiometric Bioglass^® (BG1), calcium‐excess Bioglass^® (BG2) or canasite (CAN). For all composite materials, glass‐induced partial phase transformation of the HA into the mechanically weaker β‐tricalcium phosphate (TCP) occurred but XRD data demonstrated that BG2 exhibited a lower volume fraction of TCP than BG1. Consequently, the maximum compressive strength observed for BG1 and BG2 were 30.3 ± 3.9 and 56.7 ± 6.9 MPa, respectively, for specimens sintered at 1300°C. CAN scaffolds, in contrast, collapsed when handled when sintered below 1300°C, and thus failed. The microstructure illustrated a morphology similar to that of BG1 sintered at 1200°C, and hence a comparable compressive strength (11.4 ± 3.1 MPa). The results highlight the great potential offered by honeycomb extrusion for fabricating high‐strength porous scaffolds. The compressive strengths exceed that of commercial scaffolds, and biological tests revealed an increase in cell viability over 7 days for all hybrid scaffolds. Thus it is expected that the incorporation of 10 wt% bioactive glass will provide the added advantage of enhanced bioactivity in concert with improved mechanical stability.     

Changes in the crystallinity and mechanical properties of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid)/poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="SmallCaps">l</Emphasis>-lactate) blend with annealing process

Biodegradable polymer blends of poly(l-lactic acid) (PLLA) and poly(butylene succinate-co-l-lactate) (PBSL) at various blending ratios are prepared. The blending of PLLA with PBSL results in an increase in the ductility and thermal stability of the blend. However, flexural strength and modulus, as well as loss modulus, decrease with an increase in PBSL content. Annealing is employed to increase blend crystallinity and subsequently improve the mechanical properties of the PLLA/PBSL blend. The influences of annealing time on the crystal modification, thermal properties, and mechanical properties of the PLLA/PBSL blend are investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and three-point bending test, respectively. Crystalline peaks are found in the XRD patterns of all annealed samples. DSC analysis reveals that the degree of crystallinity is enhanced with an increase in annealing time. The flexural modulus also increases with annealing time due to the change in crystalline phases. However, longer periods of annealing, especially over 20 h, result in thermal degradation and subsequently reduce the modulus value of the PLLA/PBSL blend.     

Assessment of Cytocompatibility of Bulk Modified Poly-L-lactic Acid Biomaterials

The cytocompatibility and hydrophilicity tests were performed by culturing mouse fibroblastic cells on films of poly-L-lactic acid (PLLA), poly(L-lactic-co-glycolide) (PLGA) and poly(L-lactide-co-glycolide)/ bioactive glass (PLGA/BG) or in the presence of extracts from these polymeric materials. The solvent casting method was used to prepare these films. PLLA films were most hydrophobic and PLGA/BG was least hydrophobic. Compared to the other films, PLLA showed the worst results in cytocompatibility. PLGA also showed favorable results for fibroblastic cells viability. PLGA/BG films also demonstrated improved cell compatibility due to the good biocompatibility of the bioactive glass particles. The results of this study indicate the promising biocompatibility of PLGA/BG as biomaterials in medical field.     

Preparation and Properties of Bioactive Composite Based on Bioactive Glass and Poly-L-Lactide

Bioactive and bioresorbable composite was fabricated based on poly-L-lactide (PLLA) and bioactive glass (average particle size: 4.24 µm) by the combination of solvent evaporation technique and hot pressing. Bioactive glass granules are distributed homogeneously in the composite. With the increasing of the amount of bioactive glass, the bending strength and shearing strength of composite decrease while the bending modulus increases. PLLA/bioactive glass composites present a typical morphology of brittle failure with a smooth fracture surface. The biocompatibility test shows that the bioactive glass existing in the composite facilitates both adhesion and proliferation of rat fibroblast on the PLLA/bioactive glass composite film.     

Thermal degradation behaviour of multi‐walled carbon nanotube‐reinforced poly(L‐lactide) nanocomposites

BACKGROUND: Polymer/multi‐walled carbon nanotube (MWCNT) composites are one of the most promising alternatives to conventional polymer composites filled with micrometre‐sized fillers. This approach can also be applied for the improvement of mechanical properties and thermal stability of biodegradable aliphatic polyesters, such as poly(L ‐lactide) (PLLA), which have been receiving increasing attention due to environmental concerns. Thermal degradation behaviour provides useful information for the determination of the optimum processing conditions and for identification of potential applications of final products. RESULTS: The PLLA/MWCNT composites investigated showed a higher thermal degradation peak temperature and onset temperature of degradation along with a higher amount of residue at the completion of degradation than neat PLLA. Moreover, PLLA/MWCNT composites with a greater MWCNT content showed higher activation energy of thermal degradation than those with a lower MWCNT loading, which confirmed the positive effect of MWCNT incorporation on the enhancement of PLLA thermal stability. CONCLUSION: This study explored the thermal degradation behaviour of PLLA/MWCNT composites by observing the weight loss, molecular weight and mechanical properties during non‐isothermal and isothermal degradation. The incorporation of MWCNTs into the PLLA matrix enhanced considerably the mechanical properties and thermal stability. Copyright © 2009 Society of Chemical Industry     

Enhanced mechanical and photoluminescence effect of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) reinforced with functionalized multiwalled carbon nanotubes

The poly(l-lactide) (PLLA) biocompatible and biodegradable polymer was reinforced with functionalized Multiwalled carbon nanotubes (MWCNTs) to overcome on insufficient mechanical properties of this polymer for high load bearing applications. To fully realize the potential of MWCNTs for this purpose, they have to be homogeneously dispersed in polymer matrix and have efficient load transfer across the MWCNTs/polymer interface. The pristine MWCNTs (pMWCNTs) were functionalized, at first, by Friedel–Crafts acylation, which introduced the aromatic amine groups on the sidewall of MWCNTs (MWCNT–NH₂) without shortening or cutting of pMWCNTs. And then, the PLLA chains covalently grafted from the sidewall of MWCNT–NH₂ by in situ ring-opening polymerization of l-lactide oligomers using stannous octanoate as the initiating system. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy spectra revealed that the PLLA chains grafted form the sidewall of MWCNTs strongly. The surface morphology of pristine and PLLA-grafted MWCNTs (MWCNT-g-PLLAs) was characterized by scanning electron microscopy and transmission electron microscopy. The tensile test of prepared composites of PLLA with various concentrations of MWCNT-g-PLLAs show a significant increment in tensile strength and elongation at failure of composites with increasing the concentration of MWCNT-g-PLLAs in composites. Also, it is found that the MWCNT-g-PLLAs increased the photoluminescence effect of PLLA and widened the luminescence region of PLLA.     

Fabrication and characterization of bioactive glass (45S5)/titania biocomposites

Bioactive glass (BG) (45S5) has been used successfully as bone-filling material in orthopedic and dental surgery but its lean mechanical strength limits its applications in load-bearing positions. Approaches to strengthen these materials decreased their bioactivity. In order to realize the optimal matching between mechanical and bioactivity properties, bioactive glass (45S5) was reinforced by introducing titania (TiO₂) in anatase form and treated at 1000 °C to form new bioactive glass/titania biocomposites. The prepared biocomposites were assessed by XRD, FT-IR, mechanical properties and SEM. The results verified that the increase of titania percentage to BG powder enhanced gradually the mechanical data of the prepared biocomposites. SEM and FT-IRRS confirmed the presence of a rich bone-like apatite layer post-immersion on the composite surface. It has been found that the new BG/titania biocomposite materials especially those containing high content of titania have high bioactivity properties and compressive strength values comparable to cortical bone. Therefore, these biocomposite materials are promising for medical applications such as bone substitutes especially in load-bearing sites.     

Biodegradable aliphatic/aromatic copoly(ester-ether)s: the effect of poly(ethylene glycol) on physical properties and degradation behavior

A series of high molecular weight copolymers based on poly(L-lactic acid) (PLLA) as the biodegradable aliphatic segments, poly(butylene terephthalate) (PBT) as the rigid aromatic segments and hydrophilic poly(ethylene glycol) (PEG) as the soft segments were synthesized with the aim of developing novel polymer materials which could combine high physical properties with good biodegradability. Via direct melt polycondensation of terephthalic acid (TPA), 1,4-butanediol (BDO), poly(L-lactic acid) oligomer (OLLA) and PEG, biodegradable aliphatic/aromatic copoly(ester-ether)s, poly(butylene terephthalate-co-lactate-co-ethylene glycol) (PBTLG), were prepared. The effect of the introduction of PEG soft segments on the synthesis, mechanical properties and thermal stabilities as well as the degradation behaviors of the final copolymers was investigated. When the PEG units were incorporated into the polymer main-chains, the weight-average molecular weight of the copolymers increased from 53,700 g/mol to 177,000 g/mol and the tensile strength (σ) improved by nearly two times from 6.5 MPa to 12.8 MPa for PBTLG1000-0.5. The glass-transition temperature (T _g) gradually decreased from 26.9 °C down to −5.5 °C and a depression of melting temperature was observed with the increase of PEG content. According to the in vitro hydrolytic degradation observation, all of the copolymers underwent significant degradation in phosphate buffer solution at 37 °C and the water absorption as well as the degradation rate of PBTLGs displayed a strong dependency on the PEG content.     

Preparation of chitosan-sodium alginate/bioactive glass composite cartilage scaffolds with high cell activity and bioactivity

Chitosan-sodium alginate/bioactive glass (CSB) composite cartilage scaffold with outstanding in vitro mineralization property and cytocompatibility is synthesized by freeze drying method. The effect of bioactive glass (BG) addition on the microstructure, porosity, swelling/degradation ratio, in vitro mineralization property and cytocompatibility of CSB scaffold is investigated by the characterization techniques of SEM, XRD, FTIR and BET. Results showed that CSB composite cartilage scaffold had a three-dimensional (3D) porous structure, and both porosity and average pore size met the requirements of cartilage tissue repair. Among, the typical CSB-1.0 had the largest overall pore size and lowest compressive modulus (1.083 ± 0.002 MPa). As the amount of BG increased, pore volume and porosity of CSB scaffolds gradually decreased, and the swelling and degradation ratios gradually reduced. After immersing in SBF for 3 d, cauliflower like hydroxyapatite (HA) was formed on CSB surface, indicating that the scaffold had good in vitro mineralization property. Moreover, the introduction of BG into the composite scaffold can improve the relative cell viability of MC3T3-E1 cells, and CSB-1.0 has the strongest ability to promote the proliferation of cells. Therefore, the as-obtained CSB scaffold can be used as a strong candidate for cartilage tissue engineering scaffold to meet clinical needs.     

Characterization and thermal degradation kinetics of poly(l‐lactide) nanocomposites with carbon nanotubes

The purpose of this research was to study the thermal degradation kinetics of nanocomposites of poly(l ‐lactide) (PLLA) with carbon nanotubes (CNT) in order to provide further insight into their thermal stability. Nanocomposites were prepared by solvent casting with 1, 3, and 5% by weight of pristine CNT (P‐CNT) or functionalized CNT (F‐CNT), and were characterized using infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic‐mechanical‐thermal analysis. The kinetic parameters of thermal decomposition were determined employing Coats‐Redfern method to calculate the reaction order and E₂ function model to calculate the activation energy (Ea). We found no major changes in PLLA glass transition temperatures due to CNT presence, but melt‐crystallization temperature increased slightly in some composites. In general, composites consisting of 3% or 5% of F‐CNT had superior thermal stability than did pure polymer or P‐CNT composites. This improved thermal stability was revealed by slightly higher degradation and onset temperatures, and Ea obtained from kinetic analysis. In addition, 3% or 5% of F‐CNT in PLLA composites slightly enhanced the storage modulus above the glass transition. Therefore, functionalization promoted, in some extent, better morphology and dispersion of CNT into the matrix, which was responsible for improved thermal stability and thermomechanical performance of composites at higher temperatures relative to pure polymer. POLYM. ENG. SCI., 55:710–718, 2015. © 2014 Society of Plastics Engineers     

Bioactivity behaviour of biodegradable material comprising bioactive glass

Biocomposite of bioactive glass (BG) with chitosan polymer (CH) is prepared by freeze-drying technique. Obtained material is investigated by using several physico-chemical methods. The XRD and FTIR show the interface bonding interactions between glass and polymer. The specific surface and porosity of biocomposite were determined. In vitro assays were employed to evaluate the effect of chitosan addition on the glass by studying the chemical reactivity and bioactivity of the BG and BG/CH biocomposite after soaking in a simulated body fluid (SBF). The obtained results show the formation of a bioactive hydroxycarbonate apatite (HCA) layer and highlight the bioactivity and the kinetics of chemical reactivity of bioactive glass, particularly after association with chitosan. The BG/CH biocomposite has excellent ability to form an apatite layer. Inductively coupled plasma-optical emission spectrometry (ICP-OES) highlights the negative effect of chitosan on the silicon release toward the SBF of bioactive glass when in vitro assays.     

Bio‐composites for structural applications: Poly‐l‐lactide reinforced with long sisal fiber bundles

Fully bio‐based and biodegradable composites were compression molded from unidirectionally aligned sisal fiber bundles and a polylactide polymer matrix (PLLA). Caustic soda treatment was employed to modify the strength of sisal fibers and to improve fiber to matrix adhesion. Mechanical properties of PLLA/sisal fiber composites improved with caustic soda treatment: the mean flexural strength and modulus increased from 279 MPa and 19.4 GPa respectively to 286 MPa and 22 GPa at a fiber volume fraction of V_f = 0.6. The glass transition temperature decreased with increasing fiber content in composites reinforced with untreated sisal fibers due to interfacial friction. The damping at the caustic soda‐treated fibers‐PLLA interface was reduced due to the presence of transcrystalline morphology at the fiber to matrix interface. It was demonstrated that high strength, high modulus sisal‐PLLA composites can be produced with effective stress transfer at well‐bonded fiber to matrix interfaces. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40999.     

PPDO/PLLA皮芯复合单丝的体外降解

在磷酸盐(PBS)缓冲溶液中,对熔纺得到的两种聚对二氧环己酮(PPDO)/左旋聚乳酸(PLLA)皮芯复合单丝进行体外降解性能研究。结果表明:随着降解时间的延长,两种单丝的吸水率、质量损失率不断增加,相对黏度、强度保留率、断裂伸长率和缓冲溶液的p H值不断降低;随着降解时间的延长,两种单丝的熔融焓逐步升高;随着降解时间的延长,PPDO-PLLA单丝的表面形貌变化比PLLA-PPDO单丝的大,即PPDO的降解速率比PLLA更快。     

Modeling of poly(L‐lactide) thermal degradation: Theoretical prediction of molecular weight and polydispersity index

A mathematical model to describe the molecular weight and polydispersity index (Q) in poly(L ‐lactide) (PLLA) thermal degradation has been developed. Based on the random chain scission mechanism, effects of temperature and time on the molecular weight and polydispersity index are included in this model. It incorporates the degradation and recombination reaction of PLLA thermal degradation, while taking into account the equal probability assumption. The developments of molecular weight and polydispersity index of PLLA polymer in the thermal degradation process were investigated at temperature ranging from 180–220°C, the experimental data show PLLA reaches its thermal degradation equilibrium in 2 h. The simulated results of this model are compared with the measured molecular weight and polydispersity index of the PLLA polymer. The changes of the molecular weight and polydispersity index in the PLLA thermal degradation can be predicted by this model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2557–2562, 2003     

Molecular ordering and α′-form formation of poly(l-lactide) during the hydrolytic degradation

Hydrolytic degradation ability is an intriguing characteristic of poly(l-lactide) (PLLA) and it has been intensively investigated recently. However, the microstructure evolution of PLLA during the early stage of the hydrolytic degradation process is neglected. In this work, amorphous PLLA was hydrolyzed in alkaline media at temperatures from 40 to 60 °C. The variations of weight loss and molecular weight were measured to study the degree of the hydrolytic degradation of PLLA. The effect of hydrolytic degradation on microstructure of the amorphous PLLA was investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscope (FTIR), wide angle X-ray diffraction (WAXD) and scanning electron microscope (SEM). The results clearly proves the occurrence of molecular ordering and the formation of α′-form PLLA, which is greatly related to the hydrolytic degradation conditions. At relatively low hydrolytic degradation temperature (40 and 50 °C), locally ordered structure is provoked, while a large number of α′-form crystallites are induced at relatively high temperature (60 °C). This work is very significant in understanding the microstructure evolution of PLLA during the hydrolytic degradation process.     

Toughening modification of PLLA/PBS blends via in situ compatibilization

Biodegradable polymer blends consisting of poly(L ‐lactic acid) (PLLA) and poly(butylene succinate) (PBS) were prepared in the presence of dicumyl peroxide (DCP). The effects of DCP content on the mechanical properties, thermal and rheological behavior, phase morphology as well as the toughening mechanism of the blends were investigated. The notched Izod impact strength of PLLA/PBS (80/20) blend significantly increased after the addition of 0.05–0.2 phr DCP, but the strength and modulus monotonically decreased with increasing DCP content. PBS acted as a nucleating agent at the environmental temperature below its melting temperature and accelerated the crystallization rate of PLLA but had little effect on its final degree of crystallinity. The degree of crystallinity of PBS and the cold crystallization ability of PLLA gradually reduced with increasing DCP content. The addition of DCP induced an increase in viscosity of the blends at low frequencies as well as finer dispersion of PBS particles and better interfacial adhesion between PLLA and PBS, indicating the in situ compatibilization occurred between the two components. The optical clarity of PLLA/PBS blends was significantly improved after the addition of DCP, which was in accordance with the crystallization behavior and phase structure of the blends. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Production of Hydroxyapatite/Bioactive Glass Biomedical Composites by the Hot-Pressing Technique

Biomedical composites of hydroxyapatite (HA) and bioactive glass (BG) have been difficult to obtain as a dense body without the undesirable occurrence of thermal reactions and phase degradation. Herein, HA–BG dense composites were produced by the hot-pressing technique. A range of HA–BG powder mixtures (30–50 wt% BG) was fully densified by hot pressing at temperatures as low as ∼700°–800°C. On the other hand, the HA–BG composites could not be densified by pressureless sintering because their composition was degraded due to a severe thermal reaction. The hot-pressed composites had significantly improved flexural strengths (∼60 MPa) as compared with those subjected to pressureless sintering (∼30 MPa) or the pure HA control (∼40 MPa). The hot-pressed HA–BG composites showed significantly enhanced bioactivity in a simulated body fluid, as well as osteoblast cell activity with respect to the pure HA, confirming their excellent in vitro biocompatibility.     

In vitro hydrolytic degradation of poly(para-dioxanone) with high molecular weight

The in vitro hydrolytic degradation of high molecular weight poly (para-dioxanone) was studied by examining the changes of weight retention, water absorption, pH value, tensile strength, break elongation, thermal properties, and morphology of high molecular weight PPDO in phosphate buffered saline (PBS) (pH 7.44) at 37°C for 8 weeks. During the degradation, all samples’ weight retention decreased and water absorption increased significantly, whereas hydrolysis rate of PPDO bars varied with molecular weight. Compared with lower molecular weight samples, higher molecular weight PPDO samples exhibited higher hydrolysis rate. The samples’ glass transition temperature (Tg) decreased notably, while the degrees of crystallinity (Dc) increased. The samples almost totally lost their tensile strengths and breaking elongation after 4 weeks of degradation. The results suggested that the stability of PPDO in vitro hydrolytic degradation increased with the increase of molecular weight.