PLLA Content Research Articles

Impact of Nanoconfinement on Polylactide Crystallization and Gas Barrier Properties.

The barrier properties of poly(l-lactide) (PLLA) were investigated in multinanolayer systems, probing the effect of confinement, the compatibility between the confining and the confined polymer, crystal orientation, and amorphous phase properties. The multilayer coextrusion process was used to confine PLLA between two amorphous polymers (polystyrene, PS; and polycarbonate, PC), which have different chemical affinities with PLLA. Confined PLLA layers of approximately 20 nm thickness were obtained. The multinanolayer materials were annealed at different temperatures to obtain PLLA crystallites with distinct polymorphs. PLLA annealed in PC/PLLA films at 120 °C afforded a crystallinity degree up to 65%, and PLLA annealed in PC/PLLA or PS/PLLA films at 85 °C had a crystallinity degree of 45%. WAXS measurements evidenced that the PLLA lamellas between PS layers had a mixed in-plane and on-edge orientation. PLLA lamellas between PC layers were uniquely oriented in-plane. DMA results evidenced a shift of the PC glass transition toward lower temperature, suggesting the possible presence of an interphase. The development of the rigid amorphous fraction (RAF) in the amorphous phase during annealing was impacted by the confiner polymer. The RAF content of semicrystalline PLLA was about 15% in PC/PLLA, whereas it was neglectable in PS/PLLA. The oxygen barrier properties appeared to be governed by RAF content, and no impact of the PLLA polymorph or the crystalline orientation was observed. This study shows that the confinement of PLLA on itself does not impact barrier properties but that the proper choice of the confiner polymer can lead to decrease the phase coupling which creates the RAF. It is the prevention of RAF that decreases permeability.

Fully biobased biodegradable poly(l‐lactide)‐b‐poly(ethylene brassylate)‐b‐poly(l‐lactide) triblock copolymers: synthesis and investigation of relationship between crystallization morphology and thermal properties

AbstractWell‐defined poly(l‐lactide‐b‐ethylene brassylate‐b‐l‐lactide) (PLLA‐b‐PEB‐b‐PLLA) triblock copolymer was synthesized by using double hydroxyl‐terminated PEBs with different molecular weights. Gel permeation chromatography and NMR characterization were employed to confirm the structure and composition of the triblock copolymers. DSC, wide‐angle X‐ray diffraction, TGA and polarized optical microscopy were also employed to demonstrate the relationship between the composition and properties. According to the DSC curves, the cold crystallization peak vanished gradually with decrease of the PLLA block, illustrating that the relatively smaller content of PLLA may lead to the formation of a deficient PLLA type crystal, leading to a decrease of melting enthalpy and melting temperature. Multi‐step thermal decompositions were determined by TGA, and the PEB unit exhibited much better thermal stability than the PLLA unit. Polarized optical microscopy images of all the triblock samples showed that spherulites which develop radially and with an extinction pattern in the form of a Maltese cross exhibit no ring bond. The growth rate of the spherulites of all triblock samples was investigated. The crystallization capacity of PLLA improved with incorporation of PLLA, which accords with the DSC and wide‐angle X‐ray diffraction results. © 2019 Society of Chemical Industry

Nitrate removal performance and diversity of active denitrifying bacteria in denitrification reactors using poly(L-lactic acid) with enhanced chemical hydrolyzability.

Poly(L-lactic acid) (PLLA) can be used as an external electron donor in denitrification reactors to treat drinking water, aquaculture water, and industrial wastewater with an imbalanced carbon/nitrogen ratio. However, for PLLA to function in these applications, its chemical hydrolyzability requires improvement. Although the adjustment of the crystallinity (Xc) is effective in improving the hydrolyzability of PLLA, the condition for the Xc of PLLA, in which a sufficient amount of lactic acid is released for denitrification, must be clarified. Therefore, this study investigated the effective Xc range and optimal PLLA content as an electron donor for continuous nitrate removal in denitrification reactors. This study also explored the abundance, succession, and diversity of active denitrifying bacteria in denitrification reactors. The nitrate removal activity of activated sludge using the highly crystalline PLLA (Xc = 39.4%) was 1.8 mg NO3- -N g MLSS-1 h-1, which is 2.4 times higher than that using the nearly amorphous PLLA (Xc = 0.9%). During the 57 days of operation, the denitrification reactor with 3% (w/v) highly crystalline PLLA continued to completely remove nitrate, with a maximum nitrate removal activity of 22.8 mg NO3- -N g MLSS-1 h-1. The 16S rRNA amplicon sequencing and clone library analyses are using transcripts of two nitrite reductase genes, encoding cytochrome cd1 nitrite reductase, and copper-containing nitrite reductase revealed that bacteria belonging to the families Comamonadaceae, Rhodocyclaceae, and Alcaligenaceae were active denitrifying bacteria in the denitrification reactor using PLLA.

Preparation of polylactide scaffolds for cancellous bone regeneration – preliminary investigation and optimization of the process

Abstract Polylactide scaffolds were prepared for the cancellous bone regeneration by the phase inversion method with freeze-extraction variant. A preliminary investigation and the optimization of the process were performed. For the obtained scaffolds, regression equations determining the effect: PLLA concentration by weight in 1,4-dioxane; volume ratio of the porophore/PLLA solution in 1,4-dioxane; and implant-forming solution pouring temperature, on the open porosity and mass absorbability were determined. The conditions in which the obtained implants were characterized by the maximal absorbability with the open porosity greater than 90 % were obtained.

Polyether-polyester and HMDI Based Polyurethanes: Effect of PLLA Content on Structure and Property

Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols), polytetrahydrofuran diol (PTMG diols), 4,4′-dicyclohexylmethane diisocyanate (HMDI), and 1,4-butanediol (BDO) by a two-step reaction, and the morphology and property of the resultant TPU could be adjusted by varying the PLLA contents. The soft segment was composed of PLLA and PTMG diols. By controlling the percentage of PLLA in the soft segment, the glass transition temperature and mechanical properties of the polyurethanes could be regulated. Based on the FTIR spectrum, we found that two kinds of hydrogen bonding existed individually in soft matrix and hard domain. The hydrogen bonding in soft matrix was unstable, which could be destroyed during elongation. With in situ stretching WAXS and SAXS experiments, we found that the PLLA crystal was destroyed and the PLLA domain oriented along the stretch direction. Finally, we proposed a schematic model to illustrate the microstructures of these elastomers before and after stretch.

Highly toughened and heat-resistant poly(l-lactide) materials through interfacial interaction control via chemical structure of biodegradable elastomer

Three biodegradable elastomers with different chemical structures, i.e., polyurethane (PU), poly(l-lactide)-b-polyurethane-b-poly(l-lactide) (LPUL) and poly(d-lactide)-b-polyurethane-b-poly(d-lactide) (DPUD) triblock copolymers were prepared to blend with commercial poly(l-lactide) (PLLA) to provide weak, medium and strong interfacial interactions through weak van der Walls, interfacial chain entanglement and interfacial stereocomplex (SC) crystallization, respectively. Morphology analysis indicated that the size of dispersed phase in the amorphous PLLA matrix decreased with increasing PLLA or PDLA content of the biodegradable elastomers and agglomeration of dispersed particles occurred obviously during matrix crystallization for PLLA/PU and PLLA/LPUL blends due to the relatively weak interfacial interactions, while agglomeration did not occur apparently for PLLA/DPUD blends due to the strong interfacial interaction arisen from the interfacial SC crystallites. With well-tuned and stabilized phase morphology, PLLA/DPUD exhibited the best toughening efficiency for both the amorphous and highly crystalline PLLA matrix. Moreover, the PLLA/DPUD showed the highest mechanical strength and crystallization rate, attributing to the presence of interfacial SC crystallites, which could reinforce the mechanical strength and work as efficient nucleating agents for crystallization of PLLA matrix. In addition, PLLA/DPUD blends showed superior heat resistance over PLLA/PU and PLLA/LPUL blends by processing on conventional machine. All the excellent performances were attributed to the special interfacial interaction originated from interfacial SC crystallites of PLLA/DPUD blends.

Hydrolytic degradation of PCL-PLLA semi-IPNs exhibiting rapid, tunable degradation.

Accelerating the rate of polyester hydrolytic degradation is of interest for numerous biomedical applications. Poly(ε-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) have been extensively studied as thermoplastic homo- and copolymers as well as PCL-PLLA blends. PCL-PLLA semi-interpenetrating networks (semi-IPN) prepared with thermoplastic PLLA embedded in a cross-linked PCL diacrylate (PCL-DA) network were previously shown to exhibit uniquely accelerated degradation behavior that increased with PLLA content. Herein, their properties before and during degradation were further investigated to reveal the origin of this behavior and to better understand the semi-IPNs' degradation mechanism. Initially, semi-IPNs exhibited restricted spherulite size and irregularity, as well as a phase-separated morphology and PLLA-rich surface. Under accelerated conditions (1 M NaOH, 37 °C), degradation was revealed to be initiated in PLLA regions. It was also found that the PCL-DA crosslinking and PCL-PLLA phase separation played the largest roles in degradation rates and that semi-IPNs underwent faster rates of degradation than an analogous blend largely due to the reduced crystallinity of PCL-DA. Non-accelerated conditions (PBS [pH = 7.4], 37 °C) up to 56 weeks, which had never before been studied for polyester semi-IPNs, revealed similar trends in degradation rates.

Macroporous poly (l-lactic acid)/chitosan nanofibrous scaffolds through cloud point thermally induced phase separation for enhanced bone regeneration

A new method called cloud point thermally induced phase separation (CP-TIPS) was developed to prepare poly (l-lactic acid) (PLLA) scaffolds with macropores over 300 μm in PLLA/dioxane/H2O ternary system. The concentration of PLLA was 4% (w/v), and the solvent was dioxane with 14% of deionized water. By maintaining the clear solution of the ternary system near and above the cloud point for 2 h, followed by a large enough quenching depth (−80 °C), the crystallization of the α′-form crystal became privileged, and the microstructure of the pore wall was dominated with nanofibers. In contrast, conventional TIPS process resulted in scaffolds with similar pore size but platelet-like microstructure on the pore walls. The unique macroporous nanofibrous PLLA scaffold showed well elasticity and flexibility after swelling in 70% acetone. This property further enabled a facile “mechanical squeeze and intake” of high concentration viscous chitosan solution into the porous structure to modify the composite scaffolds. The compressive modulus of macroporous nanofibrous PLLA/CS scaffolds reached about 1 MPa. The hydrophilicity of the scaffold was greatly enhanced and the pH value remained stable in the first 3 weeks after degradation in vitro. The effect of chitosan concentration in the composite scaffolds on cell affinity and the osteogenic differentiation was evaluated. Finally, a critical-size rat calvarial bone defect model was used to evaluate the osteogenesis of the scaffolds in vivo and the composite scaffold with 3% chitosan significantly enhanced bone regeneration.

One-step fabrication of functionalized poly(l-lactide) porous fibers by electrospinning and the adsorption/separation abilities

In this work, novel functionalized poly(l-lactide) (F-PLLA) porous fibers were fabricated through electrospinning using the PLLA/methylene chloride (CH2Cl2)/N,N-dimethylformamide (DMF) solution containing diethylenetriamine (DETA) and γ-aminopropyltriethoxysilane (KH-550). The effects of PLLA, DETA and KH-550 contents on the morphologies of the electrospun fibers were systematically investigated, and the results showed that at PLLA, DETA and KH-550 contents of 20% w/v, 2 wt% and 3 wt%, respectively, the electrospun F-PLLA fibers exhibited the homogeneous distribution of fiber diameters and the homogeneous porous structure on the fiber surface. Nitrogen-containing groups were successfully introduced to the electrospun fibers, which induced the great improvement of the hydrophilicity of the membrane surface. Adsorption measurements showed that the electrospun F-PLLA membrane had good adsorption ability toward Congo red (CR), and the adsorption capacity at room temperature was enhanced in 16 times compared with the common PLLA fiber membrane, and the maximum adsorption capacity was 135.7 mg g-1. Furthermore, the adsorption behavior could be well described by the pseudo second-order model. Oil/water separating measurements showed that the electrospun F-PLLA membrane exhibited high separation efficiency and the maximum water fluxes were 2018 and 1861 L m-2 h-1 in separating non-emulsified and emulsified oil/water system under atmospheric pressure, respectively.

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

AbstractThe hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry

Solvent-free preparation of porous poly(l-lactide) microcarriers for cell culture

Porous polymeric microcarriers are a versatile class of biomaterial constructs with extensive use in drug delivery, cell culture and tissue engineering. Currently, most methods for their production require potentially toxic organic solvents with complex setups which limit their suitability for biomedical applications and their large-scale production. Herein, we report an organic, solvent-free method for the fabrication of porous poly(l-lactide) (PLLA) microcarriers. The method is based on the spherulitic crystallization of PLLA in its miscible blends with poly(ethylene glycol) (PEG). It is shown that the PLLA spherulites are easily recovered as microcarriers from the blends by a water-based process. Independent control over microcarrier size and porosity is demonstrated, with a higher crystallization temperature leading to a larger size, and a higher PLLA content in the starting blend resulting in a lower microcarrier porosity. Microcarriers are shown to be biocompatible for the culture of murine myoblasts and human adipose stromal/stem cells (hASC). Moreover, they support not only the long-term proliferation of both cell types but also hASC differentiation toward osseous tissues. Furthermore, while no significant differences are observed during cell proliferation on microcarriers of two different porosities, microcarriers of lower porosity induce a stronger hASC osteogenic differentiation, as evidenced by higher ALP enzymatic activity and matrix mineralization. Consequently, the proposed organic-solvent-free method for the fabrication of biocompatible porous PLLA microcarriers represents an innovative methodology for ex vivo cell expansion and its application in stem cell therapy and tissue engineering. Statement of SignificanceWe report a new solvent-free method for the preparation of porous polymeric microcarriers for cell culture, based on biocompatible poly(l-lactide), with independently controllable size and porosity. This approach, based on the spherulitic crystallization in polymer blends, offers the advantages of simple implementation, biological and environmental safety, easy adaptability and up-scalablility. The suitability of these microcarriers is demonstrated for long-term culture of both murine myoblasts and human adipose stromal/stem cells (hASCs). We show that prepared microcarriers support the osteogenic differentiation of hASCs, provided microcarriers of properly-tuned porosity are used. Hence, this new method is an important addition to the arsenal of microcarrier fabrication techniques, which will contribute to the adoption, regulatory approval and eventually clinical availability of microcarrier-based treatments and therapies.

Preparation of an environmentally friendly antifouling degradable polyurethane coating material based on medium-length fluorinated diols

ABSTRACTA novel medium-length fluorinated diols and poly(L-lactide) (PLLA) were synthesized via Michael addition reaction and ring-opening polymerization, respectively. Subsequently, Synthetic medium-length fluorinated diols and PLLA were combined to prepare new polyurethane composites with degradability and low surface energy. The compositional analysis and structural characterization of synthetic materials were characterized by using fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance spectra (1HNMR). Thermogravimetric analysis(TGA) indicated that the introduction of medium-length fluorinated diols improved the thermal stability of the polyurethane. The biodegradation and low surface energy of the polyurethane were investigated by static hydrolysis experiment and water contact angle test. It was found that the degradation rate of the polyurethane increased as measurement time went on when the PLLA content was under 40%, and the water contact angle increased from 71.12° to 108.24° with the increase of fluorine content, which indicated that the degradable and low surface energy polyurethane has a potential as a coating material for a marine antifouling coating application.

Disclosing the crystallization behavior and morphology of poly(ϵ‐caprolactone) within poly(ϵ‐caprolactone)/poly(l‐lactide) blends

AbstractIn this work, the effect of poly(l‐lactide) (PLLA) components on the crystallization behavior and morphology of poly(ϵ‐caprolactone) (PCL) within PCL/PLLA blends was investigated by polarized optical microscopy, DSC, SEM and AFM. Morphological results reveal that PCL forms banded spherulites in PCL/PLLA blends because the interaction between the two polymer components facilitates twisting of the PCL lamellae. Additionally, the average band spacing of PCL spherulites monotonically decreases with increasing PLLA content. With regard to the crystallization behaviors of PCL, the crystallization ability of PCL is depressed with increase of the PLLA content. However, it is interesting to observe that the growth rate of PCL spherulites is almost independent of the PLLA content while the overall isothermal crystallization rate of PCL within PCL/PLLA blends decreases first and then increases at a given crystallization temperature, indicating that the addition of PLLA components shows a weak effect on the growth rate of the PCL but mainly on the generation of nuclei. © 2018 Society of Chemical Industry

Unique Ivy-Like Morphology Composed of Poly(lactic acid) and Bacterial Cellulose Cryogel.

This study examines the unique morphology and properties of enhanced poly(l-lactic acid) (PLLA) monoliths having a bacterial cellulose (BC) framework. Open-porous BC/PLLA monoliths were successfully prepared using thermally induced phase separation (TIPS) and a freeze-drying technique. The BC/PLLA monoliths exhibited a unique ivy-like structure composed of leaf-like PLLA units and a BC fiber network. We demonstrated for the first time that the interpenetrating BC fiber gives PLLA monoliths four times higher compressive strength than the pristine PLLA. Scanning electron microscopy observation and the N2 adsorption test revealed that the size of PLLA units and the surface area of the monoliths can be manipulated by varying the starting PLLA concentration during the TIPS process. Moreover, the hydrophilicity of the PLLA monoliths was easily controlled by incorporating BC; the neat PLLA monoliths showed a high static water contact angle of as high as 128.8 ± 1.1°, whereas the BC/PLLA monoliths exhibited a much lower contact angle (102.1 ± 1.7°) and greater absorbability to water.

PLLA-PHB fiber membranes obtained by solvent-free electrospinning for short-time drug delivery.

Fibers of poly(L-lactic acid) (PLLA)/polyhydroxybutyrate (PHB) with different concentrations of the drug dipyridamole (DPD) were prepared using solvent-free melt electrospinning to obtain a polymeric drug delivery system. The electrospun fibers were morphologically, structurally, thermally, and dynamically characterized. Crazes that resemble lotus root crevices were interestingly observed in the 7:3 PLLA/PHB fibers with 1% DPD. The crystallinity of PLLA slightly decreased as PHB was incorporated, and the addition of DPD significantly reduced the melting temperature of the composite. The interactions between PLLA and PHB mainly occurred at a proportion of 7:3, and drug encapsulation in the fibers was verified. The kinetic profiles of drug release demonstrated the predominant multiple patterns involving a diffusional stage in the short-term mode of release and kinetic process related to the hydrolysis of the biopolymers. Furthermore, the dynamic behavior of the polymer molecules was evaluated based on the segmental mobility using probe electron spin resonance spectroscopy. The segmental mobility in the amorphous fraction of PLLA decreased with increasing PLLA content. The 9:1 PLLA/PHB system was more resistant to polymer hydrolysis than to the 7:3 system and the rate of diffusion transport was approximately two times higher for the 7:3 PLLA/PHB fibers than for the 9:1 PLLA/PHB fibers.

Effect of Drug Carrier Melting Points on Drug Release of Dexamethasone-Loaded Microspheres.

Here, we examined the effect of melting point of drug carriers on drug release of dexamethasone (Dex)-loaded microspheres. We prepared poly(L-lactide-ran-ε-caprolactone) (PLC) copolymers with varying compositions of poly(ε-caprolactone) (PCL) and poly(L-lactide) (PLLA). As the PLLA content increased, the melting points of PLC copolymers decreased from 61 to 43°C. PLC copolymers in vials solubilized at 40-50°C according to the incorporation of PLLA into the PCL segment. Dexamethasone (Dex)-loaded PLC (MCxLy) microspheres were prepared by the oil-in-water (O/W) solvent evaporation/extraction method. The preparation yields were above 70%, and the mean particle size ranged from 30 to 90μm. The MCxLy microspheres also showed controllable melting points in the range of 40-60°C. Dex-loaded MCxLy microspheres showed similar in vitro and in vivo sustained release patterns after the initial burst of Dex. The in vitro and in vivo order of the Dex release was MC80L20>MC90L10>MC95L5, which agreed well with the melting point order of the drug carrier. Using in vivo fluorescence imaging of fluorescein (FI)-loaded microspheres implanted in animals, we confirmed the sustained release of FI over an extended period. In vivo inflammation associated with the PLC microsphere implants was less pronounced than that associated with Poly(lactide-co-glycolide) (PLGA). In conclusion, we successfully demonstrated that it is possible to control Dex release using Dex-loaded MCxLy microspheres with different melting points.

Precisely controlled two-step synthesis of cellulose-graft-poly(l-lactide) copolymers: Effects of graft chain length on thermal behavior

This study presented a method to polymerize to cellulose-graft-poly (l-lactide) (cellulose-g-PLLA) copolymers as chemical modification process to overcome disadvantage of melt processing of pristine cellulose due to the strong intermolecular hydrogen bonds. In order to maximize the chain length at the end of cellulose, we designed a precisely controlled polymerization based on a two-step synthesis; 1) short-chain copolymerization of cellulose in an ionic liquid, 2) further graft polymerization in N,N-dimethylformamide and the bulk phase. Accordingly, we could synthesize a copolymer in high yield, with the number of substitutions per glucose unit (DSPLLA) being close to the theoretical maximum value of 3 and the number of lactyl repeating units introduced per glucose unit (MSPLLA) of 212, at a high yield. While the glass transition temperature (Tg) of the copolymer was greatly decreased owing to dissociation of the hydrogen bonds of cellulose and plasticizing effects at a low PLLA content (MSPLLA = 11.2), the Tg gradually increased to attain a value close to that of pure PLLA as the content increased.The cellulose-g-PLLA with low molecular weight was amorphous phase, but the crystallinity started to show from the sample with MSPLLA of 42.0 and WPLLA = 95.0%. As the molecular weight contents of PLLA were increased, the cellulose-g-PLLA of the melting point and the heat of fusion was increased. The cellulose-g-PLLA of the strong inter- and intramolecular hydrogen bonds between the hydroxyl groups was found to affect PLLA crystallinity.

Fabrication and structural regulation of PLLA porous microspheres via phase inversion emulsion and thermally induced phase separation techniques

ABSTRACTIn this work, a facile, scalable technique was developed to produce biodegradable porous microspheres by combining an oil‐in‐oil (O/O) surfactant‐free phase inversion emulsion technique with thermally induced phase separation (TIPS) method. The effects of PLLA concentration, stirring speed, macromolecule weight, and organic solvents on the size and microstructure of microspheres were investigated by scanning electron microscopy (SEM). The results revealed a highly porous structured microsphere with controllable sizes and morphologies by tuning the synthesis conditions. The typical resulting PLLA microspheres consist of nanoscale topographic structured surface and highly microporous interior. The coarse nanotopography and microcellular inner structure lead to a high drug loading capacity up to 60% for the PLLA microspheres from THF. The cumulative release percentage of the ibuprofen could reach 80% for drug‐loaded microspheres with different microstructures. The fabricated PLLA microspheres would have potential applications in the field of drug delivery and tissue engineering. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44885.

Physical and Chemical Properties of Poly (l-lactic acid)/Graphene Oxide Nanofibers for Nerve Regeneration

ABSTRACTThe development of biodegradable polymeric nanofiber scaffolds for a potential effort to repair injured nerve cells is of great interest in nerve tissue engineering applications. Poly (L-lactic acid) (PLLA) has been widely used in nerve conduit studies due to its biocompatibility, easily shaped properties and degradation to low toxic lactic acid. However, its hydrophobicity and lack of binding sites for cellular activities restricts its use as implants. In this regard, this study involves the incorporation of graphene oxide (GO) into PLLA nanofibers for enhancing mechanical properties, electrical conductivity and hydrophilicity of PLLA to make it suitable for a potential peripheral nerve regeneration application. For this purpose, PLLA and PLLA/GO nanofibers were prepared via electrospinning. The processing parameters and solution parameters were optimized to adjust physical and mechanical properties of nanofiber in terms of size, porosity and biologically active affinity for cellular interaction. The morphology and composition of the developed electrospun fibers were characterized via, Scanning Electron Microscopy (SEM), Raman Spectroscopy, tensile testing and contact angle measurements. The morphological results showed that using chloroform/DMF ratio of 8/2 for 7wt% PLLA led to the formation of bead free and thinner PLLA fibers than fibers produced from other concentration of PLLA. Moreover, the addition of the GO resulted in decrease of the average diameter of PLLA fibers from 828 nm to 490 nm and the thinnest nanofiber structure was obtained by addition of 10 v/v % GO. The sonication time of GO highly enhanced the porosity of the nanofibers, namely the porosity of the nanofibers increased with increasing sonication time. Raman Spectroscopy exhibits peaks at bands of 1775, 873 and 1455 cm-1that are attributed to C=O stretching, C-COO stretching and CH3asymmetric deformation respectively for PLLA and 1379 and 1599 cm-1which represent structural imperfections and sp2 domain of carbon atoms respectively for GO. Hence, Raman peaks confirmed that GO was mixed in PLLA nanofibers. The incorporation of GO significantly improved the tensile strength from 2.25 MPa of pure PLLA to 8.13 MPa, 10.44 MPa and 12.93 MPa with 5, 7.5 and 10 v/v% of GO addition, respectively. The results revealed that the addition of GO led to enhanced chemical and physical properties of fibers which is promising for nerve regeneration applications.

Preparation of poly(L-lactic acid) membrane from solvent mixture via immersion precipitation

ABSTRACTPoly (L-lactic acid) (PLLA) membranes were fabricated through immersion precipitation method. 1, 4-dioxane (DX), N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethyl-acetamide (DMAc), and DX/NMP, DX/DMF and DX/DMAc were used as solvents severally. With a focus on the PLLA/DX/NMP/H2O system, the effect of solvent mixture on PLLA membrane was investigated by altering the ratio of DX/NMP. Various membrane morphologies were obtained, which were further correlated by mean of solubility parameter and viscosity of casting solution. It was found that the membrane cast with DX/NMP (1/1) exhibited ideal structure and better performance compared with membranes cast with same concentration of PLLA.