Xinhua Zong

Structure and process relationship of electrospun bioabsorbable nanofiber membranes

Abstract An electrospinning method was used to fabricate bioabsorbable amorphous poly( d , l -lactic acid) (PDLA) and semi-crystalline poly( l -lactic acid) (PLLA) nanofiber non-woven membranes for biomedical applications. The structure and morphology of electrospun membranes were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and synchrotron wide-angle X-ray diffraction/small angle X-ray scattering. SEM images showed that the fiber diameter and the nanostructured morphology depended on processing parameters such as solution viscosity (e.g. concentration and polymer molecular weight), applied electric field strength, solution feeding rate and ionic salt addition. The combination of different materials and processing parameters could be used to fabricate bead-free nanofiber non-woven membranes. Concentration and salt addition were found to have relatively larger effects on the fiber diameter than the other parameters. DSC and X-ray results indicated that the electrospun PLLA nanofibers were completely non-crystalline but had highly oriented chains and a lower glass transition temperature than the cast film.

Control of degradation rate and hydrophilicity in electrospun non-woven poly(D, L-lactide) nanofiber scaffolds for biomedical applications

Typical properties of poly(D,L-lactide) (PLA)-based scaffolds (films and foams), such as long degradation time, mechanical stiffness and hydrophobicity, are sometimes not suitable for biomedical applications. These properties can be substantially altered by electrospinning of PLA blends with miscible poly(lactide-co-glycolide) (PLGA) random copolymers, poly(lactide-b-ethylene glycol-b-lactide) (PLA-b-PEG-b-PLA) triblock copolymers, and a lactide (used as a hydrolytic catalyst). Electrospun scaffolds based on the multi-component PLA blends, comprised of randomly interconnected webs of sub-micron sized fibers, have a bulk density of 0.3-0.4 g/cm3. In this study, the concentration effects of PLA-b-PEG-b-PLA triblock copolymer and lactide on the cell proliferation and the hydrophilicity of electrospun scaffolds were investigated. Based on in vitro degradation study, we found that the electrospun scaffold having PLA (40 wt%), PLGA (LA/GA=50/50, 25 wt%), PLA-b-PEG-b-PLA (20 wt%), and lactide (15 wt%) underwent a rapid weight loss of approximately 65% in 7 weeks. The hydrophobicity of this membrane, as determined by contact angle measurements in a cell buffer solution, decreased by approximately 50% from 105 degrees (of an electrospun PLA scaffold) to 50 degrees. The selection of suitable chemical compositions in conjunction with the non-invasive electrospinning process is useful in the production of a new kind of biodegradable scaffolds suitable for different biomedical applications such as cell storage and delivery as well as prevention of post-surgical adhesion because of their porosity, mechanical flexibility and tunable biodegradability.

Control of structure, morphology and property in electrospun poly(glycolide-co-lactide) non-woven membranes via post-draw treatments

Non-woven biodegradable membranes fabricated by electrospinning have recently attracted a great deal of attention for biomedical applications. In this study, microstructure, morphology and texture of electrospun poly(glycolide-co-lactide) (GA/LA: 90:10, PLA10GA90) non-woven membranes were investigated after post-draw and thermal treatments to tailor the degradation and mechanical properties. As-prepared electrospun PLA10GA90 membranes exhibited a low degree of crystallinity. When annealed at elevated temperatures without drawing, the membrane showed a higher degree of crystallinity with distinct lamellar structure but no overall orientation. The crystal orientation improved significantly when the membrane was drawn and annealed. As the elongation ratio increased, the degree of orientation and the tensile strength were increased. The corresponding tensile retention time was also increased from 2 to 12 days during in vitro degradation. Post-drawn and annealed membranes exhibited a slower degradation rate in the beginning of incubation, but a faster rate after two weeks of degradation when compared to as-spun membranes.

Prevention of Postsurgery-Induced Abdominal Adhesions by Electrospun Bioabsorbable Nanofibrous Poly(lactide-co-glycolide)-Based Membranes

Objectives:The objective of this study was to evaluate the efficacy of nonwoven bioabsorbable nanofibrous membranes of poly(lactideco-glycolide) for prevention of postsurgery-induced abdominal adhesions. Summary Background Data:Recent reports indicated that current materials used for adhesion prevention have only limited success. Studies on other bioabsorbable materials using a new fabrication technique demonstrated the promising potential of generating an improved and inexpensive product that is suitable for a variety of surgical applications. Methods:All rats underwent a midline celiotomy. The cecum was identified and scored using an abrasive pad until serosal bleeding was noted on the anterior surface. A 1 × 1 cm2 of abdominal wall muscle was excised directly over the cecal wound. The celiotomy was then closed in 2 layers immediately (control) after a barrier was laid in between the cecum and the abdominal wall. All rats underwent a second celiotomy after 28 days to evaluate the extent of abdominal adhesions qualitatively and quantitatively. Results:Cecal adhesions were reduced from 78% in the control group to 50% in the group using biodegradable poly(lactide-co-glycolide) (PLGA) nonwoven nanofibrous membranes (n = 10, P = 0.2) and to 22% in the group using membranes containing PLGA and poly(ethylene glycol)/poly(D,L-lactide) (PEG-PLA) blends (n = 9, P = 0.03). Electrospinning method also enabled us to load an antibiotic drug Cefoxitin sodium (Mefoxin; Merck Inc., West Point, PA) with high efficacy. The electrospun PLGA/PEG-PLA membranes impregnated with 5 wt% cefoxitin sodium, which amounts to approximately 10% of the systemic daily dose typically taken after surgery in humans, completely prevented cecal adhesions (0%) in rats. Conclusions:Electrospun nonwoven bioabsorbable nanofibrous membranes of poly(lactide-co-glycolide) were effective to reduce adhesions at the site of injury using an objective rat model. The membrane acted as a physical barrier but with drug-delivery capability. The combined advantages of composition adjustment, drug-loading capability, and easy placement handling (relatively hydrophobic) make these membranes potentially successful candidates for further clinical evaluations.

Structural changes during deformation of Kevlar fibers via on-line synchrotron SAXS/WAXD techniques

Abstract On-line studies of structure and morphology changes in Kevlar 49 fibers during stretching were carried out using synchrotron simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. A unique two-dimensional (2D) image analysis method was used to extract quantitative information of crystal, amorphous and mesomorphic fractions from 2D WAXD patterns. Results showed that about 20% of the fraction (mass) in the Kevlar 49 fiber was mesophase, 50% was crystalline and 30% was amorphous. There were transitions between crystal, amorphous and mesomorphic fractions during deformation. The crystal orientation was obtained in terms of the Hermans orientation function f2 from the azimuthal scan of the (200) crystal reflection. The crystal orientation was found to be quite high in the Kevlar 49 fiber and increased with the stretch ratio. The fibril length and misorientation were also obtained from 2D SAXS patterns by using the Ruland method. Results showed that the fibril length decreased with the stretch ratio until 2.0% and then increased. The misorientation decreased with increasing stretch ratio.

Novel image analysis of two-dimensional X-ray fiber diffraction patterns : example of a polypropylene fiber drawing study

On-line studies of the structural development during continuous drawing of a polypropylene fiber were carried out using synchrotron wide-angle X-ray diffraction. A unique image analysis method was introduced to extract quantitative information on the crystal, amorphous and mesomorphic fractions. In addition, the unit-cell parameters and the crystal orientation were obtained under various draw conditions. It was found that the mesophase remained about constant during drawing. At draw ratios less than 6.0, the crystallinity increased and the crystal density decreased as a result of the stress-induced crystallization of crystals with a large degree of disordering. At draw ratios above 6.0, the crystallinity increased slowly and the decrease in crystal density was also retarded because of the draw-induced melting. The crystal orientation increased with increasing draw ratio up to a ratio of 6.0 and then decreased, probably because of chain breakage.

Morphological development in absorbable poly(glycolide), poly(glycolide-co-lactide) and poly(glycolide-co-caprolactone) copolymers during isothermal crystallization

Abstract Morphological development of the homopolymer, poly(glycolide), PGA; its random copolymers, poly(glycolide-co-lactide), PGA-co-PLA (5:95 and 90:10) and segmented block copolymer, poly(glycolide-co-caprolactone), PGA-co-PCL (75:25) during isothermal crystallization was studied using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques with synchrotron radiation. It was found that the lamellar morphology could best describe the superstructure of these polymers. During crystallization, both average long period (L) and lamellar thickness (lc) exhibited notable decreases with time, which were attributed to the mechanism of secondary crystallization in the form of lamellar-stacks insertion. Both values of L and lc were found to increase with temperature. In the chosen crystallization temperature range (100–200°C), homopolymer PGA exhibited the fastest crystallization rate and the lowest values of L and lc, probably due to the largest degree of supercooling. As a result, in copolymers with higher content of PGA, the crystallization rate increased and the values of L and lc decreased. The value of amorphous layer thickness (la) was the highest in PGA-co-PLA (5:95), but those in PGA, PGA-co-PLA (90:10) and PGA-co-PCL (75:25) were about the same. In addition, the values of L, lc and the crystallinity were the highest in PGA-co-PLA (5:95). Corresponding degrees of crystallinity in PGA homopolymer and PGA-co-PCL (75:25) and PGA-co-PLA (90:10) copolymers were relatively low.

Studies of the mesophase development in polymeric fibers during deformation by synchrotron SAXS/WAXD

On-line structural and morphological studies on Kevlar 49 and isotactic polypropylene (iPP) fibers during deformation were carried out using synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). A novel image analysis method was used to extract quantitative fractions of the crystal phase, the amorphous phase and a “mesomorphic” (intermediate) phase from two-dimensional (2D) WAXD patterns. Results showed that about 20 wt% in the Kevlar 49 fiber had an intermediate mesophase morphology. The transitions between crystal phase, amorphous phase and mesophase were not obvious during deformation of Kevlar 49 fiber at room temperatures. 2D SAXS patterns indicated that the superstructure of the Kevlar 49 fiber was fibril in nature. 2D WAXD results of iPP fibers showed that the α-form crystals were quite defective in the initial state and were converted to the well-known mesomorphic form by drawing at room temperatures. The mesophase in Kevlar 49 fibers was then compared with that in iPP fibers. The shape of one-dimensional equatorial peak of the mesophase in the iPP fiber was similar to that in the Kevlar fiber, indicating that the mesophase in both iPP and Kevlar fibers could be similar in some aspects of molecular arrangement. Corresponding 2D SAXS patterns showed that there was no obvious long period in the mesophase of the drawn iPP fiber. We speculate that the constituents of the mesomorphic fraction extracted in the drawn iPP fibers may consist of partially oriented bundles of helical chains with random helical hands as well as oriented chains with no helical structures (consisting of stereo/tacticity defects). The latter is similar to the mesophase of rigid chains in Kevlar fibers, consisting of only oriented chains with no helical structures.