Dufei Fang

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.

High-flux thin-film nanofibrous composite ultrafiltration membranes containing cellulose barrier layer

A novel class of thin-film nanofibrous composite (TFNC) membrane consisting of a cellulose barrier layer, a nanofibrous mid-layer scaffold, and a melt-blown non-woven substrate was successfully fabricated and tested as an ultrafiltration (UF) filter to separate an emulsified oil and water mixture, a model bilge water for on-board ship bilge water purification. Two ionic liquids: 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate, were chosen as the solvent to dissolve cellulose under mild conditions. The regenerated cellulose barrier layer exhibited less crystallinity (determined by wide-angle X-ray diffraction, WAXD) than the original cotton linter pulps, but good thermal stability (determined by thermal gravimetric analysis, TGA). The morphology, water permeation, and mechanical stability of the chosen TFNC membranes were thoroughly investigated. The results indicated that the polyacrylonitrile (PAN) nanofibrous scaffold was partially imbedded in the cellulose barrier layer, which enhanced the mechanical strength of the top barrier layer. The permeation flux of the cellulose-based TFNC membrane was significantly higher (e.g. 10×) than comparable commercial UF membranes (PAN10 and PAN400, Sepro) with similar rejection ratios for separation of oil/water emulsions. The molecular weight cut-off (MWCO) of TFNC membranes with cellulose barrier layer was evaluated using dextran feed solutions. The rejection was found to be higher than 90% with a dextran molecular weight of 2000 KDa, implying that the nominal pore size of the membrane was less than ∼50 nm. High permeation flux was also observed in the filtration of an emulsified oil/water mixture as well as of a sodium alginate aqueous solution, while high rejection ratio (above 99.5%) was maintained after prolonged operation. A variation of the barrier layer thickness could dramatically affect the permeation flux and the rejection ratio of the TFNC membranes, while different sources of cellulose, ionic liquids, and non-woven supports did not. As ionic liquids can be recycled and reused without obvious decomposition, the chosen method also demonstrates a benign pathway to fabricate the cellulose barrier layer for other types of membranes.

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.

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.

Combined techniques of Raman spectroscopy and synchrotron two-dimensional x-ray diffraction for in situ study of anisotropic system: Example of polymer fibers under deformation

Simultaneous measurements of Raman spectroscopy and synchrotron two-dimensional (2D) wide-angle x-ray diffraction (WAXD) have been successfully demonstrated for in situ study of an anisotropic system: isotactic polypropylene (iPP) fiber under tensile deformation. A fiber-optic probe was used to remotely deliver the incident laser beam on the sample as well as to collect the Raman signal based on the confocal arrangement, whereas high resolution 2D WAXD patterns were obtained simultaneously at the same position during deformation of polymers. The combined techniques yielded complementary information on the molecular structural evolution in both crystalline and amorphous phases. 2D WAXD results showed that the α-form iPP crystals were converted into the mesophase upon stretching at room temperature. Corresponding Raman spectra showed that characteristic bands from the crystal phase became weaker or disappeared during the transition from the crystal phase to the mesophase. However, the bands associated with ...

Shear-Induced Precursor Relaxation-Dependent Growth Dynamics and Lamellar Orientation of β-Crystals in β-Nucleated Isotactic Polypropylene

Although a shear flow field and β-nucleating agents (β-NAs) can separately induce the formation of β-crystals in isotactic polypropylene (iPP) in an efficient manner, we previously encountered difficulty in obtaining abundant β-crystals when these two factors were applied due to the competitive growth of α- and β-crystals. In the current study, to induce the formation of a high fraction of β-crystals, a strategy that introduces a relaxation process after applying a shear flow field but before cooling to crystallize β-nucleated iPP was proposed. Depending on the relaxation state of the shear-induced oriented precursors, abundant β-crystals with a refined orientation morphology were indeed formed. The key to producing these crystals lay in the partially dissolved shear-induced oriented precursors as a result of the relaxation processs ability to generate β-crystals by inducing the formation of needlelike β-NAs. Therefore, the content of β-crystals gradually increased with relaxation time, whereas the overall crystallization kinetics progressively decreased. Moreover, more time was required for the content of the β-phase to increase to the (maximum) value observed in quiescent crystallization than for the effect of flow on crystallization kinetics to be completely eliminated. The c-axis of the oriented β-lamellae was observed to be perpendicular, rather than parallel, to the fiber axis of the needlelike β-NAs, as first evidenced by the unique small-angle X-ray scattering patterns obtained. The significance of the relaxation process was manifested in regulating the content and morphology of oriented β-crystals in sheared, β-nucleated iPP and thus in the structure and property manipulation of iPP.