聚乙二醇-b-聚乳酸的合成及其电纺形成超细纤维研究

为了提高聚乳酸的亲水性,以辛酸亚锡为催化剂、聚乙二醇单甲醚(mPEG)为大分子引发剂进行丙交酯(LLA)开环聚合,合成聚乙二醇-b-聚乳酸两嵌段共聚物(PELA).以红外光谱1、H核磁共振谱、接触角测试、差热扫描量热分析等方法对PELA的结构及性能进行表征.结果表明,通过调控mPEG与LLA的投料比可以控制PELA的相对分子质量,而随着mPEG组分含量或链长增加,共聚物亲水性增强,但其Tg、Tcc、Tm有所降低.由普通电纺制备PELA超细纤维,并分别由乳液电纺和同轴电纺得到以水溶性聚氧化乙烯(PEO)为芯、PELA为壳的芯/壳结构复合超细纤维(E-PEO/PELA和C-PEO/PELA).扫描电镜和透射电镜结果表明,PELA、E-PEO/PELA和C-PEO/PELA超细纤维形貌良好.随着PELA中mPEG含量的增加,电纺PELA纤维膜的吸水率增强,而由乳液电纺和同轴电纺制备的PEO/PELA芯/壳结构超细纤维膜,亲水性均好于PELA超细纤维膜.     

Mimetics of Eggshell Membrane Protein Fibers by Electrospinning

Summary: Mimetics of eggshell membrane protein fibers have been obtained with an electrospinning technique based on soluble eggshell membrane protein (SEP) prepared previously. Poly(ethylene oxide), a biocompatible and water soluble polymer, is used to improve the processability of SEP. Blends of SEP/PEO aqueous solutions were electrospun. The diameters of the fibers are 0.3–20 μm depending on the concentration of the solution and the proportion of SEP/PEO. Two “cross‐linking” methods are investigated in order to improve the anti‐water property of the fibers.

Scanning electron micrograph of electrospun fibers.     

Centrifugally spun poly(ethylene oxide) fibers rival the properties of electrospun fibers

Centrifugal force spinning (CFS), also known as centrifugal spinning, forcespinning, or rotary jet spinning, provides considerably higher production rates than electrospinning (ES), but the more widespread use of CFS as an alternative depends on the ability to produce fibers with robust thermal and mechanical properties. Here, we report the CFS of poly(ethylene oxide) (PEO) fibers made using a spinning dope formulated with acetonitrile (AcN) as the volatile solvent, and we describe the thermal and mechanical properties of the centrifugally-spun fibers. Even though the formation, diameter, and morphology of electrospun and centrifugally-spun PEO fibers are relatively well-studied, the article presents three crucial contributions: the pioneering use of PEO solutions in AcN as spinning dope, characterization of crystallinity and mechanical properties of the centrifugally-spun PEO fibers, and a comparison with the corresponding properties of electrospun fibers. We find that fiber formation occurrs for the chosen CFS conditions if polymer concentration exceeds the entanglement concentration, determined from the measured specific viscosity. Most significantly, the centrifugally spun PEO fibers display crystallinity, modulus, elongation-at-break, and fiber diameter that rival the properties of electrospun PEO fibers reported in the literature.     

Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers

This paper elucidates the means to control precisely the morphology of electrospun liquid crystal/polymer fibers formed by phase separation. The relative humidity, solution parameters (concentration, solvent), and the process parameter (feed rate) were varied systematically. We show that the morphology of the phase‐separated liquid crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads‐on‐a‐string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liquid‐crystal (LC) core. The width of the polymer sheath and the diameter of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liquid crystals and because of their large surface area, they have potential applications as thermo‐, chemo‐, and biosensors. Because the size and shape of the liquid‐crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphology will be crucial in developing these applications.     

Electrospinning of polystyrene/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) blends

Ultrafine polystyrene (PS)/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) (MEH‐PPV) fibers were successfully prepared by electrospinning of PS/MEH‐PPV solutions in chloroform, 1,2‐dichloroethane, and tetrahydrofuran (THF). Three concentrations of the solutions were prepared: 8.5, 16, and 23.5% (w/v), with the compositional weight ratios between PS and MEH‐PPV being 7.5:1, 15:1, and 22.5:1, respectively. Smooth fibers only observed from 23.5% (w/v) PS/MEH‐PPV solution in chloroform. Improvement in the electrospinnability of 8.5% (w/v) PS/MEH‐PPV solution in chloroform was achieved by addition of an organic salt, pyridinium formate (PF), or by addition of a minor solvent with a high dielectric constant value. The average diameters of the as‐spun PS/MEH‐PPV fibers were between 0.30 and 5.11 μm. Last, photoluminescence of 8.5% (w/v) solutions of PS/MEH‐PPV in a mixed solvent system of chloroform and 1,2‐dichloroethane of various volumetric compositions and the resulting as‐spun fibers was investigated and compared. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1881–1891, 2005     

Effects of poly(ethylene oxide) and pH on the electrospinning of whey protein isolate

Poly(ethylene oxide) (PEO) is known for facilitating the electrospinning of biopolymer solutions, which are otherwise not electrospinnable. The objective of this study was to improve the understanding of the positive effects of PEO on the electrospinning of whey protein isolate (WPI) solutions under different pH conditions. Alterations in protein secondary structure and polymer solution properties (viscosity, conductivity, and dynamic surface tension), as induced by pH changes, significantly affected the electrospinning behavior of WPI/PEO (10% w/w: 0.4% w/w PEO) solutions. Acidic solutions resulted in smooth fibers (707 ± 105 nm) while neutral solutions produced spheres (2.0 ± 1.0 μm) linked with ultrafine fibers (138 ± 32 nm). In comparison, alkaline solutions produced fibers (191 ± 36 nm) that were embedded with spindle‐like beads (1.0 ± 0.5 μm). ¹³C NMR and FTIR spectroscopies showed that the increase in random coil and α‐helix secondary structures in WPI were the main contributors to the formation of bead‐less electrospun fibers. The electrospinning‐enabling properties of PEO on aqueous WPI solutions were attributed to physical chain entanglement between the two polymers, rather than specific polymer–polymer interactions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Preparation of Core‐Sheath Composite Nanofibers by Emulsion Electrospinning

Summary: Uniform core‐sheath nanofibers are prepared by electrospinning a water‐in‐oil emulsion in which the aqueous phase consists of a poly(ethylene oxide) (PEO) solution in water and the oily phase is a chloroform solution of an amphiphilic poly(ethylene glycol)‐poly(L ‐lactic acid) (PEG‐PLA) diblock copolymer. The obtained fibers are composed of a PEO core and a PEG‐PLA sheath with a sharp boundary in between. By adjusting the emulsion composition and the emulsification parameters, the overall fiber size and the relative diameters of the core and the sheath can be changed. A mechanism is proposed to explain the process of transformation from the emulsion to the core‐sheath fibers, i.e., the stretching and evaporation induced de‐emulsification. In principle, this process can be applied to other systems to prepare core‐sheath fibers in place of concentric electrospinning and it is especially suitable for fabricating composite nanofibers that contain water‐soluble drugs.

Schematic mechanism for the formation of core‐sheath composite fibers during emulsion electrospinning.     

Liquid crystal fibers produced by using electrospinning technique

This paper investigates the electrospinning process of liquid crystalline polysiloxane with cholesterol as side chain (LCPC) and the influence on the morphology of the formed fibers by mixing LCPC solution with small-molecule liquid crystal, triethylamine, and poly(ethylene oxide)(PEO). The mechanical properties of single fibers were characterized by a novel approach. The results indicate that, under appropriate conditions, fine liquid crystal fibers can be obtained and the preferable mechanical properties can be achieved, especially after annealing. WXRD was used to investigate the orientation of polymer molecules in the formed fibers, suggesting that strong interaction exists between LCPC and PEO molecule in the resulting composite fibers, and polymer molecular tends to arrange regularly during electrospinning processing. This research work provides a new and facile method of using electrospinning to prepare liquid crystal fibers, which would be useful for designing the related high-performance materials.     

Thermodynamic modeling and investigation of the formation of electrospun collagen fibers

Electrospun type I collagen fibers are very promising materials for tissue scaffold applications, but are typically fabricated from toxic solvents. Recently, electrospinning of type I collagen fibers by using environmentally friendly phosphate buffer saline (PBS)/ethanol solution has been explored. PBS/ethanol solvent systems offer better cell compatibility, but the high surface tension and high boiling point of the solvent system make the collagen difficult to electrospin and can cause inferior fiber morphology. In this study, the influence of solvent surface tension on the morphology of electrospun collagen fibers has been experimentally investigated and analyzed from a thermodynamics perspective. The analytical results indicate that solvents with high surface tension drive the formation of beads along the smaller, thinner fibers. In addition, beads with relatively small angular eccentricity were thermodynamically favorable. The experimental results presented herein corroborate the theoretical analysis and conclusions drawn from this study. The surface tension of the solvent has significant influence on the bead formation, especially in an aqueous system. The environmental humidity for the electrospinning process and the collagen concentration were also investigated. These parameters may result in variations of the evaporation-solidification rates, which consequently impact the formation and morphologies of electrospun collagen fibers. According to the thermodynamic analysis, uniform electrospun collagen fibers without beads can be obtained by manipulating solvent surface tension during the electrospinning process.     

Polymer entanglement loss in extensional flow: Evidence from electrospun short nanofibers

High strain rate extensional flow of a semidilute polymer solution can result in fragmentation caused by polymer entanglement loss, evidenced by appearance of short nanofibers during electrospinning. The typically desired outcome of electrospinning is long continuous fibers or beads, but, under certain material and process conditions, short nanofibers can be obtained, a morphology that has scarcely been studied. Here we study the conditions that lead to the creation of short nanofibers, and find a distinct parametric space in which they are likely to appear, requiring a combination of low entanglement of the polymer chains and high strain rate of the electrospinning jet. Measurements of the length and diameter of short nanofibers, electrospun from PMMA dissolved in a blend of CHCl₃ and DMF, confirm the theoretical prediction that the fragmentation of the jet into short fibers is brought about by elastic stretching and loss of entanglement of the polymer network. The ability to tune nanofiber length, diameter and nanostructure, by modifying variables such as the molar mass, concentration, solvent quality, electric field intensity, and flow rate, can be exploited for improving their mechanical and thermodynamic properties, leading to novel applications in engineering and life sciences. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1377–1391     

Carbon nanofibers with nanoporosity and hollow channels from binary polyacrylonitrile systems

Carbon nanofibers with new structural features, e.g. nanoporosity, hollow, U-shape cross-section, were generated by utilizing the phase separation behavior of polymer additive with polyacrylonitrile (PAN). The approach involved the formation of precursor fibers by electrospinning of binary mixtures of PAN with poly(ethylene oxide) (PEO), cellulose acetate (CA) or poly(methyl methacrylate) (PMMA), the removal of the polymer and the carbonization of the remaining PAN. The carbon nanofiber yield was ca 50% of PAN in all cases. Nanoporous carbon nanofibers with an average diameter of 100 nm were generated from the water treated PAN/PEO precursors. Multi-channel hollow fibers (90-190 nm diameters) were produced from the acetone treated PAN/CA precursors. Carbon fibers produced from the chloroform treated PAN/PMMA precursors were 250-400 nm in diameters and consisted of varied hollow structures, i.e., hollow and U-shape cross-sections from those containing 30% and 50% PAN, respectively, and multi-channel hollow fibers from the 70/30 PAN/PMMA precursor. Carbonization of equal-mass PAN/PMMA as-spun fibers also produced similarly U-shape cross-sections as the chloroform treated ones, showing promise of direct carbonization. This simple and yet versatile approach to create new structural features in carbonized fibers has shown to depend on the distinct phase separation as well as the pyrolytic behaviors of the second polymer component.     

Electrospinnability study of pea (Pisum sativum) and common bean (Phaseolus vulgaris L.) using the conformational and rheological behavior of their protein isolates

Pea protein isolate (PPI) and bean protein concentrate (BPC) were evaluated as fiber-forming vegetal source materials through electrospinning using various solvents. The effects of hexafluoroisopropanol (HFIP), trifluoroethanol (TFE), trifluoroacetic acid (TFA), formic acid (FA) and water on rheological and conformational properties of the protein solutions were determined. The morphology and molecular organization of the electrospun structures were studied. All PPI and BPC solutions displayed pseudoplastic behavior. Circular dichroism spectroscopy revealed that β-type turns and β-sheets were the dominant protein conformations in water, HFIP, and TFE. After electrospinning, most of the solutions afforded beads. Fiber-like morphologies were only obtained when BPC was dissolved in HFIP. BPC demonstrated better performance in the electrospinning process than PPI. Denaturation of the protein isolates was not sufficient to form fibers, the viscosity of the solution as well as the vapor pressure of the solvents played an important role in defining the morphology.     

Atmospheric plasma treatment of pre‐electrospinning polymer solution: A feasible method to improve electrospinnability

The electrospinnability of polyethylene oxide (PEO) was manipulated by atmospheric plasma treatment of pre‐electrospinning solutions. Conductivity, viscosity, and surface tension of PEO solutions increased after plasma treatment, and the plasma effect remained longer when the solution concentrate increased. Both untreated and treated solutions were then electrospun, and the morphology of the resultant nanofibers was observed by SEM. Atmospheric plasma treatment improved the electrospinnability of PEO solutions and led to less beads and finer diameter distribution in the resultant nanofibers. Additionally, plasma treatment of the pre‐electrospinning solutions affected the crystal structure of resultant nanofibers. These results suggest that atmospheric plasma treatment is a feasible approach to improve the electrospinnability of polymer solutions and can used to control the structure of electrospun nanofibers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Studies on poly(aquahydroxychromium diphenylphosphinate)

The novel inorganic polymer poly(aquahydroxychromium diphenylphosphinate) was investigated to obtain information concerning its degree of polydispersity and properties when dissolved in organic solvents. Viscometric, infrared absorption spectroscopic, and electrical conductimetric techniques were employed to ascertain the characteristics of the polymer dissolved in benzene, chlorobenzene, and chloroform. Gel permeation chromatography was used to determine the degree of heterogeneity of the polymer. Results indicate that the polymer, as prepared, is quite polydisperse. The polymer main chains do not undergo radical reactions with the solvents. High values of the Huggins interaction constant K′ suggest that polymer–solvent association reactions involving chain-endgroups are probable. Such reactions are also indicated by association constant values and by the shapes of phoreograms obtained from electrical conductance data. Both “local” and “bulk” solvent properties, such as the dielectric constant, appear to influence the characteristics of the polymer when dissolved in the different solvents.     

Electrospinning and cutting of ultrafine bioerodible poly(lactide‐co‐ethylene oxide) tri‐ and multiblock copolymer fibers for inhalation applications

Triblock copolymers made up of poly(ethylene oxide) (PEO) and polylactide (PLA) were synthesized and converted to fibers by the electrospinning process. A two‐step in situ‐synthesis in bulk was applied to extend PLA‐PEO‐PLA triblock copolymers with relatively short block length and low molecular weight in order to obtain electrospinnable materials. DL‐lactide was polymerized to the hydroxyl chain ends of PEO via the stannous octoate route. Hexamethylene diisocyanate (HDI) was added as chain extender in the second step, leading to poly(ether‐ester‐urethane) multiblock copolymers. The materials were electrospun from solutions in chloroform. Different concentrations and voltages were analyzed. The ether and ester blocks were varied in their block length and their effects on the fiber morphology was studied. Variations in the electrical conductivity of the chloroform solutions were investigated by adding triethyl benzyl ammonium chloride (TEBAC) in different amounts. Finally, with high quality electrospun PLA‐PEO‐PEO triblock copolymer fibers mechanical cutting was possible. Copyright © 2009 John Wiley & Sons, Ltd.     

Controlling electrospun nanofiber morphology and mechanical properties using humidity

Electrospinning is a fiber spinning technique used to produce nanoscale polymeric fibers with superior interconnectivity and specific surface area. The fiber diameter, surface morphology, and mechanical strength are important properties of electrospun fibers that can be tuned for diverse applications. In this study, the authors investigate how the humidity during electrospinning influences these specific properties of the fiber mat. Using two previously uninvestigated polymers, poly(acrylonitrile) (PAN) and polysulfone (PSU) dissolved in N,N‐Dimethylformamide (DMF), experimental results show that increasing humidity during spinning causes an increase in fiber diameter and a decrease in mechanical strength. Moreover, surface features such as roughness or pores become evident when electrospinning in an atmosphere with high relative humidity (RH). However, PAN and PSU fibers are affected differently. PAN has a narrower distribution of fiber diameter regardless of the RH, whereas PSU has a wider and more bimodal distribution under high RH. In addition, PSU fibers spun at high humidity exhibit surface pores and higher specific surface area whereas PAN fibers exhibit an increased surface roughness but no visible pores. These fiber morphologies are caused by a complex interaction between the nonsolvent (water), the hygroscopic solvent (DMF), and the polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Preparation and characterization of poly(ethylene oxide)‐loaded hydroxypropyl‐β‐cyclodextrin nanofibers

Hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) is a modified β‐cyclodextrin (β‐CD) derivative, which is toxicologically harmless to mammals and other animals. HP‐β‐CD is electrospun from an aqueous solution by blending with a non‐toxic, biocompatible, synthetic polymer poly(ethylene oxide) (PEO). Aqueous solutions containing different HP‐β‐CD/PEO blends (50:50–80:20) with variable concentrations (4 wt%–12 wt%) were used. Scanning electron microscope was used to investigate the morphology of the fibers, and Fourier transform infrared spectroscopy analysis confirmed the presence of HP‐β‐CD in the fiber. Uniform nanofibers with an average diameter of 264, 244, and 236 nm were obtained from 8 wt% solution of 50:50, 60:40, and 70:30 HP‐β‐CD/PEO, respectively. The average diameter of the fiber was decreased with increasing of HP‐β‐CD/PEO ratio. However, a higher proportion of HP‐β‐CD in the spinning solution increased beads in the fibers. The polymer concentration had no significant effect on the fiber diameter. The most uniform fibers with the narrowest diameter distribution were obtained from the 8 wt% of 50:50 solution. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced orientation of PEO polymer chains induced by nanoclays in electrospun PEO/clay composite nanofibers

Polymer fibers composed of poly(ethylene oxide) (PEO) and nanoclay were fabricated by electrospinning. The morphology of the composite nanofibers was characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), which showed aligned nanoclays in the fibers. Polarized Fourier transform infrared (FT-IR) spectroscopy revealed that the PEO chains in the composite fibers exhibit a higher degree of orientation than that in PEO nanofibers containing no nanoclay. It is believed that spatial confinement is present in the electrospun nanofibers, which results in the enforcement of the mutual restriction. The anisotropic hierarchical nanostructure may have potential applications in optics, mechanical materials, and biomedical materials for cell culture.     

核-壳结构壳聚糖/聚乙烯醇-聚碳酸亚丙酯超细纤维的制备

利用同轴电纺丝技术制备出具有核-壳结构的壳聚糖/聚乙烯醇-聚碳酸亚丙酯电纺丝纤维,考察了溶剂复配对成纤的影响,采用扫描电镜和透射电镜对纤维的形貌、结构、直径分布等进行了探索,并在优化的工艺条件下,将羟基磷灰石负载在内层结构中.研究表明,采用氯仿/N,N-二甲基甲酰胺(1/1)复配溶剂可有效避免聚合物溶液在喷丝口处的凝结现象.同单纺纤维相比,核壳结构的纤维直径分布较宽,纤维壳层和核层界限清晰;红外谱图分析证明羟基磷灰石可负载在纤维的核结构中.