Preparation and properties of antibacterial,biocompatible core–shell fibers produced by coaxial electrospinning

Coaxial electrospinning is a method for producing fibrous mats with optional features, such as antibacterial properties, controllable release, and hydrophobicity based on shell materials. Because these features are important in biomedical applications, in this study, biocompatible hydrophobic polymer (polycaprolactone) and hydrophilic polymer [poly(vinyl alcohol)] with silver nanoparticles loaded in the core solution were coaxially electrospun. The effect of silver addition on the conductivity and viscosity of the solutions, chemical structure of the fiber mats, mechanical properties, porosity, hydrophobicity, water vapor transmission rate (WVTR), silver release, and antibacterial properties were investigated. Fibers with silver exhibited less porosity and a lower WVTR and a greater contact angle than the fibers without silver. Furthermore, the core–shell fibers reduced the burst release of silver and successfully prevented the growth of Escherichia coli and Staphylococcus aureus bacteria. Therefore, it seems that these fibers are suitable for providing electrospun mats with long‐term antibacterial properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44979.     

Fibrous membranes of cellulose acetate and poly(vinyl pyrrolidone) by electrospinning method: Preparation and characterization

Fibrous membranes of cellulose acetate (CA), poly(vinyl pyrrolidone) (PVP) and composite membranes of these polymers, were obtained by the electrospinning method. Using systematic method, the optimal conditions for preparation of fibrous membranes were found. Both CA and PVP a concentration of 8% weight was found. The CA was dissolved in a acetone:water solution, volume ratio 80 : 20 and the PVP is dissolved in ethanol:water solution, ratio volume 85 : 15. The flow rate for both polymers was 1.5 mL h^?1. The same applied voltage value and the distance between the needle and collection plate were for polymer both, 15 kV and 15 cm respectively. The morphology of fibrous membranes and composite membranes were evaluated by scanning electron microscopy (SEM). The CA fibers showed ribon morphology, while the PVP fibers were cilindric, in both cases with diameters in the micrometer range. Thermogravimetric analysis showed that CA had a complete degradation to 445°C, while the fibrous membranes PVP required a value of temperature for degradation of up to 571°C. Fibrous composite membrane PVP/CA/PVP shows a higher value of strain at break (%), and a lower value of tensile strength (MPa) compared to CA/PVP/CA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology of ultrafine polysulfone fibers prepared by electrospinning

Ultrafine fibers of bisphenol‐A polysulfone (PSF) were prepared by electrospinning of PSF solutions in mixtures of N,N‐dimethylacetamide (DMAC) and acetone at high voltages. The morphology of the electrospun PSF fibers was investigated by scanning electron microscopy. Results showed that the concentration of polymer solutions and the acetone amount in the mixed solvents influenced the morphology and the diameter of the electrospun fibers. The processing parameters, including the applied voltage, the flow rate, and the distance between capillary and collection screen, were also important for control of the morphology of electrospun PSF fibers. It was suggested that uniform ultrafine PSF fibers with diameter of 300–400 nm could be obtained by electrospinning of a 20 % (wt/v) PSF/DMAC/acetone (DMAC:acetone = 9:1) solution at 10–20 kV voltages when the flow rate was 0.66 ml h^?1 and capillary–screen distance was 10 cm. Copyright © 2004 Society of Chemical Industry     

Fabrication and properties of core‐shell structure P(LLA‐CL) nanofibers by coaxial electrospinning

In this article, core‐shell structure nanofibers were fabricated by coaxial electrospinning with biodegradable copolymer Poly(L ‐Lactic‐ε‐Caprolactone) [P(LLA‐CL) 50 : 50] as shell and bovine serum albumin (BSA) as core. Morphology and microstructure of the nanofibers were characterized by scanning electron microscopy and transmission electron microscopy. The mechanical properties were investigated by stress‐strain tests. In vitro degradation rates of the nanofibrous membranes were determined by measuring their weight loss when immersed in phosphate‐buffered saline (pH 7.4) for a maximum of 14 days. Release behavior of BSA was measured by an ultraviolet‐visible spectroscopy, and the results demonstrated that BSA could release from P(LLA‐CL) nanofibers in a steady manner. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

基于静电纺丝技术的PLGA载药纳米纤维膜的制备工艺

同轴静电纺丝法制备的聚乳酸-乙醇酸(PLGA)纳米纤维具有良好的生物相容性和生物可降解性, 加之其高孔隙率和高透氧率, 使其能成为优良的药物载体。本文初步摸索了PLGA的同轴静电纺丝的工艺条件, 并通过同轴静电纺丝法制备了PLGA载氟比洛芬酯(FA)的纳米纤维膜, 应用扫描电子显微镜、红外光谱分析观察纤维的表观形貌并确定其微观结构。重点探究了不同溶剂配比的混合溶剂对载药纤维膜药物释放性能影响。研究结果表明在U⁺为+15.00kV, U^-为-2.50kV, 接受距离为15cm, 壳层推进速度为0.4mm/min, 芯层推进速度为0.1mm/min进行静电纺丝时, 所制备的PLGA(壳)/PVP+FA(核)复合载药纤维膜壳核结构良好, 且成功载了约0.5%的FA。当改变壳层混合溶剂(DCM和DMF)和芯层混合溶剂(无水乙醇和DMF)体积比时, 纤维直径会随着DMF的减少而增大。     

The toughening behavior of PLLA and its asymmetric PLLA/PDLA blends with lower optical purity

Linear poly(d ‐lactide) (PDLA) with various molecular weights is synthesized and incorporated into commercial poly(l ‐lactide) (PLLA) with different optical purities. And then, the crystallization, mechanical and thermal properties of the PLLA and PLLA/PDLA cast films are investigated. In the PLLA and PDLA/PLLA specimens with lower optical purity, few homochiral crystallites (HC) form in all the specimens and only a small amount of PLA stereocomplex crystallites (SC) are observed in the blends. The elongation at break of all the specimens is extraordinary high, >300%. Dynamic mechanical analyses indicate that the destruction temperature increases at first, and then depresses as enlarging the molecular weight of PDLA in these blends. For the PLLA and PLLA/PDLA with higher optical purity, more content of HC develops in neat PLLA, and both SC and HC produce in the PLLA/PDLA specimens. However, the strains of neat specimens and binary blends are much lower than that of specimens with lower optical purity. The specimens with higher optical purity exhibit higher destruction temperatures and lower loss factors. The high content of crystals (SC and HC) would act as the physical cross‐linking points and provide a key factor to impede the deformation of neat PLLA and binary blends during stretching, which should result in the fragile behavior of the PLLA and PLLA/PDLA blends with higher optical purity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44730.     

One-step fabrication of branched poly(vinyl alcohol) nanofibers by magnetic coaxial electrospinning

Branching has been emerging in 3-D interconnecting building blocks. Branched and hyperbranched poly(vinyl alcohol) (PVA) nanofibers were fabricated by coaxially electrospinning two-liquids under an alternating magnetic field in a facile manner. Both the PVA nanofiber trunks with diameter of 100–200 nm and the PVA nanofiber branches with diameter of 10–30 nm were formed in a single step. The length and the morphology of the branched PVA nanofibers could be controlled through a rational design of the magnetic field. The facile technique may readily be extended to prepare 3-D branched nanofibers from other materials such as various polymers and polymer–ceramic materials. Moreover, the multifunctional and multicomponent materials with branched nanostructure could be expected by using the magnetic coaxial electrospinning technique. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication and morphology control of poly(methyl methacrylate) hollow structures via coaxial electrospinning

A modified electrospinning method known as coaxial electrospinning was used to fabricate poly(methyl methacrylate) (PMMA) hollow structures. In this study to understand morphology control, the effect of processing parameters such as concentration of polymer sheath solution, size of core/sheath capillaries, feed rate, and applied voltage had been evaluated. Morphological observations via scanning electron microscope (SEM) revealed that via the control of polymer concentration within the sheath solution, morphologies such as hollow particles and fibers could be obtained. With the use of fine core/sheath capillaries, micron hollow fibers with walls of less than 20 nm were obtained. This study has demonstrated how the investigated processing parameters have a direct influence on the structures and how these parameters have supported the notion that effective encapsulation process is the key to the dual layer bicomponent structures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Acoustic analysis of composite soft materials. I. Characterization of the core and boundary layer from compressibility of core/shell particles dispersed in poly(vinyl chloride)

The sound velocity of butyl acrylate rubber particles modified by poly(methyl methacrylate) in poly(vinyl chloride) was measured as a function of particle concentration. A model for estimating the adiabatic compressibility of the particle and the boundary layer was proposed. From the model, the partial specific adiabatic compressibility of the particles and the rubber core were evaluated. The adiabatic compressibility of the rubber core was estimated as 3.82 × 10⁻¹⁰ Pa⁻¹. The adiabatic compressibility of the poly(methyl methacrylate) shell is discussed based on the modified model. The study indicates that the shell, including the boundary layer between butyl rubber and poly(methyl methacrylate), is perturbed by the butyl acrylate molecules and is so soft as to be comparable to the rubber. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2089–2094, 2001     

Poly(lactide) nanofibers produced by a melt‐electrospinning system with a laser melting device

A new melt‐electrospinning system equipped with a CO₂‐laser melting device was developed. Rod‐like samples were prepared from poly(lactide) pellets, and then fibers were produced from the samples using the new system. The effects of producing conditions on the fiber diameter were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were obtained: (i) in a special case, fibers having an average fiber diameter smaller than 1 μm could be obtained using the system developed; (ii) the fiber diameter could be decreased with increased laser output power, but the physical properties of the fibers such as the melting point and the molecular weight were decreased; and (iii) the electrospun fibers exhibited an amorphous state, and the annealed fibers exhibited an isotropic crystal orientation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1640–1645, 2007     

Preparation and property of antibacterial filter membrane by coaxial electro-spraying/electrospinning technology

Herein, a novel technology named coaxial electro-spraying/electrospinning was successfully introduced, which can simultaneously prepare nanofibers and nanoparticles. First, the device contains an outer nozzle and an inner nozzle, which combine electrospinning with electro-spraying technology. Then, the polyamide 6 (PA6) was spun to prepare the nanofibers from the inner nozzle, and the silver nanoparticles (Ag NPs) into the PA6 solution were sprayed to prepare the nanoparticles from the outer nozzle. PA6 nanofibers (NFs)/Ag nanoparticles (NPs) antibacterial composite membranes for the filtration of fine particulate pollutants were successfully prepared using coaxial electro-spraying/electrospinning. The microstructure, physical properties, and antibacterial properties of the composite membrane were investigated. The results show that Ag NPs are successfully loaded in situ onto PA6 NFs of approximately 100 nm to form a three-dimensional (3D) structure. The filtration efficiency of the 3D structured filtration membrane reaches 90.98%, compared to only 12.78% for the melt-blown cloth mask filter material when tested with polystyrene microspheres (PS) of 200 nm. The contact angle of the composite membrane decreased from 145.47° to 44.11°, indicating a significant improvement in the hydrophilicity of the membrane. Furthermore, depositing Ag on the surface fibers resulted in an impressive antibacterial rate of 99.75% against Penicillium.     

Preparation of polystyrene/poly(vinyl acetate) nanocomposites with a core–shell structure via emulsifier‐free emulsion polymerization

Polystyrene/poly(vinyl acetate) latex nanoparticles with a core–shell morphology in an emulsifier‐free emulsion polymerization system were prepared with purified styrene and vinyl acetate (VAc) as monomers and 2,2′‐azo bis(2‐amino propane) dihydrochloride (ABA,2HCl) as the initiator and emulsifier. The optimized conditions of polymerization of VAc, on top of the already‐formed polystyrene as a core polymer, with a core–shell morphology were obtained using various parameters such as volume ratio of the first and second stages, type of process, and reaction time. The morphologic structure of the nanoparticles was studied by scanning electron microscopy and transmission electron microscopy. The latex nanoparticles and polymers were characterized by differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2409–2414, 2006     

Synthesis of ultrafine poly(styrene‐maleic anhydride) and polystyrene fibers by electrospinning

Fiber formation from atactic polystyrene (aPS) and alternating poly(styrene‐maleic anhydride) (PSMA) synthesized by free radical polymerization (AIBN, 90°C, 4 h) were investigated by electrospinning from various solutions. aPS was soluble in dimethylformamide (DMF), tetrahydrofuran (THF), toluene, styrene, and benzene, whereas PSMA was soluble in acetone, DMF, THF, dimethylsulfoxide (DMSO), ethyl acetate, and methanol. aPS fibers could be electrospun from 15 to 20% DMF and 20% THF solutions, but not from styrene nor toluene. PSMA, on the other hand, could be efficiently electrospun into fibers from DMF and DMSO at 20 and 25%, respectively. Few PSMA fibers were, however, produced from acetone, THF, or ethyl acetate solutions. Results showed that solvent properties and polymer–solvent miscibility strongly influenced the fiber formation from electrospinning. The addition of solvents, such as THF, generally improved the fiber uniformity and reduced fiber sizes for both polymers. The nonsolvents, however, had opposing effects on the two polymers, i.e., significantly reducing PSMA fiber diameters to 200 to 300 nm, creating larger and irregularly shaped aPS fibers. The ability to incorporate the styrene monomer and divinylbenzene crosslinker in aPS fibers as well as to hydrolyze PSMA fibers with diluted NaOH solutions demonstrated potential for post‐electrospinning reactions and modification of these ultrafine fibers for reactive support materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Formation of core/shell ultrafine fibers of PVDF/PC by electrospinning via introduction of PMMA or BTEAC

Core/shell structured ultrafine fibers of poly(vinylidene fluoride) (PVDF)/polycarbonate (PC) were prepared by electrospinning their dispersions in a mixed solvent of N,N-dimethylformamide and tetrahydrofuran. The morphology of the obtained fibers viewed under a scanning electron microscope and a transmission electron microscope could be adjusted via introduction of poly(methyl methacrylate) (PMMA) or triethylammonium chloride (BTEAC). The viscosity of the dispersions increased with the increasing amount of PMMA in the range of 10-15 wt%, while the diameter of the dispersive spheral phase in the dispersions decreased. A proper amount of PMMA could decrease the resistance of the dispersive phase transformation in PVDF/PC dispersions, so that the uniform fibrous morphology and distinct core/shell structure were easily formed in the electrospun fibers. Because of the significant increase of the conductivity of the PVDF/PC dispersion, addition of 2 wt% BTEAC could also promote formation of the core/shell structure of electrospun PVDF/PC ultrafine fibers. Comparison between electrospun fibers of PVDF/PC, PVDF/PC/PMMA and PVDF/PC with BTEAC etched by chloroform showed that the core/shell structure of PVDF/PC with BTEAC was in the highest quality.     

Preparation and in vitro degradation of novel bioactive polylactide/wollastonite scaffolds

Composite scaffolds for applications in bone engineering from poly(D,L ‐lactide) (PDLLA) incorporated with different proportional bioactive wollastonite powders were prepared through a salt‐leaching method, using NH₄HCO₃ as porogen. The pore structures and morphology of the scaffolds were determined by scanning electron microscopy (SEM). The bioactivity of composite materials was evaluated by examining its ability to initiate the formation of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂)(HAp) on its surface when immersed in simulated body fluids (SBF). The in vitro degradation behaviors of these scaffolds were systematically monitored at varying time periods of 1, 2, 4, 6, 8, 11, 14, 17, 20, 24, and 28 weeks postimmersion in SBF at 37°C. FT‐IR, XPS, XRD, and SEM measurements revealed that hydroxyapatite commenced to form on the surface of the scaffolds after 7 days of immersion in SBF. The measurements of weight loss, pH, and molecular weight of the samples indicated that PDLLA/wollastonite composite scaffolds degraded slower than the pure PDLLA scaffolds do. Addition of wollastonite enhanced the mechanical property of the composite scaffolds. The in vitro osteoblast culture experiment confirmed the biocompatibility of the scaffold for the growth of osteo‐blasts. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009.     

Electrospun poly(D,L)‐lactide nonwoven mats for biomedical application: Surface area shrinkage and surface entrapment

Nanofibrous poly(D,L )‐lactide mats prepared by electrospinning are useful for numerous biomedical applications. However, it was observed that these mats tend to shrink under physiological conditions. In this research, a physical entrapment method to modify the polymer surface with poly(ethylene glycol) was developed to ensure dimensional stability and to increase the hydrophilicity of the surface of the mats. Nanofiber morphology was characterized by scanning electron microscopy. Surface element analysis was performed by high resolution X‐ray photoelectron spectroscopy. Water contact angles were determined to identify surface properties before and after surface entrapment. Canine fibroblasts were prepared and seeded onto the poly(D,L)‐lactide mats, followed by cell morphology study by SEM and cell viability tests by MTT assay, which confirmed the improvement of biocompatibility by surface modification. Taking the results into account, hydrophilic and area‐stable nanofibrous nonwoven mats were successfully produced, with potential applications as in vivo biomedical material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

熔体微分静电纺PBAT纤维膜的制备工艺研究

探究了聚己二酸对苯二甲酸丁二醇酯（PBAT）熔体静电纺性能,并研究了熔体微分静电纺工艺参数与PBAT纤维性能之间的关系。结果表明,随着纺丝温度的升高,纤维直径减小,纤维直径分布呈先减小后增大的趋势;随着纺丝电压的升高,纤维直径减小且分布均匀,纤维膜力学性能逐渐提高;当纺丝距离为9 cm,纺丝温度为260 ℃,纺丝电压为45 kV时,制备的纤维细度及均匀度最佳,其直径为4.31 μm,直径分布标准差为0.76,纤维膜拉伸强度为9.9 MPa、断裂伸长率为111.2 %。     

核／壳型可遮盖聚合物乳液的研制

采用了种子乳液聚合法,以可被碱溶胀的丙烯酸类聚合物为核,交联型的丙烯酸类高聚物为壳,合成了新型的可以代替部分钛白粉等颜料的可遮盖聚合物。讨论了乳化剂、单体、核壳比等对聚合物性能的影响,其中核壳比在1:15-1:25时,聚合物具有较好的遮盖效果。     

Enzymatic degradation of poly(D,L‐lactide) and its blends with poly(vinyl acetate)

The enzymatic degradation of poly(D ,L ‐lactide) (PLA) was investigated using two different lipases, Novozym 435 and Lipolase. The optimum temperature was 50°C for the enzymatic degradation of PLA. The effect of various solvents on the degradation of PLA was investigated at 50°C using Novozym 435, and toluene was found to be the best solvent among the solvents investigated. The enzymatic degradation of the blends of PLA and PVAc was investigated at 50°C in toluene. The enzymatic degradation of the blends of PLA and PVAc showed that there is an interaction between the polymers during degradation, which results in the reduction of degradation rate of both polymers in the blend. A continuous distribution model was used to determine the rate coefficients for polymer degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 657–680 2006     

Process Optimization and Empirical Modeling for Electrospun Poly(D,L‐lactide) Fibers using Response Surface Methodology

Summary: Ultrafine fibers were spun from poly(D ,L ‐lactide) (PDLA) solution using a homemade electrospinning set‐up. Fibers with diameter ranging from 350 to 1 900 nm were obtained. Morphologies of fibers and distribution of fiber diameters were investigated varying concentration and applied voltage by scanning electron microscopy (SEM). Average fiber diameter and distribution were determined from about 100 measurements of the random fibers with an image analyzer (SemAfore 5.0, JEOL). A more systematic understanding of process parameters of the electrospinning was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by response surface methodology (RSM). It was concluded that the concentration of polymer solution played an important role in the diameter of fibers and standard deviation of fiber diameter. Lower concentration tended to facilitate the formation of bead‐on‐string structures. Fiber diameter tended to increase with polymer concentration and decrease with applied voltage. Fibers with lower variation in diameter can be obtained at lower concentration regardless of applied voltage. Fibers with uniform diameter and lower variation in diameter can be obtained at higher concentration and higher applied voltage. Process conditions for electrospinning of PDLA could be chosen according to the model in this study.

Contour plots of average fiber diameter as a function of concentration and applied voltage.