界面聚合法合成手性掺杂剂诱导螺旋形聚苯胺纳米纤维

以手性试剂D-樟脑磺酸(D-CSA)和L-樟脑磺酸(L-CSA)为掺杂剂和构象诱导剂,采用界面聚合法合成了螺旋形聚苯胺纳米纤维。通过FESEM、TEM、FTIR和UV-Vis吸收光谱等测试技术对螺旋形聚苯胺纳米纤维结构进行了表征。结果表明,所得聚苯胺纤维具有螺旋形构象,形貌均一,平均直径约为50nm,长度为300～600nm,具有较高的长径比(6:1～12:1)。在水溶液中,聚苯胺纳米纤维以伸展的螺旋形分子链构象存在,调节溶液的pH值,螺旋形聚苯胺纳米纤维表现出可逆的掺杂和脱掺杂性质。循环伏安(CV)测试表明,螺旋形聚苯胺纳米纤维在0.5mol/LHCl溶液中表现出良好的电化学活性。     

Chemomechanical and morphological properties with proliferation of keratinocyte cells of electrospun poyhydroxyalkanoate fibers incorporated with essential oil

Delivery systems based on electrospun polymeric nanofibers have shown potential for delivery of bioactive and plant extract formulations. This research focused on the fabrication of polyhydroxyalkanoate (PHA) copolymer nanofibers as a vehicle for loading of the Thai traditional herbal extract of Plai oil (Zingiber cassumunar Roxb). Nanofibers were formed by dissolving PHA and Plai oil together in dichloromethane solvent, with the PHA concentration being varied (5, 8, and 10%), followed by electrospinning for 4 hours. Based on the submicron diameters of the nanofibers, 8% PHA proved to be the optimal concentration. The concentration of Plai oil (10, 20, and 30%) was used, and hence, the solution viscosity influenced the nanofiber synthesis and physical properties of the nanofibers were obtained. Scanning electron microscope results indicated that the average diameters of cylindrical PHA nanofibers loaded with Plai oil (10%, 20%, and 30%) were 1.10, 1.01, and 1.11 μm, respectively, highlighting that fibers composed of 20% Plai oil were classifiable as nanofibers. Tensile testing of 20% Plai oil‐loaded nanofibers indicated that stiffness and elongation at break were within the acceptable range. Fourier transform infrared and differential scanning calorimetry measurements highlighted the presence of terpenen‐4‐ol, a component found in Plai oil, in the nanofiber film samples of PHA/Plai oil, confirming its inclusion in the systems. In addition, cell proliferation was set up to confirm the morphology and toxicity of skin keratinocyte cell line, and the results show that the HaCaT cells were attached on the PHA nanofibers which the nanofibers containing 20% Plai oil may affect cell behavior in spite the fact that it is not toxic to the cells.     

Surface‐treated and multilayered poly(ε‐caprolactone) nanofiber webs exhibiting enhanced hydrophilicity

To improve the hydrophilic properties of poly(ε‐caprolactone) (PCL) nano/microfiber webs for tissue engineering scaffolds, PCL webs of various structures were fabricated by electrospinning with single or double nozzles connected to an auxiliary electrode. Surface‐modified and layered PCL fiber webs were made by including water‐soluble poly(ethylene oxide) (PEO) in the PCL electrospinning solution (single‐nozzle method) or by electrospinning of alternating PCL and PEO solutions using two nozzles (double‐nozzle method), respectively. When the PEO component within the resulting webs was removed by dissolution with distilled water, the remnant PCL webs exhibited two distinct structures. Those made by the single‐nozzle method consisted of nanofibers with high surface roughness, whereas those made by the double‐nozzle method consisted of stacked layers of PCL nanofibers. Both types of structured PCL web showed improved hydrophilicity characteristics compared with those of nanofiber webs generated from a pure PCL solution using a typical electrospinning process. Cell culturing and scanning electron microscopy showed that the interactions between human dermal fibroblasts and the structured PCL scaffolds were very favorable. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2038–2045, 2007     

Preparation of electrospun shape memory polyurethane fibers in optimized electrospinning conditions via response surface methodology

Herein, the electrospinning method, as an effective approach, was utilized to fabricate poly (ε‐caprolactone)‐based polyurethane (PCL‐based PU) fibers. PCL was synthesized by ring‐opening polymerization, and characterized by proton nuclear magnetic resonance (¹H NMR) and Fourier‐transform infrared (FTIR) spectroscopies. Afterward, PU was prepared by step‐growth polymerization. The effects of solution concentration and solvent type on fibers' diameter were investigated. Scanning electron microscopy (SEM) images revealed that the optimum solution was N, N‐dimethylformamide(DMF): chloroform with a ratio of 60:40. In addition, results showed that bead‐less nanofibers could be achieved by a concentration of 5 w/v% (polymer to solvent). Various optimum practical parameters, such as applied voltage, feeding rate, and needle‐to‐collector distance, were obtained and compared with the results of response surface methodology (RSM). On the other hand, the mechanical evaluations indicated that the porous structure of scaffolds caused them to possess lower mechanical properties, as well as shape fixity ratios than those of bulk samples.     

In vitro and in vivo evaluations of nanofibrous nanocomposite based on carboxymethyl cellulose/polycaprolactone/cobalt-doped hydroxyapatite as the wound dressing materials

These days, Ophthalmic wound treatment is a major problem; due to its nature, bio/materials are the best choices as wound dressing materials. The main objective of the current survey is to develop and investigate effective wound dressing materials for skin care applications. In these ways, we combined the good biological properties of Cobalt-doped hydroxyapatite particles (CoHAp) with the structural properties of Polycaprolactone (PCL)/ carboxymethyl cellulose (CMC) nanofibers. Electrospinning and co-precipitation methods were used to synthesize nanofibers and CoHAp particles, respectively. Nanocomposites were synthesized in the absence and different percentages of CoHAp. The PCL/CMC, PCL/CMC/CoHA 5 %, PCL/CMC/CoHA 10 %, and PCL/CMC/CoHA 15 % formulated nanocomposites have the diameter of 383 ± 50, 391 ± 84, 441 ± 65, and 495 ± 99 nm, respectively. The synthesized nanofibrous wound dressing porosity and water absorption capacity were in the range of 40 to 60 % and 32 to 63 %, respectively. Hemo and cytocompatibility of the nanofibrous wound dressing were analyzed by in vitro evaluation, and the results were satisfactory and the structures were fully biocompatible. The PCL/CMC/CoHA 10 % wound dressing, were selected as the best nanocomposites for wound healing based on our animal studies on the healing outcomes. The results showed that the PCL/CMC nanofibers-Cobalt-doped HAp wound dressing is an effective bioactive nano-biomaterials for the wound healing process.     

Double‐layered composite nanofibers and their mechanical performance

Continuous polymer nanofibers are available through electrospinning, but most have the same structure in their cross section. This article focuses on the fabrication and the structural and mechanical characterization of pencil‐like double‐layered composite nanofibers coaxially electrospun from solutions of two different biodegradable materials, i.e., gelatin and poly(ε‐caprolactone) (PCL). Transmission electron microscopy and water contact angle measurements confirmed that a gelatin inner fiber was wrapped with a PCL outer layer. Possible applications of such nanofibers include a controlled degradation rate when used as a medical device in human body. It has been found that the tensile performance of the composite nanofibers was better than those of both the pure constituent, i.e. gelatin and PCL, nanofibers alone. The ultimate strength and ultimate strain of the composite nanofibers with 7.5% w/v gelatin in the core and 10% w/v PCL as shell were at least 68% and 244% higher, respectively, than those of the same concentration pure gelatin and PCL nanofibers. Thus, a coaxial electrospinning technique as used in this article can be applicable, not only in developing functionalized nanofibers but also in elevating their mechanical property. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2852–2861, 2005     

Alkali‐Mediated Miscibility of Gelatin/Polycaprolactone for Electrospinning Homogeneous Composite Nanofibers for Tissue Scaffolding

Electrospun natural‐synthetic composite nanofibers, which possess favorable biological and mechanical properties, have gained widespread attention in tissue engineering. However, the development of biomimetic nanofibers of hybrids remains a huge challenge due to phase separation of the polymer blends. Here, aqueous sodium hydroxide (NaOH) solution is proposed to modulate the miscibility of a representative natural‐synthetic hybrid of gelatin (GT) and polycaprolactone (PCL) for electrospinning homogeneous composite nanofibers. Alkali‐doped GT/PCL solutions and nanofibers examined at macroscopic, microscopic, and internal molecular levels demonstrate appropriate miscibility of GT and PCL after introducing the alkali dopant. Particularly, homogeneous GT/PCL nanofibers with smooth surface and uniform diameter are obtained when aqueous NaOH solution with a concentration of 10 m is used. The fibers become more hydrophilic and possess improved mechanical properties both in dry and wet conditions. Moreover, biocompatibility experiments show that stem cells adhere to and proliferate better on the alkali‐modified nanofibers than the untreated one. This study provides a facile and effective approach to solve the phase separation issue of the synthetic‐natural hybrid GT/PCL and establishes a correlation of compositionally and morphologically homogeneous composite nanofibers with respect to cell responses.     

Preparation and characterization of composite nanofibers of polycaprolactone and nanohydroxyapatite for osteogenic differentiation of mesenchymal stem cells

Nanocomposites of nanohydroxyapatite (nHAP) dispersed in poly(?-caprolactone) (PCL) were prepared by electrospinning (ES) to obtain PCL/nHAP nanofibers. Nanofibers with similar diameters (340 ± 30 nm) but different nHAP concentrations (0-50%) were fabricated and studied for growth and osteogenic differentiation of bone marrow mesenchymal stem cells (MSCs). The nanofibrous membranes were subjected to detailed analysis for its physicochemical properties by scanning electron microscopy (SEM), thermogravimetric analysis, X-ray diffraction, Fourier-transform infrared spectroscopy, and mechanical tensile testing. nHAP particles (~30 nm diameter) embedded in nanofibers increased the nanofibrous membrane's ultimate stress and the elastic modulus, while decreased the strain at failure. When cultured under an osteogenic stimulation condition on nanofibers, MSCs showed normal phenotypic cell morphology, and time-dependent mineralization and osteogenic differentiation from SEM observations and alkaline phosphatase activity assays. The nanofibers could support the growth of mesenchymal stem cells without compromising their osteogenic differentiation capability up to 21 days and the enhancement of cell differentiation by nHAP is positively correlated with its concentration in the nanofibers. Energy dispersive X-ray analysis of Ca and P elements indicated mineral deposits on the cell surface. The mineralization extent was significantly raised in nanofibers with 50% nHAP where a Ca/P ratio similar to that of bone was found. The present study indicated that electrospun composite PCL/nHAP nanofibrous membranes are suitable for mineralization of MSCs intended for bone tissue engineering.     

Bicomponent aligned nanofibers of N-carboxyethylchitosan and poly(vinyl alcohol)

Bicomponent nanofibers of N-carboxyethylchitosan (CECh) and poly(vinyl alcohol) (PVA) were obtained by electrospinning of mixed aqueous solutions. The electrospinning of CECh-containing nanofibers was enabled by the ability of PVA to form an elastically deformable entanglement network based on hydrogen bonds. The average diameters of the bicomponent fibers were in the range 100-420 nm. Water-resistant nanofibrous mats were obtained by thermal crosslinking at 100 °C for 10 h. Nanofibrous materials with 1D-, 1D-transversery or 3D fiber alignment were obtained depending on the type of the collector used.     

Control of diameter,morphology, and structure of PVDF nanofiber fabricated by electrospray deposition

Poly(vinylidene fluoride) (PVDF) nanofibers were prepared by electrospray deposition (ESD). To control the diameter, morphology, and structure of PVDF nanofibers, some parameters were investigated, such as polymer concentration, nozzle‐to‐ground collector distance, feeding rate of the polymer solution, and applied voltage. The fabricated fiber was 80–700 nm in diameter. The increase in the polymer concentration caused an increase in the polymer viscosity and fiber diameter. At low polymer concentration (5 wt %), polymer nanoparticles were formed. An increase in applied voltage will increase the fiber diameter. Variation in the nozzle‐to‐ground collector distance did not result in significant changes in the fiber diameter. Increase in the feeding rate of the polymer solution decreased the fiber diameter. Differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) measurements showed that the melting point and total crystallinity were decreased. Fourier transform infrared spectroscopy (FTIR) measurement revealed that ESD process induced the formation of the oriented β‐phase PVDF structures. It was also demonstrated that the addition of hydrofluorocarbon solvent to polymer solution remarkably enhanced the formation of β‐phase crystalline structure of PVDF nanofiber. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 779–786, 2006     

Simple fabrication of cellulose nanofibers via electrospinning of dissolving pulp and tunicate

This work demonstrates a simple fabrication of cellulose nanofibers by direct electrospinning of dissolved cellulose solutions. The hard- and softwood pulps and the outer mantles of tunicate were dissolved in a mixture of trifluoroacetic acid and dichloroethane by stirring and ultrasonication to give highly viscoelastic, clear solutions. These solutions were electrospun to form continuous nanofibers made of unsubstituted cellulose, which were confirmed by scanning electron microscopy (SEM) and IR spectroscopy. Statistical analysis of the SEM images of the nanofibers suggested that there are positive correlations between diameters of the nanofibers and concentration of the cellulose solution. The mean diameters of the nanofibers obtained from softwood pulp (DP of cellulose ≈ 1200) solutions were larger than those from hardwood pulp (DP of cellulose ≈ 500) at the same concentrations. This indicates that the DP of cellulose is one of the important parameters to control the diameters of the electrospun cellulose nanofibers.     

Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance

Uniaxially oriented cellulose nanofibers were fabricated by electrospinning on a rotating cylinder collector. The fiber angular standard deviation (a parameter of fiber orientation) of the mats was varied from 65.6 to 26.2^o by adjusting the rotational speed of the collector. Optically transparent epoxy resin composite films reinforced with the electrospun cellulose nanofibrous mats were then prepared by the solution impregnation method. The fiber content in the composite films was in the range of 5–30 wt%. Scanning electron microscopy studies showed that epoxy resin infiltrated and completely filled the pores in the mats. Indistinct epoxy/fiber interfaces, epoxy beads adhering on the fiber surfaces, and torn fiber remnants were found on the fractured composite film surfaces, indicating that the epoxy resin and cellulose fibers formed good interfacial adherence through hydrogen-bonding interaction. In the visible light range, the light transmittance was 88–92% for composite films with fiber loadings of 16–32 wt%. Compared to the composite films reinforced with 20 wt% randomly oriented fibers, the mechanical strength and Young’s modulus of the composite films reinforced with same amount of aligned fibers increased by 71 and 61%, respectively. Dynamical mechanical analysis showed that the storage moduli of the composite films were greatly reinforced in the temperature above the glass transition temperature of the epoxy resin matrix.     

Structure and nanomechanical characterization of electrospun PS/clay nanocomposite fibers

Electrospinning has been emerging as one of the most efficient methods to fabricate polymer nanofibers. In this paper, PS/clay nanocomposite fibers with varying diameters were electrospun onto solid substrates. The fiber diameters were adjusted from 4 microm to 150 nm by changing the solution concentration. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) were used to characterize the fiber morphology. Shear modulation force microscopy (SMFM) was utilized to investigate the surface nanomechanical properties of electrospun fibers as a function of the fiber diameter and temperature. In the absence of clay, no change in T(g) was observed, even though a large increase of shear modulus below the glass transition temperature was found. This effect was postulated to result from the molecular chain alignment during electrospinning. The addition of functionalized clays to the spinning solution produced fibers with a highly aligned montmorillonite layer structure at a clay concentration of 4 wt %. Clay agglomerates were observed at higher concentrations. The existence of clay further enhanced the shear modulus of fibers and increased the glass transition temperature by nearly 20 degrees C.     

Highly porous core-shell polymeric fiber network

Core-shell nanofibers are of great interest in the field of tissue engineering and cell biology. We fabricated porous core-shell fiber networks using an electrospinning system with a water-immersed collector. We hypothesized that the phase separation and solvent evaporation process would enable the control of the pore formation on the core-shell fiber networks. To synthesize porous core-shell fiber networks, we used polycaprolactone (PCL) and gelatin. Quantitative analysis showed that the sizes of gelatin-PCL core-shell nanofibers increased with PCL concentrations. We also observed that the shapes of the pores created on the PCL fiber networks were elongated, whereas the gelatin-PCL core-shell fiber networks had circular pores. The surface areas of porous nanofibers were larger than those of the nonporous nanofibers due to the highly volatile solvent and phase separation process. The porous core-shell fiber network was also used as a matrix to culture various cell types, such as embryonic stem cells, breast cancer cells, and fibroblast cells. Therefore, this porous core-shell polymeric fiber network could be a potentially powerful tool for tissue engineering and biological applications.     

Carbon nanofibers grown on sodalime glass at 500°C using thermal chemical vapor deposition

Carbon nanofibers are grown homogeneously on a large area of nickel-deposited sodalime glass substrate by thermal chemical vapor deposition of acetylene at 500°C. The diameters of carbon nanofibers are uniformly distributed in the range between 50 and 60 nm. Most of the carbon nanofibers are curved or bent in shape, but some fractions are twisted. They consist of defective graphitic sheets with a herringbone morphology. The maximum emission current density from the carbon nanofibers is 0.075 mA/cm² at 16 V/μm, which is sufficient for commercializing the carbon-nanofibers-based field emission displays.     

Electrospinning Process of Thermo-sensitive Poly(N-isopropylacrylamide) /poly (2-acrylamido-2-methylpropanesulfonic acid) Nanofibers

Poly (N-isopropylacrylamide)/poly (2-acrylamido-2-methylpropanesulfonic acid) (PNIPAAm/PAMPS) nanofibers was prepared using the electrospinning technique. The electrospinning process parameters such as solution concentration, voltage, receiver distance and flow rate were determined by the orthogonal experiments. The appropriate electrospinning parameters were 7.0% of solution concentration, 10.0 kV of voltage, 20 cm of distance and 3.1 μL·min^?1 of flow rate, respectively. The major factor affecting the nanofibers diameter was the solution concentration and the diameter increased with the solution concentration. The Fourier-transform infrared spectroscopy (FTIR) was conducted to characterize the structure of the components for electrospinning. Scanning electron microscopy (SEM) was taken to observe the morphology, and the contact angle (CA) measuring was carried out to determine the wettability of the nanofibers with temperatures. The results of SEM observation showed that the surfaces of nanofibers were smooth with uniform fibrous diameters and without the formation of beads. The CA detections showed that the electrospun PNIPAAm/PAMPS nanofibers exhibited thermo-sensitivity of hydrophilicity at 20°C and hydrophobicity at 40°C.     

Direct electrochemistry and voltammetric determination of midecamycin at a multi-walled carbon nanotube coated gold electrode

Magnesium l-ascorbic acid 2-phosphate (MAAP) and α-tocopherol acetate (α-TAc), as the stable vitamin C and vitamin E derivative, respectively, are often applied to skin care products for reducing UV damage. The encapsulation of MAAP (0.5%, g/mL) and α-TAc (5%, g/mL) together within the polyacrylonitrile (PAN) nanofibers was demonstrated using a coaxial electrospinning technique. The structure and morphology characterizations of the core-shell fibers MAAP/α-TAc-PAN were investigated by SEM, FTIR and XRD. As a negative control, the blend nanofibers MAAP/α-TAc/PAN were prepared from a normal electrospinning method. The results from SEM indicated that the morphology and diameter of the nanofibers were influenced by concentration of spinning solution, the polymer component of the shell, the carrying agent of the core and the fabricating methods, and the core-shell nanofibers obtained at the concentration of 8% had finer and uniform structure with the average diameters of 200 ± 15 nm. From in vitro release studies it could be seen that both different fiber specimens showed a gradual increase in the amount of α-TAc or MAAP released from the nanofibers. Furthermore, α-TAc and MAAP released from the blend nanofibers showed the burst release at the maximum release of ～15% and ～40% during the first 6 h, respectively, but their release amount from the core-shell nanofibers was only 10–12% during the initial part of the process. These results showed that core-shell nanofibers alleviated the initial burst release and gave better sustainability compared to that of the blend nanofibers. The present study would provide a basis for further optimization of processing conditions to obtain desired structured core-shell nanofibers and release kinetics for practical applications in dermal tissue.     

Electrospun EGNPs reinforced precursor carbon nanofibril composites by using RSM

Response surface methodology (RSM),based on five‐level, four variable Box‐Benkhen technique was investigated for modeling the average fiber diameter of electrospun polyacrylonitrile (PAN) nanofibers. The four important electrospinning parameters were studied including applied voltage (kV), Berry's number, deposition distance from nozzle to collector (cm), and spinning angle (? in degree). The measured fiber diameters were in a good agreement with the predicted results by using RSM technique. High‐regression coefficient between the variables and the response (R² = 87.74%) indicates excellent evaluation of experimental data by second‐order polynomial regression model. The optimum PAN average fiber diameters of 208 and 37‐nm standard deviation were collected at 19 kV, Berry's number = 10, 25^° spinning angle, and 16‐cm deposition distance. The PAN/N,N‐dimethylformamide (DMF) polymer solution with the optimum weight concentration (10 wt.%) was selected to study the effect of dispersing exfoliated graphite nanoplatelets (EGNPs) in PAN/DMF solution on the electrospun EGNP/PAN fibril composite diameter. Five different EGNPs weight concentrations (2, 4, 6, 8, and 10 wt.%) were dispersed in the optimized PAN/DMF polymer solution. Morphology of EGNPs/PAN fibril composites and its distribution were investigated by scanning electron microscopy (SEM) to show the minimum fiber diameter for the above‐mentioned 5 wt. % of EGNPs. A minimum fibril composite diameter of 182 nm was obtained at 10 wt.% of EGNPs. Morphological characteristics of electrospun fibers and their distribution were tested by Raman spectroscopy, SEM, differential light scattering, and high‐resolution transmission electron microscopy.     

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     

The Cooperative Effect of Both Molecular and Supramolecular Chirality on Cell Adhesion

Although helical nanofibrous structures have great influence on cell adhesion, the role played by chiral molecules in these structures on cells behavior has usually been ignored. The chirality of helical nanofibers is inverted by the odd–even effect of methylene units from homochiral l ‐phenylalanine derivative during assembly. An increase in cell adhesion on left‐handed nanofibers and weak influence of cell behaviors on right‐handed nanofibers are observed, even though both were derived from l ‐phenylalanine derivatives. Weak and negative influences on cell behavior was also observed for left‐ and right‐handed nanofibers derived from d ‐phenylalanine, respectively. The effect on cell adhesion of single chiral molecules and helical nanofibers may be mutually offset.