Preparation of nylon-6/chitosan composites by nanospider technology and their use as candidate for antibacterial agents

Electrospun nylon-6/chitosan (nylon-6/Ch) nanofibers were prepared by nanospider technology. Quaternary ammonium salts as antibacterial agent were immobilized onto electrospun nylon-6/Ch nanofibers via surface modification by soaking the mat in aqueous solution of glycidyltrimethylammonium chloride (GTMAC) at room temperature overnight to give nylon-6/N-[(2-hydroxy-3-trimethylammonium)propyl] chitosan chloride (nylon-6/HTCC). The morphological, structural and thermal properties of the nylon-6/ch nanofibers were studied by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). Biological screening has demonstrated the antibacterial activity of the electrospun nanofibers against Gram negative bacteria, Escherichia coli 35218, and Pseudomonas aeruginosa and Gram positive bacteria, Staphylococcus aureus 24213 among the tested microbes. Thus, the study ascertains the value of the use of electrospun nanofibers, which could be of considerable interest to the development of new antibacterial materials for biomedical applications.     

Phase behavior study of chitosan/polyamide blends

Blends of chitosan with strongly crystalline polyamides (nylon-4 and nylon-6) and weakly crystalline polyamides (caprolactam/laurolactam and Zytel®) were investigated. Phase behavior, morphology, interactions with water, mechanical properties, and catalytic reactivity were studied. Films were made from formic acid solutions with the chitosan concentrations ranging from 5% to 95% (w/w). The 80% deacetylated chitosan is in the salt, neutral, or copper chelate form. All the blends have higher relative water contents than does the pure chitosan. Dry neutral chitosan shows a relaxation centered at approximately 90°C which is attributed to local motion. The phase behavior of the blends is influenced by preparation conditions such as the drying temperature. Characterization of blends by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) suggests partial miscibility of chitosan with nylon-4 and lack of miscibility in the remaining cases. Blending with nylon-4 enhances mechanical properties with marked antiplasticization in blends containing 90% chitosan. Catalytic activity of the chitosan is enhanced by blending with nylon-4. Salt and neutral forms of chitosan appear to be equally effective. © 1996 John Wiley & Sons, Inc.     

Effects of gamma irradiation on the thermal and mechanical properties of chitosan/PVA nanofibrous mats

Chitosan/poly(vinyl alcohol) (PVA) nanofibrous mats were prepared by the electrospinning method. The morphology and structure of electrospun nanofibers were investigated by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. SEM images showed that the uniform and bead-free fibers were obtained at concentrations greater than 8 wt%. Chitosan/PVA mats were irradiated with different doses (50–200 kGy) of ⁶⁰Co gamma rays. The effect of irradiation dose on the mechanical and thermal properties of these films was also investigated. Increasing the irradiation dose led to a decrease in tensile strength. FT-IR and DSC demonstrated that there were strong intermolecular hydrogen bonds between the chitosan and PVA molecules.     

Effect of lactic acid on polymer crystallization chain conformation and fiber morphology in an electrospun nylon-6 mat

The role of lactic acid (LA) on the polymer crystallization chain conformation and the surface modification of the electrospun nylon-6 fibers were examined. The effect of different amounts of LA on the polymer crystallization chain conformation of nylon-6 mat was evaluated using XRD, FT-IR and Raman spectroscopy whereas the surface modification of the electrospun mats was examined by FE-SEM, contact angle and mechanical properties measurement. It was found that the transition of meta-stable γ-form into the thermodynamically stable α-form was achieved by increasing the amounts of LA in the blend mixture. The adhesive property of LA was found to be responsible for the transformation from non-bonded to the point-bonded structure of nanofibers in the electrospun nylon-6 mat. The resultant LA/nylon-6 hybrid mat with improved hydrophilicity and mechanical properties may be a potential candidate for tissue scaffold.     

Mechanical and Physical Properties of Cassava Starch-Gelatin Composite Films

The effect of gelatin concentrations on the mechanical properties and solubility of cassava starch-based films containing glycerol was studied. Increasing concentration of gelatin increased tensile strength but reduced elongation at break and water solubility of the composite films. Films containing 30% gelatin showed the highest tensile strength. Fourier transform infrared spectroscopy (FT-IR) spectra indicated intermolecular interactions between cassava starch and gelatin in composite films. The X-ray diffraction (XRD) technique demonstrated pseudo-crystalline regions in the cassava starch-gelatin composite films, and it is supposed that the interactions between cassava starch and gelatin were shown in the diffractograms by shifts in scattering angles. The differential scanning calorimetry (DSC) thermograms and scanning electron microscopy (SEM) micrographs confirmed homogeneity of cassava starch-gelatin films. Cassava starch-gelatin composite films have the potential to replace conventional packaging, and the films developed in this work are suggested to be suitable for low-moisture food and pharmaceutical products.     

Fabrication of ethyl cellulose microspheres: Chitosan solution as a stabilizer

Ethyl cellulose was dissolved in ternary mixture, which consisted of 10 ml dichloroethane, 20 ml methanol and 10 ml acetone. Then, the ethyl cellulose microspheres were shaped in 1–6% chitosan solution and at 40 °C, 70 °C and 100 °, respectively. The characteristics of these ethyl cellulose microspheres were also investigated based on the characterization of XRD, SEM, IR and DSC. The results showed that the most suitable conditions for ethyl cellulose microsphere preparation were in 6% chitosan solution and at 70 °C, in which the ethyl cellulose microsphere prepared were small and uniform. Moreover, from the XRD, IR and DSC data, the crystallization of ethyl cellulose microspheres decreased with the increase of the temperature; on the other hand, there some interactions happened between ethyl cellulose and chitosan, which shows a strong evidence for the intermolecular interactions and good molecular compatibility between ethyl cellulose and chitosan.     

Preparation and characterization of chitosan/poly(vinyl alcohol) blend fibers

Chitosan and poly(vinyl alcohol) blend fibers were prepared by spinning their solution through a viscose‐type spinneret at 25°C into a coagulating bath containing aqueous NaOH and ethanol. The influence of coagulation solution composition on the spinning performance was discussed, and the intermolecular interactions of blend fibers were studied by infrared analysis (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM) and by measurements of mechanical properties and water‐retention properties. The results demonstrated that the water‐retention properties and mechanical properties of the blend fibers increase due to the presence of PVA in the chitosan substract, and the mechanical strength of the blends is also related to PVA content and the degree of deacetylation of chitosan. The best mechanical strength values of the blend fibers, 1.82 cN/d (dry state) and 0.81 cN/d (wet state), were obtained when PVA content was 20 wt % and the degree of deacetylation of chitosan was 90.2%. The strength of the blend fibers, especially wet tenacity could be improved further by crosslinking with glutaraldehyde. The water‐retention values (WRV) of the blend fibers were between 170 and 241%, obviously higher than pure chitosan fiber (120%). The structure analysis indicated that there are strong interaction and good miscibility between chitosan and poly(vinyl alcohol) molecular resulted from intermolecular hydrogen bonds. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2558–2565, 2001     

Chitosan nanoparticles with controlled size and zeta potential

Optimization of chitosan nanoparticles (ChNs) production process employing a 2^(5–2) fractional factorial design was performed to analyze the influence of viscosity average molecular weight (40–120 kDa), the initial concentration of chitosan (2–5 g/L), the initial tripolyphosphate (TPP) concentration (0.8–1.2 g/L), the ratio chitosan/TPP (4/1–10/1) (V/V), and the stirring speed (300–700 rpm), on final nanoparticles size and zeta potential. The measured responses of average particle size and surface charge were determined on Zetasizer Nano ZS. ChNs were prepared using ionotropic cross-linking of chitosan and TPP and were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), and differential scanning calorimetry (DSC). The experiments showed that the size of synthesized nanoparticles depended on initial concentration and molecular weight of chitosan, TPP concentration and stirring speed within the chosen levels. However, the zeta potential was significantly influenced by chitosan molecular weight, chitosan concentration and stirring speed. The FTIR analysis confirmed the interaction between negative charge of TPP with positive charge of chitosan through the appearance of new peaks at 1222 and 895 cm⁻¹ in produced ChNs. XRD and DSC analysis were used to evaluate the effect of crosslinking of chitosan on crystal structure of ChNs.     

芳纶纳米纤维增强聚乙烯醇复合膜的制备与性能

以芳纶纤维Kevlar@49为原料,在温和条件下制备了芳纶纳米纤维分散体(ANFS),并利用分散体制备了芳纶纳米纤维/聚乙烯醇(ANFs/PVA)复合膜。通过傅里叶红外光谱(FTIR)仪、差示扫描量热(DSC)仪、原子力显微镜(AFM)、扫描电子显微镜(SEM)、电子万能试验机及透光度/雾度测定仪等考察了复合膜的微观结构、热学、光学及力学性能。FTIR证明,复合膜中ANFs与PVA具有一定的分子间氢键作用,促进了ANFs在PVA基体中的分散。由AFM和SEM可以清晰观察到直径为20~30 nm的芳纶纳米纤维分散体,并且通过SEM观察到复合膜表面较为平整。当芳纶纳米纤维质量分数为6.0%时,复合膜的抗拉强度为17.86 MPa,断裂伸长率为442%;透光度为82.63%,雾度为27.56%;玻璃化温度,熔融温度和结晶温度分别为75.20、208.82和174.51℃,表明其透光性良好,力学和热学性能达到最佳。     

Synthesis and Characterization of Poly(vinyl alcohol)/Poly(vinyl pyrrolidone)-Iodine Nanofibers with Poloxamer 188 and Chitosan

This study focuses on the fabrication of poly(vinyl alcohol)/ poly(vinyl pyrrolidone)-Iodine nanofibers via electrospinning. Electrospun fibers were characterized by FT-IR, DSC and SEM techniques. DSC results indicated that the thermal stability of nanofibers were improved after the addition of chitosan and poloxamer 188. SEM images showed that the spongiform structure is much more compact and fibrous in the case of added chitosan, with an average fiber diameter of 374 nm, whereas the addition of poloxamer 188 resulted in a more porous and beaded composition, with average fiber diameter of 489 nm.     

小麦蛋白/聚乙烯醇复合纳米纤维的制备及其表征

以小麦蛋白、聚乙烯醇(PVA)为原料,采用静电纺丝法制备小麦蛋白/PVA共混复合纳米纤维,重点研究纺丝液质量分数、电压、接收距离对纤维形态的影响,利用扫描电镜、傅里叶变换红外光谱、X-射线衍射光谱对纤维的形态与结构进行表征。结果表明:在纺丝液质量分数10%、小麦蛋白与PVA质量比8∶2、电压12 kV、接收距离10 cm的条件下,可以制备平均直径为280 nm左右的均一、表面光滑的纳米纤维。小麦蛋白与PVA复合后,分子间以氢键结合。     

Preparation and properties of castor oil‐based polyurethane/α‐zirconium phosphate composite films

Novel castor oil‐based polyurethane/α‐zirconium phosphate (PU/α‐ZrP) composite films with different α‐ZrP loading (0–1.6 wt %) and different NCO/OH molar ratios were synthesized by a solution casting method. The characteristic properties of the PU/α‐ZrP composite films were examined by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and tensile testing. The results from Fourier transform infrared spectroscopy indicated that strong intermolecular hydrogen bonding formed between α‐ZrP and PU, XRD and SEM results revealed that the α‐ZrP particles were uniformly distributed in the PU matrix at low loading, and obvious aggregation existed at high loading. Because of hydrogen bonding interactions, the maximum values of tensile strength were obtained with 0.6 wt % α‐ZrP loading and 1.5 of NCO/OH molar ratio in the matrix. Evidence proved that the induced α‐ZrP used as a new filler material can affect considerably the mechanical and thermal properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of electrospun polyurethane–polypyrrole nanofibers and films

Polyurethane (PU)–polypyrrole (PPy) composite films and nanofibers were successfully prepared for the purpose of combining the properties of PU and PPy. Pyrrole (Py) monomer was polymerized and dispersed uniformly throughout the PU matrix by means of oxidative polymerization with cerium(IV) [ceric ammonium nitrate Ce(IV)] in dimethylformamide. Films and nanofibers were prepared with this solution. The effects of the PPy content on the thermal, mechanical, dielectric, and morphological properties of the composites were investigated with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Fourier transform infrared (FTIR)–attenuated total reflection (ATR) spectroscopy, dielectric spectrometry, and scanning electron microscopy. The Young's modulus and glass-transition temperatures of the composites exhibited an increasing trend with increases in the initially added amount of Py. The electrical conductivities of the composite films and nanofibers increased. The crystallinity of the composites were followed with DSC, the mechanical properties were followed with DMA, and the spectroscopic results were followed with FTIR–ATR spectroscopy. In the composite films, a new absorption band located at about 1650 cm⁻¹ appeared, and its intensity improved with the addition of Py. The studied composites show potential for promising applications in advanced electronic devices. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of polyelectrolyte complex films of chitosan and gelatin

A series of chitosan–gelatin complexes was prepared by varying the ratio of constituents. Differential scanning calorimetry was used to determine the amount of the different states of water. The interaction between chitosan and gelatin was checked by IR and X-ray analysis and was related to mechanical strength. The results indicate that the water take-up of a chitosan–gelatin complex is depressed by strong interactions within networks. Chitosan can improve the tensile strength of complex films, and even with high water content these can keep appropriate tensile strength and higher elongation. © 1999 Society of Chemical Industry     

Effects of hard and soft components on the structure formation,crystallization behavior and mechanical properties of electrospun poly(l-lactic acid) nanofibers

The effects of multi-wall carbon nanotubes (MWCNTs) and poly(ethylene oxide) (PEO) on the structure formation, morphology, crystallization behavior and mechanical property of electrospun poly (l-lactic acid) (PLLA) nanofiber mats were investigated by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) and mechanical test. If incorporate hard filler, MWCNTs into electrospun PLLA nanofiber, the crystallinity, chain orientation, and crystallization behaviors were almost not influenced by the MWCNTs content owing to the MWCNTs mainly acted as impeding the crystal growth and chain diffusion. If incorporate small content of soft and miscible component, PEO (10 wt%) into the electrospun PLLA and PLLA/MWCNTs nanofibers, the crystallinity and crystallization rate of PLLA in nanofibers were obviously enhanced. The synergistic effect of PEO and MWCNTs in PLLA nanofibers was observed during melt-crystallization behaviors of PLLA/MWCNTs fibers. Based on those results, we found that the chain mobility is an important factor to influence the structure formation and crystallization behaviors in the electrospun nanofibers. Our results indicated that the structure and properties of electrospun nanofibers could be optimized by compounding with hard inorganic filler and soft polymer components.     

Synthesis and characteristics of the interpenetrating polymer network hydrogel composed of chitosan and polyallylamine

A temperature‐ and pH‐dependent hydrogel was studied with interpenetrating polymer network (IPN) hydrogels constructed with water‐insoluble chitosan and polyallylamine. Various IPNs were prepared from different weight ratios of chitosan–polyallylamine. Crosslinked‐IPN hydrogels exhibited relatively high equilibrium water content (EWC) in the range 80–83%. The EWC of IPN hydrogels depended on pH and the amount of complex, which is the content of chitosan and polyallylamine. The differential scanning calorimeter (DSC) thermogram of fully swollen IPN hydrogels appeared between 3 to 4 °C. The IPNs exhibited two glass‐transition temperatures (T_gs), indicating the presence of phase separation in the IPNs as exhibited by dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 498–503, 2002     

Preparation and characterization of biomimetic silk fibroin/chitosan composite nanofibers by electrospinning for osteoblasts culture

ABSTRACT: In this study, we have successfully fabricated electrospun bead-free silk fibroin [SF]/chitosan [CS] composite nanofibers [NFs] covering the whole range of CS content (0%, 25%, 50%, 75%, and 100%). SF/CS spinning solutions were prepared in a mixed solvent system of trifluoroacetic acid [TFA] and dichloromethane. The morphology of the NFs was observed by scanning electron microscope, and the average fiber diameter ranges from 215 to 478 nm. Confocal laser scanning microscopy confirms the uniform distribution of SF and CS within the composite NFs. To increase biocompatibility and preserve nanostructure when seeded with cells in culture medium, NFs were treated with an ethanol/ammonia aqueous solution to remove residual TFA and to change SF protein conformation. After the chemical treatment, SF/CS NFs could maintain the original structure for up to 54 days in culture medium. Properties of pristine and chemically treated SF/CS NFs were investigated by Fourier transform infrared spectroscopy [FT-IR], X-ray diffraction [XRD], and thermogravimetry/differential scanning calorimetry [TG/DSC]. Shift of absorption peaks in FT-IR spectra confirms the conformation change of SF from random coil to β-sheet by the action of ethanol, which is also consistent with the SF crystalline diffraction patterns measured by XRD. From TG/DSC analysis, the decomposition temperature peaks due to salt formation from TFA and protonated amines disappeared after chemical treatment, indicating complete removal of TFA by binding with ammonium ions during the treatment. This was also confirmed with the disappearance of F1s peak in X-ray photoelectron spectroscopy spectra and disappearance of TFA salt peaks in FT-IR spectra. The composite NFs could support the growth and osteogenic differentiation of human fetal osteoblastic [hFOB] cells, but each component in the composite NF shows distinct effect on cell behavior. SF promotes hFOB proliferation while CS enhances hFOB differentiation. The composite SF/CS NFs will be suitable for bone tissue engineering applications by choosing a suitable blend composition.PACS: 87.85.jf; 87.85.Rs; 68.37.Hk.     

聚合物浓度对PA6／氯化钙冻胶体系结构与性能的影响

以氯化钙为络合剂,将聚酰胺6（PA6）粉末与氯化钙溶解在甲酸,氯仿混合溶液中制得冻胶样品,采用DTA、XRD、FTIR、SEM等方法对冻胶结构与性能进行分析,探讨了PA6质量浓度对冻胶样品结构和性能的影响。结果表明,氯化钙可以部分屏蔽PA6的氢键,降低其结晶能力;随着PA6浓度的增大,冻胶样品的分子间作用力增强,熔点升高,不同浓度间的冻胶样品结构和性能以及络合剂的络合效果有一定的差异。     

In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers

Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC₆H₄-NH₂) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.     

Investigating the effect of PGA on physical and mechanical properties of electrospun PCL/PGA blend nanofibers

In the field of tissue engineering there is always a need for new engineered polymeric biomaterials which have ideal properties and functional customization. Unfortunately the demands for many biomedical applications need a set of properties that no polymers can fulfill. One method to satisfy these demands and providing desirable new biomaterials is by mixing two or more polymers. In this work, random nanofibrous blends of poly (ε‐caprolactone) (PCL) and polyglycolic acid (PGA) with various PCL/PGA compositions (100/0, 80/20, 65/35, 50/50, and 0/100) were fabricated by electrospinning method and characterized for soft‐tissue engineering applications. Physical, chemical, thermal, and mechanical properties of PCL/PGA blend nanofibers were measured by scanning electron microscopy (SEM), porosimetry, contact angle measurement, water uptake, attenuated total reflectance Fourier transform‐infrared spectroscopy (ATR‐FT‐IR), X‐ray diffraction (XRD), differential scanning calorimetric (DSC), dynamic mechanical thermal analysis (DMTA), and tensile measurements. Morphological characterization showed that the addition of PGA to PCL results in an increase in the average diameter of the nanofibers. According to these results, when the amount of PGA in the blend solution increased, the hydrophilicity and water uptake of the nanofibrous scaffolds increased concurrently, approaching those of PGA nanofibers. Differential scanning calorimetric studies showed that the PCL and PGA were miscible in the nanofibrous structure and the mechanical characterization under dry conditions showed that increasing PGA content results in a tremendous increase in the mechanical properties. In conclusion, the random nanofibrous PCL/PGA scaffold used in this study constitutes a promising material for soft‐tissue engineering. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012