A novel electrospun silk fibroin/hydroxyapatite hybrid nanofibers

A novel electrospinning of silk fibroin/hydroxyapatite hybrid nanofibers with different composition ratios was performed with methanoic acid as a spinning solvent. The silk fibroin/hydroxyapatite hybrids containing up to 30% hydroxyapatite nanoparticles could be electrospun into the continuous fibrous structure. The electrospun silk fibroin/hydroxyapatite hybrid nanofibers showed bigger diameter and wider diameter distribution than pure silk fibroin nanofibers, and the average diameter gradually increased from 95 to 582 nm. At the same time, the secondary structure of silk fibroin/hydroxyapatite nanofibers was characterized by X-ray diffraction, Fourier transform infrared analysis, and DSC measurement. Comparing with the pure silk fibroin nanofibers, the crystal structure of silk fibroin was mainly amorphous structure in the hybrid nanofibers. X-ray diffraction results demonstrated the hydroxyapatite crystalline nature remained as evidenced from the diffraction planes (002), (211), (300), and (202) of the hydroxyapatite crystallites, which was also confirmed by Fourier transform infrared analysis. The thermal behavior of hybrid nanofibers exhibited the endothermic peak of moisture evaporation ranging from 86 to 113 °C, and the degradation peak at 286 °C appeared. The SF/HAp nanofibers mats containing 30% HAp nanoparticles showed higher breaking tenacity and extension at break for 1.1688 ± 0.0398 MPa and 6.55 ± 1.95%, respectively. Therefore, the electrospun silk fibroin/hydroxyapatite hybrid nanofibers should be provided potentially useful options for the fabrication of biomaterial scaffolds for bone tissue engineering.     

Physical structure behavior to wettability of electrospun poly(lactic acid)/polysaccharide composite nanofibers

Poly(lactic acid) has been electrospun into submicron fibers with embedded cassava starch matrix. The fibers had average fiber diameters between 140 and 680?nm. The starch content varied from 10 to 20% in total solids. Water contact angles were measured on sheets of these fiber materials and correlated with the fiber size and starch content. Water contact angles varied from 80 to 120° which shows that the fiber composition can control the mat properties from hydrophilic to hydrophobic. The results also showed variation in the average fiber diameters alone did not always affect sheet wettability. These results show the importance of the relationship between the electrospun fiber sheet topography and material composition to the wettability of polysaccharide electrospun nanofibers.     

Novel silk fibroin/hydroxyapatite composite films: Structure and properties

Novel composite films of Bombyx mori silk fibroin (SF) and hydroxyapatite (HA) composite films, with glycerin as an additive, were fabricated by means of co-precipitation, where the theoretical HA content was varied from 2 (w/w)% to 31 (w/w)%. The structure and properties of the composite films were investigated by SEM, XRD, AFM, TGA and tensile testing. The results showed that the composite films were smooth and transparent with the uniform distribution of HA into the composites when the final HA content was lower than 21 (w/w)%. XRD and TGA data showed that the silk fibroin in the composites was predominantly in a β-sheet crystalline structure, which was induced not only by the addition of glycerin, also by the HA crystal growth during the composite fabrication, leading to the thermal stable composite films. On the other hand, the HA crystals had the anisotropic growth with high extent of lattice imperfection and the preferential orientation along c-axis, probably promoted by the silk fibroin. The mechanical testing results showed that both break strain and stress were declined with the increase of HA content in the composites, presumably due to the original brittleness of HA compound.     

聚乳酸/乙基纤维素复合膜的制备及其性能

以烯基琥珀酸酐( ASA) 作为新型增塑剂, 使用三氯甲烷作为聚乳酸( PLA) 和乙基纤维素( EC) 的共溶剂, 采用溶液浇铸法成功制备了聚乳酸/ 乙基纤维素复合膜。用红外光谱( FT IR) 、X 射线衍射(XRD) 表征了复合膜结构, 并测试了其吸水性和力学性能。FTIR 测试结果显示, 复合膜中存在强烈的氢键相互作用。XRD 表明,ASA 显著提高了PLA 和EC 2 种高聚物的界面黏合性。力学测试结果表明, ASA 对该复合膜具有良好的增塑效果。当膜中PLA 质量分数[ 37%时, PLA 对复合膜起增强作用。复合膜的吸水性随ASA 含量的增大而降低, 随PLA 含量的增大而提高。该复合膜作为一种潜在的药物缓释材料, 将具有广阔应用前景。      

Mechanical properties of electrospun PVA/MWNTs composite nanofibers

Composites of polyvinyl alcohol (PVA) and multi-walled carbon nanotubes (MWNTs) were prepared by electrospinning. A PVA/MWNTs solution was electrostatically spun to form filler wrapped nanofibers, with a diameter of ∼ 100-200 nm. As the concentration of filler in the composite was varied, the coloration of the fiber sheets changed. The SEM and TEM analyses of the fiber sheets revealed that the deformation of the fiber increases with increasing nanotube concentration. The mechanical properties were studied using a universal testing machine (UTM). The analysis is presented in detail. It is argued that the degree of dispersivity orientation and anisotropy of the nanotubes and the amount of interfacial stress in the filler/polymer are the predominant factors determining the variation in the tensile properties of the composites with the filler concentration.     

纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维的制备及表征

通过静电纺丝法制备出纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维,利用扫描电镜、红外光谱仪、X射线衍射仪对纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维形貌和结构进行表征,并进行了拉伸测试。结果表明,随着超细纤维中羟基磷灰石含量的增加,纤维的直径逐渐降低,纤维中聚己内酯的结晶逐渐变差。相比于丝素蛋白/聚己内酯超细纤维,含有质量比为30%羟基磷灰石的复合超细纤维仍具有较好的力学性能。体外小鼠成纤维细胞(L929)培养表明,纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维对细胞没有毒性。     

Nanodiamond/poly (lactic acid) nanocomposites: Effect of nanodiamond on structure and properties of poly (lactic acid)

Nanodiamond (ND)/poly (lactic acid) (PLA) nanocomposites with potential for biological and biomedical applications were prepared by using melting compound methods. By means of transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analyses (TGA), Dynamic mechanical analyses (DMA), Differential scanning calorimetry (DSC) and Tensile test, the ND/PLA nanocomposites were investigated, and thus the effect of ND on the structural, thermal and mechanical properties of polymer matrix was demonstrated for the first time. Experimental results showed that the mechanical properties and thermal stability of PLA matrix were significantly improved, as ND was incorporated into the PLA matrix. For example, the storage modulus (E′) of 3 wt% ND/PLA nanocomposites was 0.7 GPa at 130 °C which was 75% higher than that of neat PLA, and the initial thermal decomposition was delayed 10.1 °C for 1 wt% ND/PLA nanocomposites compared with the neat PLA. These improvements could be ascribed to the outstanding physical properties of ND, homogeneous dispersion of ND nanoclusters, unique ND bridge morphology and good adhesion between PLA matrix and ND in the ND/PLA nanocomposites.     

Characteristics of curcumin-loaded poly (lactic acid) nanofibers for wound healing

Curcumin (Cur) is a well-known extract of the root of Curcuma longa L. that has multi biological functions such as anti-oxidation, anti-inflammatory, anti-cancer, and wound healing properties. In the present study, poly (lactic acid) (PLA) nanofibers were used as a carrier for Cur because PLA nanofibers are biocompatible and have a high-specific surface area and high porosity, which can enhance the functional properties of Cur. The chemical and biological characteristics of Cur/PLA blended nanofibers containing varied amounts of Cur were examined. An increase from 0.125 to 6.250 wt% Cur in PLA caused a decrease in the diameters of the nanofibers from 971 ± 274 to 562 ± 177 nm. At Cur concentrations of <1.250 wt%, PLA and Cur showed good miscibility in the blended nanofibers, as shown by FTIR analysis and tensile tests. The inclusion of Cur in the blended nanofibers at concentration as low as 0.125 wt% promotes the attachment and proliferation of cells. The in vivo wound healing capability of Cur-loaded PLA nanofibers was assessed in a mouse model; treatment with Cur-loaded PLA nanofibers significantly increased the rate of wound closure (87 %) by day 7 compared with that of PLA nanofibers (58 %). The results of this study suggest that Cur-loaded nanofibers with appropriate Cur concentration are nontoxic and have potential as component of wound-healing patches.     

Preparation and bending properties of three dimensional braided single poly (lactic acid) composite

New three dimensional (3D) braided single poly (lactic acid) composites (PLA–SPCs) were obtained by combining 3D and five (5)-direction braiding technique and hot-compression technical process. 3D and 5-direction braided preforms with different braiding angles, thicknesses and fiber volume fractions were prepared. Preforms were preheated in the specially designed die system in order to make all of the fibers partially melted. In the next stage, the preforms were consolidated under a certain pressure (from 7.8 to 10 MPa) at temperatures ranging from 130 up to 150 °C. Under the controlled processing conditions, one part of fiber body formed matrix while the other part retained its fibrous form.At the same consolidation temperature, the maximum bending stress values resulted to be substantially dependent on the fiber volume fraction of PLA–SPCs, while the bending modulus values were largely subjected to the fiber content in the length direction. The increases of consolidation pressure gave rise to better fusion of neighboring fibers with the result that the maximum stress and modulus were increased. As the consolidation temperature increases, the fusion bonding was improved, the bending failure feature was converted from plastic to brittle, both maximum bending stress and modulus values were increased. It is expected that this study could provide a new approach for the manufacture of high-performance single polymer composites (SPCs) by using thermoplastic polymer fibers.     

Scaffolds for drug delivery,part I: electrospun porous poly(lactic acid) and poly(lactic acid)/poly(ethylene oxide) hybrid scaffolds

This is the first in a series of papers, focused on the development of a biodegradable, controlled, and potentially targeted drug delivery system. In this paper, we describe the production of highly porous biodegradable fibrous structures suitable for biomedical applications and as a matrix for drug delivery. Two structures are described below. The first structure is composed of electrospun poly(lactic acid) (PLA) fibers and is unique due to (1) the uniformity if its constitute fibers’ diameter, (2) consistent surface pore dimensions of each fiber, (3) the use of only a single solvent, (4) interior nano-size porosity throughout each individual fiber, and (5) the independency of surface pore dimensions on fiber diameter. The produced matrix will be further impregnated with cargo loaded nanoparticles—Red clover necrotic mosaic virus (RCNMV)—to achieve a controlled drug delivery system (described in Part III) for cancer treatments. Such a structure can also be used as tissue engineering scaffolds and filter media. The second electrospun structure has enhanced hydrophilicity compared to PLA matrix and is formed by blending poly(lactic acid)/poly(ethylene oxide) (PEO) polymers. The incorporation of PEO in the matrix introduces preferable sites for aqueous compounds to be attached to while retaining the overall structural integrity and porous morphology. It is hypothesized that the existence of alternative hydrophilic and hydrophobic segments in the structure may reduce post-implantation complications such as platelet adhesion.     

The effects of cellulose nanowhiskers on electrospun poly (lactic acid) nanofibres

The effects of cellulose nanowhiskers on the microstructure and thermal behaviour of electrospun poly (lactic acid) (PLA) nanofibres have been investigated in this study. The PLA/cellulose nanowhiskers composite nanofibres are successfully produced by electrospinning the mixtures of cellulose whiskers with PLA solution. The diameters of PLA and its composites are around 300 nm. The scanning electron micrographs show that the cellulose nanowhiskers do not protrude out of the outer surfaces of PLA nanofibres. The existence of cellulose nanowhiskers in the electrospun PLA matrix nanofibres, and the microstructural evolution are investigated by using X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) analysis shows the formation trend of PLA α crystal with the addition of cellulose nanowhiskers. The electrospun PLA and PLA/cellulose nanowhiskers composites reveal very low crystallinity due to the rapid solvent evaporation and relatively slow crystallisation kinetics character of PLA. The electrospun nanofibres show particularly different thermal behaviour from that of the solution cast films. The nanofibres of pure PLA and PLA/cellulose nanowhiskers experience two consecutively overlapping crystallisation processes. The cellulose nanowhiskers act as heterogeneous sites for nucleation of PLA by decreasing the cold crystallisation onset temperature. The incorporation of cellulose nanowhiskers into PLA nanofibres is expected to improve mechanical properties and bring new functionalities to the electrospun matrix nanofibres.     

大黄素/聚乳酸物复合薄膜的制备及抗凝血研究

药物洗脱支架具有良好的抗增生性能,对血管支架内再狭窄起到很好的抑制作用,但其抗凝血性能仍有待改善.大黄素(emodin)是一类具有抗增生以及抑制血小板黏附聚集等特性的中药提取物,有望成为药物洗脱支架的选用药物.本文以可降解高分子材料聚乳酸(PLA)为载体制备了浓度为3%(质量分数)、5%(质量分数)的大黄素复合薄膜.采用傅立叶变换红外光谱研究了复合薄膜的组成成分,用体外血小板粘附实验和部分凝血活酶时间(APTT)表征复合薄膜的体外抗凝血性能.结果显示大黄素与PLA的特征峰在复合薄膜的红外图谱中均有出现,复合薄膜的血小板粘附和聚集数量减少且APTT长于纯PLA薄膜,这都表明大黄素/聚乳酸复合薄膜的抗凝血性能优于纯PLA薄膜.     

Stacked-lamellar structure of electrospun poly(heptamethylene terephthalate) nanofibers

Poly(heptamethylene terephthalate) (poly(7GT)), which is an aromatic polyesters was synthesized, and nanofibers of poly(7GT) were prepared via electrospinning from its solution in 1,1,1,3,3,3-hexafluoro-2-propanol. Uniaxially oriented thin films were also prepared by applying shear strain to molten poly(7GT). Morphology of as-spun and annealed nanofibers and that of uniaxially oriented thin films were investigated by transmission electron microscopy. Selected-area electron diffraction (SAED) of bundles of the annealed nanofibers gave a highly oriented fiber pattern. In addition, dark-field images of the poly(7GT) nanofibers, which had been annealed at 85 °C for 48 h, were taken by using some of the reflections on/near the equator. The images showed a stacked-lamellar structure, in which crystalline lamellae appearing as bright striations oriented perpendicularly to the fiber axis were stacked in the direction of the fiber axis, and the corresponding average long period was estimated at about 19 nm. As for the uniaxially oriented thin films, SAED also gave an oriented fiber pattern. When the annealing of the films was performed similar to nanofibers, crystallization occurred and a stacked-lamellar structure was constructed parallel to the shearing direction. The corresponding average long period was estimated at about 27 nm. By comparing the fiber patterns between annealed nanofibers and thin films, it seems that electrospinning is more effective than uniaxial stretching in enhancing the molecular orientation in the case of poly(7GT).     

玉米秸秆微晶纤维素/聚乳酸复合膜的制备与性能

采用玉米秸秆微晶纤维素(CSCMC)作为增强材料, 生物可降解材料聚乳酸(PLA)作为基体, 制备了CSCMC/PLA复合膜材料, 并对复合膜的结晶度、热稳定性能、力学性能进行了测试。结果表明, 复合膜材料的热稳定性能和力学性能优于纯聚乳酸膜。当CSCMC的质量分数为10%时, 复合膜的热稳定性能和力学性能达到最佳, 与纯PLA膜相比, 起始分解温度提高了34.38 ℃, 拉伸强度提高了58.3%, 断裂伸长率提高了31.1%。      

Characterization and mechanical properties of electrospun cellulose acetate/graphene oxide composite nanofibers

Graphene oxide incorporated cellulose acetate composite nanofibers were prepared via an electrospinning technique. The weight percentage of graphene oxide varied from 0.05 to 1.5 wt.% in the polymer solution. The morphologies and crystal structures of the resultant composite nanofibers were investigated by scanning electron microscopy and X-ray diffraction. The specific interaction was demonstrated by Fourier-transform infrared spectroscopy. Tensile test was performed to measure the mechanical properties of the prepared cellulose acetate/graphene oxide composite nanofibers. 1.5 wt.% cellulose acetate/graphene oxide composite nanofibers showed the highest tensile strength and Young's modulus.     

以电纺丝蛋白纤维为模板的pH响应性介孔SiO2纳米管的制备及药物释放

以资源丰富的家蚕丝为原料,氯化钙/甲酸为溶解体系,利用静电纺丝法制得丝素蛋白（SF）纳米纤维;以SF纤维为模板在其表面涂覆SiO₂,经煅烧后获得了介孔SiO₂纳米管（MSNTs）;在MSNTs管壁上接枝醛基（-CHO）,利用醛基与盐酸阿霉素（DOXHCl）氨基之间的动态共价键制得了pH响应性药物释放体系。通过SEM、TEM、TG、比表面积（BET）分析、FTIR及紫外-可见吸收（UV-Vis）光谱对MSNTs的微观结构、功能化及载药体系的pH响应性进行了表征。结果表明:当SF浓度在15wt%~17wt%时,可获得圆柱状且直径在（113±27）~（134±32）nm范围内可调的SF纤维模板;通过调整涂覆液中十六烷基三甲基溴化铵（CTAB）的浓度来调节MSNTs管壁的厚度,当CTAB用量从1.25 mg/mL增加到3.75 mg/mL时,MSNTs管壁厚度从30~39 nm增加到63~65 nm,对应的比表面积从154 m2/g下降到98 m2/g,介孔平均孔径从12.5 nm下降到10.0 nm;醛基修饰的MSNTs载DOXHCl（MSNT-CHO-DOX）体系,在pH值分别为7.4、6.5和5.5的磷酸氢二钾-磷酸二氢钾（PB）缓冲溶液中进行释放,100 h时释药率分别达到23%、35%和75%,实现了MSNT-CHO-DOX载药体系的pH响应性释放。      

甲壳素纳米晶须/聚乳酸复合纤维膜的制备及表征

采用静电纺丝技术制备了甲壳素纳米晶须/聚乳酸复合纳米纤维膜并对其进行了表征分析.借助扫描电子显微镜(SEM) 及相关测试软件,测出复合纳米纤维平均直径在500～1000nm之间;当甲壳素纳米晶须含量低于7％时,对复合纳米纤维的可纺性及形貌影响较小;但当其含量高于7％时,复合纳米纤维表面变得粗糙.傅立叶红外变换光谱仪(FT-IR)和X射线衍射仪(XRD)观察分析表明,甲壳素纳米晶须已成功加入到聚乳酸纤维中.拉伸试验结果表明,当纳米晶须含量为3％时,复合膜的拉伸强度提高了63.65％,进一步增加纳米晶须含量,其增强作用呈下降趋势,甚至出现负增强.     

碳纤维/聚乳酸复合材料的结晶性能和流变特性

以碳纤维（CF）作填料,制备了CF/聚乳酸（CF/PLA）复合材料,CF的质量比（CF∶PLA）为1%、3%、5%、10%和15%。研究了PLA及CF/PLA复合材料的结晶性能和流变特性。结果表明,质量比≤3%时,CF在基体中起到了异相成核的作用,提高了PLA的结晶性能,XRD衍射峰强度增强,CF/PLA复合材料结晶温度和结晶度分别提高到112.5℃和30.7%,流变特性与纯PLA相似。CF的质量比增加到5%时,达到"渗流阈值",黏度激增,限制了分子链段的自由运动,导致CF/PLA复合材料结晶性能下降。CF质量比为15%时,CF/PLA复合材料结晶温度降低至93.1℃,结晶度只有2.5%。     

增容纳米纤维素/聚乳酸复合材料的制备与性能

采用接枝共聚法制备了马来酸酐和丙烯酸丁酯双单体接枝聚乳酸（PLA）共聚物（mPLA）,然后以mPLA为增容剂,通过溶液浇铸法制备纳米纤维素（NCC）/PLA复合材料。采用SEM、DSC、TG、广角X射线衍射（WXRD）、力学和降解性能测试研究了mPLA对NCC/PLA复合材料的结构和性能的影响。结果表明:mPLA在PLA与NCC之间起到了良好的界面增容作用,促进了NCC在PLA基体中的分散。更精细分散的NCC促进了PLA的结晶成核,复合材料的结晶温度降低,结晶度提高;NCC/mPLA/PLA复合材料的力学性能随着mPLA含量增加呈先上升后下降的趋势,当mPLA含量为8%时,复合材料的拉伸强度和弹性模量与未添加mPLA的复合材料相比,分别提高了30.2%和41.4%;亲水性的NCC加速了NCC/PLA复合材料的降解,加入mPLA后,复合材料的降解速率有所减慢,但仍然快于纯PLA的降解。      

同轴静电纺再生丝素/丝胶蛋白纤维的制备及其形态结构表征

模仿蚕丝的组成和结构,利用同轴静电纺丝法制备了以再生丝素蛋白（RSF）为＂芯＂、丝胶蛋白（SS）为＂皮＂的双组分静电纺纤维。通过扫描电镜和透射电镜研究了内层纺丝液流速（Qc）、电压（U）、接收距离（D）以及场强（E）等参数对同轴静电纺RSF/SS纤维形态结构的影响。研究结果表明纤维的平均直径在1400～2100nm左右,皮-芯层结构清晰;Qc对纤维皮-芯层结构的影响较大,过大的内层纺丝液流速会因外层丝胶对内层丝素的包裹不均匀而导致偏芯现象;随E的增加（U增加或D减小）,纤维的直径及其分布显著减小,皮-芯层结构清晰;相同E下,高电压、长距离利于纤维的细化,使直径变细且分布均匀,皮-芯层结构明显。