Fabrication and characterization of bioactive silk fibroin/wollastonite composite scaffolds

Composite scaffolds of silk fibroin (SF) with bioactive wollastonite were prepared by freeze-drying. X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy analysis showed that random coil and β-sheet structure co-existed in the SF scaffold. The mechanical performance, surface hydrophilicity and water-uptake capacity of the composite scaffolds were improved compared with those of pure SF scaffold. The bioactivity of the composite scaffold was evaluated by soaking in a simulated body fluid (SBF), and formation of a hydroxycarbonate apatite (HCA) layer was determined by FT-IR and XRD. The results showed that the SF/wollastonite composite scaffold was bioactive as it induced the formation of HCA on the surface of the composite scaffold after soaking in SBF for 5 days. In vitro cell attachment and proliferation tests showed that the composite scaffold was a good matrix for the growth of L929 mouse fibroblast cells. Consequently, the incorporation of wollastonite into the SF scaffold can enhance both the mechanical strength and bioactivity of the scaffold, which suggests that the SF/wollastonite composite scaffold may be a potential biomaterial for tissue engineering.     

New poly(butylene succinate)/layered silicate nanocomposites: preparation and mechanical properties

New poly(butylene succinate) (PBS)/layered silicate nanocomposites have been successfully prepared by simple melt extrusion of PBS and octadecylammonium modified montmorillonite (C18-mmt) at 150 degrees C. The d-spacing of both C18-mmt and intercalated nanocomposites was investigated by wide-angle X-ray diffraction analysis. Bright-field transmission electron microscopic study showed several stacked silicate layers with random orientation in the PBS matrix. The intercalated nanocomposites exhibited remarkable improvement of mechanical properties in both solid and melt states as compared with that of PBS matrix without clay.     

Preparation and characterization of bioactive collagen/wollastonite composite scaffolds

A novel biodegradable collagen/wollastonite composite was prepared as three-dimensional scaffolds by freeze-drying method. Scanning electron microscope (SEM) micrographs of scaffolds showed a continuous structure of interconnected pores, and pore size was about 100 m. The tensile strength of the scaffolds was improved by incorporation of wollastonite and the in vitro bioactivity of the scaffolds was evaluated by examining the hydroxyapatite (HA) deposition on their surface in simulated body fluid (SBF). After soaking in SBF for 7 days, collagen reconstituted to fibers and HA nodules formed on collagen fibers. The result suggests that the incorporation of wollastonite could improve the mechanical strength and the in vitro bioactivity of the composite. The scaffolds could be a potential biomaterial for bone tissue engineering.     

聚丁二酸丁二醇酯/水滑石纳米复合材料的制备及性能研究

采用双螺杆挤出机制备了聚丁二酸丁二醇酯/水滑石(PBS/HT)纳米复合材料,并详细研究了复合材料的形貌及分散、结晶和熔融行为,晶体结构和球晶形态以及力学性能。采用SEM、TEM、DSC、XRD、POM和DMA进行了表征测试,结果表明层状水滑石纳米粒子较好地分散在PBS基体中,加入HT具有明显的异相成核能力,显著地提高了PBS的结晶温度。偏光显微镜结果显示,随着HT加入量的增加PBS球晶密度增加,球晶尺寸细化。HT添加量为1%(质量分数)时复合材料的拉伸强度增大,随着HT加入量增加断裂伸长率下降而弹性模量增加。动态机械测试表明复合材料的储能模量显著提高。     

Formation of bone-like apatite layer on chitosan fiber mesh scaffolds by a biomimetic spraying process

Bone-like apatite coating of polymeric substrates by means of biomimetic process is a possible way to enhance the bone bonding ability of the materials. The created apatite layer is believed to have an ability to provide a favorable environment for osteoblasts or osteoprogenitor cells. The purpose of this study is to obtain bone-like apatite layer onto chitosan fiber mesh tissue engineering scaffolds, by means of using a simple biomimetic coating process and to determine the influence of this coating on osteoblastic cell responses. Chitosan fiber mesh scaffolds produced by a previously described wet spinning methodology were initially wet with a Bioglass((R))-water suspension by means of a spraying methodology and then immersed in a simulated body fluid (SBF) mimicking physiological conditions for one week. The formation of apatite layer was observed morphologically by scanning electron microscopy (SEM). As a result of the use of the novel spraying methodology, a fine coating could also be observed penetrating into the pores, that is clearly within the bulk of the scaffolds. Fourier Transform Infrared spectroscopy (FTIR-ATR), Electron Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analysis also confirmed the presence of apatite-like layer. A human osteoblast-like cell line (SaOs-2) was used for the direct cell contact assays. After 2 weeks of culture, samples were observed under the SEM. When compared to the control samples (unmodified chitosan fiber mesh scaffolds) the cell population was found to be higher in the Ca-P biomimetic coated scaffolds, which indicates that the levels of cell proliferation on this kind of scaffolds could be enhanced. Furthermore, it was also observed that the cells seeded in the Ca-P coated scaffolds have a more spread and flat morphology, which reveals an improvement on the cell adhesion patterns, phenomena that are always important in processes such as osteoconduction.     

微米六方BN-KH550/聚丁二酸丁二醇酯耐热性复合膜的制备及性能

为进一步改善聚丁二酸丁二醇酯(PBS)的力学性能和耐热性能,采用硅烷偶联剂KH550改性微米六方氮化硼(h-BN),对PBS进行共混改性,通过熔融共混与开炼压延工艺制备了具有较高耐热性的h-BN-KH550/PBS复合膜。对h-BN-KH550粒子结构和复合膜的力学性能、聚集态结构、断面形貌、结晶性能及热稳定性进行了测试和表征。结果表明:与PBS相比,h-BN-KH550/PBS复合膜的力学性能得到改善,当KH550与h-BN质量比为2∶50、h-BN-KH550与PBS质量比为3∶50时,综合力学性能最优;h-BN-KH550粒子可在PBS中均匀分散;在PBS结晶过程中,h-BN-KH550作为成核剂,使PBS的结晶速率加快,结晶度增大;h-BN-KH550/PBS复合膜的热稳定性显著提高,当h-BN-KH550与PBS质量比为3∶50时,复合膜热分解过程中质量损失为5%、10%、50%时的温度(T5d、T10d、T50d)和热分解峰值温度(Tp)分别提高了30.0、22.6、9.5和10.0℃。     

微晶纤维素/聚丁二酸丁二醇酯复合材料的流变行为

采用熔融共混法制备了微晶纤维素/聚丁二酸丁二醇酯(MCC/PBS)复合材料,用高级毛细管流变仪和旋转流变仪分别测定复合材料的稳态流变性能和动态流变性能,研究了不同MCC含量、不同温度对复合材料流变行为的影响。结果表明,复合材料的黏度与剪切速率的流变曲线符合幂律流体的特征,可以用幂律模型对其进行拟合;复合材料的黏度与温度的关系可用Arrhenius方程对其进行描述。在线性黏弹区,复合材料的储能模量(G′)维持恒定,当应变(γ)超过临界值(γ_c)时,复合材料进入非线性黏弹区,出现了"Payne"效应,并且随着MCC含量的增加,γ_c下降。在角频率(ω)扫描范围内,复合材料的储能模量(G′)、损耗模量(G″)和复数黏度|η*|均随着MCC含量的增加而增大。在相同的MCC含量下,G″的值始终大于G′的值,损耗因子(tanδ)均大于1。在低频区,G′出现第二平台。MCC/PBS复合材料加工流变特性的研究,对指导MCC/PBS复合材料的成型加工具有一定的价值。     

Ectopic bone formation in cell-seeded poly(ethylene oxide)/poly(butylene terephthalate) copolymer scaffolds of varying porosity

Scaffolds from poly(ethylene oxide) and poly(butylene terephthalate), PEOT/PBT, with a PEO molecular weight of 1,000 and a PEOT content of 70 weight% (1000PEOT70PBT30) were prepared by leaching salt particles (425–500 μm). Scaffolds of 73.5, 80.6 and 85.0% porosity were treated with a CO₂ gas plasma and seeded with rat bone marrow stromal cells (BMSCs). After in vitro culture for 7 days (d) in an osteogenic medium the scaffolds were subcutaneously implanted for 4 weeks in nude mice. Poly(d, l-lactide) (PDLLA) and biphasic calcium phosphate (BCP) scaffolds were included as references. After 4 weeks (wks) all scaffolds showed ectopic formation of bone and bone marrow. For the scaffolds of different porosities, no significant differences were observed in the relative amounts of bone (7–9%) and bone marrow (6–11%) formed, even though micro computed tomography (μ-CT) data showed considerable differences in accessible pore volume and surface area. 1000PEOT70PBT30 scaffolds with a porosity of 85% could not maintain their original shape in vivo. Surprisingly, 1000PEOT70PBT30 scaffolds with a porosity of 73.5% showed cartilage formation. This cartilage formation is most likely due to poorly accessible pores in the scaffolds, as was observed in histological sections. μ-CT data showed a considerably smaller accessible pore volume (as a fraction of the total volume) than in 1000PEOT70PBT30 scaffolds of 80.6 and 85.0% porosity. BMSC seeded PDLLA (83.5% porosity) and BCP scaffolds (29% porosity) always showed considerably more bone and bone marrow formation (bone marrow formation is approximately 40%) and less fibrous tissue ingrowth than the 1000PEOT70PBT30 scaffolds. The scaffold material itself can be of great influence. In more hydrophobic and rigid scaffolds like the PDLLA or BCP scaffolds, the accessibility of the pore structure is more likely to be preserved under the prevailing physiological conditions than in the case of hydrophilic 1000PEOT70PBT30 scaffolds. Scaffolds prepared from other PEOT/PBT polymer compositions, might prove to be more suited.     

Surface wetting phenomena of plasma polymer-coated sheets of poly(l-lactic acid)/poly(butylene succinate)

Water-repellent surfaces were fabricated on blend sheets of poly(l-lactic acid)/poly(butylene succinate) with various blending ratios by the successive processing; (1) plasma etching, followed by (2) the hydrophobic plasma polymer coating. Rough morphology was formed effectively on the mosaic structured surface of blend sheets via the oxidative etching, and advanced water repellency was achieved after the thin membrane coating was synthesized with a hydrophobic plasma polymer coating by use of hexamethyldisiloxane or hexamethyldisilazane. High water repellency is expressed through the columnar hair-like structured model, where the air-water surface interaction in the voids is taken into account.     

Preparation of poly (vinyl alcohol)/silica composite nanofibers membrane functionalized with mercapto groups by electrospinning

Membranes of poly vinyl alcohol (PVA)/silica functionalized with mercapto groups are synthesized by electrospinning. Scanning electron microscopy (SEM) studies showed that the fiber diameters are in the range of 200-300 nm. The thickness of nanofiber decreases with an increase in calcination temperature. The results of Fourier transform infrared (FTIR) indicated that PVA/silica nanofibers are functionalized by mercapto groups via the hydrolysis poly-condensation method. N₂ adsorption-desorption showed that organic molecules can be removed completely when the PVA/silica composite fibers are calcinated at 800 °C. The fibers calcinated at 800 °C were pure inorganic silica species with a mesoporous structure. These mercapto groups functionalized PVA/silica nanofibers have a great potential application in the field of adsorption of heavy metal ions.     

纳米氧化石墨烯/聚丁二酸丁二醇酯复合材料的制备与性能

以天然石墨为原料,利用改进的HUMMERS'法制备了氧化石墨烯(GO);采用原位复合方式制备了纳米氧化石墨烯/聚丁二酸丁二醇酯(GO/PBS)复合材料,并对其性能进行了研究。结果表明:适量GO的加入能更有效地加快GO/PBS复合材料的结晶速度;GO的加入,提高了GO/PBS复合材料的力学性能和酶降解速率;随着GO添加量的增加,复合材料晶体尺寸减小,GO起到了成核剂的作用。     

Study on morphology and characterization of poly(mphenylene isophtalamide)/multi-walled carbon nanotubes composite nanofibers by electrospinning

Electrospinning technique is the main method of preparing polymer nanofiber simply, directly and continuously at present. In this work, electrospinning blend solution was prepared by in-situ polymerization using acid-modified multi-walled carbon nanotubes (MWNTs), m-phenylenediamine (MPD) and isophthaloyl chloride (IPC). And then composite nanofibers were prepared by electrospinning. MWNTs played an important role in nanofiber's properties. The effects of MWNTs on the morphology and characterization of the MWNTs/PMIA composite nanofibers were investigated. Scanning electron microscopy (SEM), thermal gravimetric analyzer (TGA), and X-ray diffraction (XRD) were utilized to characterize the MWNTs/PMIA nanofibers morphology and properties. The experimental results indicated that the nanofibers diameter decreased and solution dynamic viscosity increased with increasing MWNTs contents. XRD data demonstrated that PMIA composite nanofibers had the same crystal type as the pure PMIA nanofiber, and crystallinity was improved with increasing MWNTs loading. Transmission electron microscopy (TEM) was used to confirm MWNTs aligned along the axis of composite nanofibers.     

生物质基降解塑料PBS的研制

以玉米和小麦秸秆为原料,通过粉碎、闪蒸等化学和物理处理和加工,并进行初步糖化,使其可作为微生物可发酵的糖源。以新的琥珀酸产生菌株-产琥珀酸放线杆菌及重组微生物作为发酵的微生物菌株对生物质基糖源进行厌氧发酵,在液体深层厌氧培养条件下制备琥珀酸。通过正交实验研究了发酵液中葡萄糖、酵母膏、磷酸盐、尿素、K+、Mg2+、Mn2+等因素对琥珀色产量的影响。通过离子色谱柱脱色,分离得到纯度为95%以上琥珀酸,秸秆转化率达到75%。利用生物法制备的琥珀酸在Sn-Ti系纳米催化剂作用下通过一步法合成了重均分子量超过20万降解塑料聚(琥珀酸丁二醇酯)。     

高分子量聚丁二酸丁二醇酯的制备及性能研究

以1,4-丁二醇和丁二酸为原料,通过加入少量的扩链剂,利用直接缩聚法在短时间内合成了高分子量的聚丁二酸丁二醇酯(PBS).采用GPC、DSC以及TGA等方法对产物进行了表征,同时研究了扩链剂的加入对聚合物性能的影响.结果表明,当扩链剂加入量为PBS预聚物的2.5％时,扩链产物的性能最佳,重均分子量由3万上升到17万,拉...     

Thermal and thermomechanical properties of poly(butylene succinate) nanocomposites

This article describes the thermal and thermomechanical properties of poly(butylene succinate) (PBS) and its nanocomposites. PBS nanocomposites with three different weight ratios of organically modified synthetic fluorine mica (OMSFM) have been prepared by melt-mixing in a batch mixer at 140 degrees C. The structure and morphology of the nanocomposites were characterized by X-ray diffraction (XRD) analyses and transmission electron microscopy (TEM) observations that reveal the homogeneous dispersion of the intercalated silicate layers into the PBS matrix. The thermal properties of pure PBS and the nanocomposite samples were studied by both conventional and temperature modulated differential scanning calorimetry (DSC) analyses, which show multiple melting behavior of the PBS matrix. The investigation of the thermomechanical properties was performed by dynamic mechanical analysis. Results reveal significant improvement in the storage modulus of neat PBS upon addition of OMSFM. The tensile modulus of neat PBS is also increased substantially with the addition of OMSFM, however, the strength at yield and elongation at break of neat PBS systematically decreases with the loading of OMSFM. The thermal stability of the nanocomposites compared to that of the pure polymer sample was examined under both pyrolytic and thermo-oxidative environments. It is shown that the thermal stability of PBS is increased moderately in the presence of 3 wt% of OMSFM, but there is no significant effect on further silicate loading in the oxidative environment. In the nitrogen environment, however, the thermal stability systematically decreases with increasing clay loading.     

生物质基聚丁二酸丁二醇酯(PBS)应用研究进展

由于石油资源的日益枯竭,通过生物资源发酵得到琥珀酸来生产聚丁二酸丁二醇酯(PBS),以替代现在石油基产品为原料的PBS,是PBS产业发展的新方向,丁二酸发酵的商业化促进了生物质基PBS的发展和应用,通过对PBS进行各种改性以及加工成型,制得各类制品,使PBS产品能够应用于不同领域,生物质基PBS作为一种绿色塑料具有广阔的发展前景。     

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

Multiblock copolyester (PBS-b-PES) containing poly(butylene succinate) (PBS) and poly(ethylene succinate) (PES) was successfully synthesized by chain-extension of dihydroxyl terminated PBS (HO-PBS-OH) and PES (HO-PES-OH) using 1,6-hexmethylene diisocyanate (HDI) as a chain extender. The chemical structures, molecular weights, crystallization behaviors, thermal and mechanical properties of the copolyesters were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), wide-angle X-ray diffraction (WAXD), tensile testing and hydrolytic degradation. High-molecular-weight copolyesters with M_w more than 2.0 × 10⁵ g mol⁻¹ were easily obtained through chain-extension. The copolyesters showed a single glass transition temperature (T_g) which increased with PES content. The melting point temperature (T_m) and relative degree of crystallinity (X_c) of the copolyesters decreased first and then increased with PES content. The copolyesters manifested excellent mechanical properties, for example, PBS₅-b-PES₅ had fracture stress of 61.8 MPa and fracture strain of 1173%. The chain-extension reaction provided a very effective way to produce high molecular weight multiblock copolyesters.     

Fabrication of poly(3-methylthiophene)/poly(ethylene oxide)/ruthenium oxide composite electrospun nanofibers for supercapacitor application

Journal of Materials Science: Materials in Electronics - In the present work, composites of poly(3-methylthiophene)/poly(ethylene oxide)/ruthenium oxide nanofibers (PMT/PEO/RuO2) were fabricated by...     

Fabrication of HA/PHBV composite scaffolds through the emulsion freezing/freeze-drying process and characterisation of the scaffolds

Biodegradable polymer-based scaffolds containing osteoconductive hydroxyapatite (HA) particles can be very useful for bone tissue engineering. In this investigation, HA nanoparticles were incorporated in poly(hydroxybutyrate-co-valerate) (PHBV) polymer to fabricate osteoconductive composite scaffolds. PHBV and HA/PHBV scaffolds were made using an emulsion freezing/freeze-drying technique. The scaffolds produced were subsequently characterized using several techniques. It was found that the scaffolds were highly porous and had interconnected porous structures. The pore size ranged from several microns to around 300 mum. The spherical HA nanoparticles which were produced in-house through a nanoemulsion process could be incorporated into composite scaffolds although some of these nanoparticles existed on the surface of pore walls when a relatively large amount of HA was used for composite scaffolds. The incorporation of HA nanoparticles also enhanced compressive mechanical properties of the scaffolds.