纳米硅酸镁锂-壳聚糖-海藻酸钠复合支架材料的制备与性能

利用真空冷冻干燥技术, 将不同质量的纳米硅酸镁锂(nLMS)与壳聚糖(CA)和海藻酸钠(SA)混合, 制备了纳米硅酸镁锂-壳聚糖-海藻酸钠(nLMS-CS-SA)复合支架材料. 研究了不同质量分数(1%, 2%, 3%, 4%)的nLMS对nLMS-CS-SA复合支架材料的外形、 微观形貌、 溶胀率、 孔隙率、 体外降解性能和生物相容性的影响, 以确定nLMS-CS-SA复合支架材料中最佳nLMS含量. 研究结果显示, nLMS-CS-SA复合支架材料是具备形态可塑性的多孔状固体, 各组材料纵断面呈片层状, 其结构疏松且内部孔隙具有高度连通性; 随着nLMS含量的增加, nLMS-CS-SA复合支架材料的孔隙率呈现先降后升的趋势; 当nLMS的质量分数为3%时, 其溶胀比最小, 体外降解速率最慢; nLMS的添加降低了nLMS-CS-SA复合支架材料的毒性. 因此, nLMS在nLMS-CS-SA复合支架材料中的最佳含量为3%.     

海藻酸钠和壳聚糖静电复合弹性支架的制备和表征

通过静电作用和相分离技术制备海藻酸钠/壳聚糖静电复合弹性支架,研究了冷冻温度和固含量对支架材料孔径的影响及组分比对材料力学性能、亲水性、降解性能和生物相容性的影响.固含量为2%(质量分数)及冷冻温度为-24℃时,支架孔径为110~170μm,并且亲水性良好,平衡溶胀度大于1400%.改变固含量和组分比可调控材料的力学性能;循环力学测试表明,湿态支架具有良好的弹性和一定的耐疲劳性;降解速率可由组分比调控;兔脂肪干细胞(rASCs)在支架上的培养结果表明,羧基和氨基摩尔比为2∶1和1∶1时细胞以聚集体存在;羧基和氨基摩尔比为1∶2时细胞黏附于支架上,实现细胞黏附/聚集体的调控.     

石墨烯-Li2MnSiO4复合正极材料的合成与电化学性能研究

采用水热辅助溶胶凝胶法成功合成了石墨烯-Li₂MnSiO₄锂离子电池复合正极材料. 利用XRD,SEM及TEM等手段表征了复合正极材料的组成和形貌,并测试了不同氧化石墨烯复合量正极材料样品（质量分数为2%,4%,6%,8%,10%,及未复合氧化石墨烯）的电化学性能. 研究结果表明,石墨烯与Li₂MnSiO₄材料均匀地复合在一起;添加适量的氧化石墨烯能促使Li₂MnSiO₄粒子的分布趋向疏松,并形成微孔结构;氧化石墨烯复合量为6%时形成的石墨烯- Li₂MnSiO₄样品电化学性能最佳,扣除碳含量后,以10 mA/g为电流密度,首周放电比容量为166 mAh/g,循环20周后放电比容量仍保持在101 mAh/g. 此外,与石墨烯复合后的Li₂MnSiO₄材料倍率性能也得到了明显的改善. 石墨烯的存在提高了复合材料的导电性,提升了Li₂MnSiO₄正极材料的可逆嵌脱锂容量.     

聚丙烯腈/氧化石墨烯复合纳米纤维的制备与性能研究

以氧化石墨烯为添加物,采用静电纺丝的方法制备不同质量分数的聚丙烯腈/氧化石墨烯(PAN/GO)复合纳米纤维。使用扫描电镜(SEM)、透射电镜(TEM)对复合纳米纤维的微观结构进行观察;采用差示扫描量热仪(DSC)和热重分析仪(TGA)研究复合纳米纤维的热学性能随着氧化石墨烯添加量增加的变化;采用微机控制电子万能试验机对复合纳米纤维的力学性能进行研究。结果表明,加入氧化石墨烯后,纺制的PAN/GO纳米复合纤维会变细,但随着GO添加量的增多出现珠节现象,降低了纤维的粗细均匀度,同时加入GO后对PAN的氧化具有一定的抑制作用,而且GO的加入也使PAN的力学性能增加,当加入量为0.1%时断裂强力增加了一倍,但添加量为1%时,断裂强力又会降低,综合实验结果显示当加入氧化石墨烯的质量分数为0.1%时最适宜。     

聚乳酸-聚己内酯复合纳米纤维支架的制备和表征

在二氧六环/乙醇溶剂体系中,采用凝胶抽提相分离法制备了聚乳酸-聚己内酯(PLLA-PCL)复合纳米纤维支架,研究了凝胶温度、聚合物比例、聚合物浓度、致孔剂及二氧六环/乙醇(溶剂/非溶剂)比例对复合纳米纤维支架结构与性能的影响.结果表明,当凝胶温度处于-20~-10℃,PCL含量为30%~50%,非溶剂含量不超过15%,致孔剂与溶质质量比不超过20∶1时,均能得到具有类似于天然细胞外基质的纳米纤维(50~500 nm)结构的PLLA-PCL复合纤维支架.随着PCL含量的增加,复合纤维支架的弹性模量减小;PCL含量为30%时,复合支架的相容性和结晶性最好.该复合纤维支架具有良好的生物活性和一定的降解性能.     

纳米羟基磷灰石/丝素蛋白复合支架材料的降解特性及生物相容性研究

应用共混法制备了纳米羟基磷灰石/丝素蛋白复合支架材料, 通过体外降解和细胞培养实验研究了复合支架材料的降解特性和生物相容性. 体外降解实验结果显示, 复合支架材料具有稳定的降解能力; 在降解过程中, 羟基磷灰石由于与降解液发生钙、磷等离子的交换, 使其结晶得到了进一步生长和完善. 利用细胞计数法、四甲基偶氮唑盐(MTT)比色法和碱性磷酸酶(ALP)活性测定等分析了复合支架材料的生物相容性, 结果表明, MG63细胞在复合支架材料上具有良好的粘附、增殖能力, 并可引起早期的骨分化. 因此, 纳米羟基磷灰石/丝素蛋白复合支架作为骨组织工程的支架材料具有良好的应用前景.     

改性氧化石墨烯/聚醚砜杂化荷正电纳滤膜的制备及表征

以壳聚糖荷正电改性的氧化石墨烯为无机添加剂,以聚醚砜为膜材料,聚乙烯吡咯烷酮为致孔剂,以N,N-二甲基乙酰胺为溶剂,采用相转化法制备了有机无机杂化纳滤膜.考察了不同改性氧化石墨烯添加量对膜分离性能的影响.研究结果表明,随着改性氧化石墨烯含量的增加,荷正电纳滤膜的断面形态结构并未发生明显改变,但杂化膜的纯水通量、分离选择性明显增加.从研究结果可以看出,改性氧化石墨烯的最佳添加质量分数在0.5%左右.     

聚酯多孔支架降解液对骨髓基质干细胞活力和成骨分化的影响

通过室温模压/粒子浸出方法制备得到聚乙交酯丙交酯(PLGA)多孔支架,每个质量50 mg、孔径200～300μm、孔隙率略大于90%的PLGA85/15多孔支架在10 mL磷酸盐缓冲液(PBS)中37℃体外降解24周.降解液每周换一次,不同时间点的降解液被收集、并加入骨髓基质干细胞(MSC)的培养液或者成骨诱导液中,利用胞外乳酸脱氢酶含量检测、细胞死活染色、四唑盐检测、碱性磷酸酶染色和定量检测的方法考察降解液对MSC的活力和成骨分化能力的影响.实验结果表明,PLGA多孔支架材料在PBS中逐渐降解,其质量、尺寸、孔径、孔与孔的连通性、分子量有不同程度的降低;其降解液在本研究的实验条件下未发现对MSC有明显的细胞毒性,对MSC的活力、增殖以及成骨分化均无显著的负面影响.     

改性氧化石墨烯稳定Pickering乳液法制备高导热相变整体材料

采用表面引发原子转移自由基聚合法(SI-ATRP)改性氧化石墨烯(GO), 并用其稳定Pickering高内相乳液, 一步成型制得高导热氧化石墨烯/石蜡复合整体相变材料. 通过SI-ATRP方法, 在氧化石墨烯表面引入分子刷, 提高GO的分散性, 实现了低GO含量下优异的导热强化效果. 当GO添加量仅为相变复合材料整体的0.4%(质量分数)时, 其热导率(3.968 W?m^-1?K^-1)比纯石蜡的热导率(0.608 W?m^-1?K^-1)有较大提升. 通过测试发现, 在1000次循环后相变材料的泄漏率仅为1.1%~1.3%, 表现出良好的形状稳定性和热可靠性. 制备的新型形状稳定相变材料在温控、 储能应用中具有潜在的用途.     

基于乳酸和β-丙氨酸的聚酯酰胺共聚物合成及降解

采用直接熔融共缩聚方法成功地制备了L-乳酸/β-丙氨酸共聚物, 用红外光谱、核磁共振、凝胶色谱和DSC等方法对共聚物结构进行了表征; 考察了催化剂用量、投料比、聚合反应时间和反应温度等聚合条件对产物分子量及其结晶性能的影响. 实验结果表明, 采用质量分数为1.5%的亚锡复合催化剂在180 ℃下真空反应15 h为最佳聚合条件, 所得到的产物具有相对最大的分子量; 随着β-丙氨酸投料比增加, 相应共聚物的分子量明显下降. 所得到的L-乳酸/β-丙氨酸共聚物具有良好的降解性能, 聚合时间和β-丙氨酸含量对材料的结晶性能和降解性能均有较大的影响.     

Fabrication and Evaluation of Alginate/Bacterial Cellulose Nanocrystals–Chitosan–Gelatin Composite Scaffolds

It is common knowledge that pure alginate hydrogel is more likely to have weak mechanical strength, a lack of cell recognition sites, extensive swelling and uncontrolled degradation, and thus be unable to satisfy the demands of the ideal scaffold. To address these problems, we attempted to fabricate alginate/bacterial cellulose nanocrystals-chitosan-gelatin (Alg/BCNs-CS-GT) composite scaffolds using the combined method involving the incorporation of BCNs in the alginate matrix, internal gelation through the hydroxyapatite-d-glucono-δ-lactone (HAP-GDL) complex, and layer-by-layer (LBL) electrostatic assembly of polyelectrolytes. Meanwhile, the effect of various contents of BCNs on the scaffold morphology, porosity, mechanical properties, and swelling and degradation behavior was investigated. The experimental results showed that the fabricated Alg/BCNs-CS-GT composite scaffolds exhibited regular 3D morphologies and well-developed pore structures. With the increase in BCNs content, the pore size of Alg/BCNs-CS-GT composite scaffolds was gradually reduced from 200 μm to 70 μm. Furthermore, BCNs were fully embedded in the alginate matrix through the intermolecular hydrogen bond with alginate. Moreover, the addition of BCNs could effectively control the swelling and biodegradation of the Alg/BCNs-CS-GT composite scaffolds. Furthermore, the in vitro cytotoxicity studies indicated that the porous fiber network of BCNs could fully mimic the extracellular matrix structure, which promoted the adhesion and spreading of MG63 cells and MC3T3-E1 cells on the Alg/BCNs-CS-GT composite scaffolds. In addition, these cells could grow in the 3D-porous structure of composite scaffolds, which exhibited good proliferative viability. Based on the effect of BCNs on the cytocompatibility of composite scaffolds, the optimum BCNs content for the Alg/BCNs-CS-GT composite scaffolds was 0.2% (w/v). On the basis of good merits, such as regular 3D morphology, well-developed pore structure, controlled swelling and biodegradation behavior, and good cytocompatibility, the Alg/BCNs-CS-GT composite scaffolds may exhibit great potential as the ideal scaffold in the bone tissue engineering field.     

Fabrication,Crosslinking and in vitro Biocompatibility of a Novel Degradable Nano-structure Urethral Tubular Scaffold

A degradable poly(lactic-co-glycolic acid, LA:GA=80:20)(PLGA) urethral tubular scaffold was fabricated by electrospinning. In order to enhance the mechanical properties, the scaffold was crosslinked with glutaraldehyde. The structure and properties of the crosslinked scaffolds were investigated by the mechanical property testing, scanning electron microscopy(SEM), degradability test in vitro and 3-(4,5)-dimethylthiahiazo(-z-yl)-3,5-diphenytetrazo- liumromide(MTT). The results show that the scaffold has the nano-structure. The pore size and the porosity are suitable for cell seeding, growth and extracellular matrix production. Although influenced by the crosslinking slightly, the pore size and the porosity could still support cell proliferation and tissuse formation. The mechanical properties are remarkably increased by the crosslinking of glutaraldehyde, and it could meet the demands of a urethral stent. The scaffold could completely collapse within 70 d. The results of the biocompatibility test show that the PLGA scaffold had no cytotoxicity.     

聚乙烯醇/壳聚糖复合水凝胶的物理化学性质

测定了聚乙烯醇(PVA)和壳聚糖(CS)复合水凝胶的平衡含水量、熔融焓、等温溶胀动力学和非等温失水动力学等性质,讨论了水凝胶的组成和制备参数对这些性质的影响.结果显示:PVA/CS复合水凝胶具有适宜于软骨修复替代材料的网络结构和平衡含水量.CS与PVA复合减弱了凝胶的结晶度,但却增强了水与凝胶支架的相互作用.尽管水凝胶力学拉伸强度有所降低,但却优化了凝胶的生物相容性和降解能力.PVA/CS复合水凝胶是一种潜在的软骨修复材料,作为一种理论研究的模型体系,它将促进热力学在复杂医用材料方面的应用.     

胺解改性聚L-谷氨酸苄酯引导骨再生膜的制备

以聚L-谷氨酸苄酯(PBLG)为原料, 通过溶剂浇铸与粒子沥滤法分别构建PBLG单层致密和PBLG单层多孔膜, 利用乙醇胺对薄膜表面改性, 构筑双层引导骨再生膜. 研究了不同胺解改性时间对PBLG-s-PHEG双层膜亲水性和力学性能的影响, 结果表明, 随着PBLG分子量的增大, 薄膜的力学性能增强而降解速率减缓. 延长胺解改性时间可提高薄膜亲水性和体内外降解速率. 细胞实验结果表明, 双层薄膜的致密结构能够有效阻隔成纤维细胞的侵入, 多孔结构能够支持细胞贴壁黏附和铺展. 体外生物活性评价结果表明, 表面改性的PBLG基材料可用于体内骨缺损修复. 本文所构建的双层引导骨再生膜在体外具有良好的力学性能和降解性能, 与组织具有一定的贴合性, 同时可有效阻碍成纤维细胞侵入, 具有潜在应用价值.     

Effect of starch content on the biodegradation of polycaprolactone/starch composite for fabricating in situ pore-forming scaffolds

Bone tissue engineering is an efficient approach to regenerating bone-related defects. The optimal scaffold used for bone tissue engineering must possess adequate porosity and suitable mechanical properties. This work described the development of a biodegradable polymeric composite based on polycaprolactone (PCL) and starch that can form a porous structure in situ. The scaffold exhibited the required mechanical properties at the initial stage of implantation by controlling in situ degradation and subsequent pore formation. PCL/starch (SPCL) scaffolds with 100/0, 70/30, and 50/50 ratios were developed. Degradation studies were performed in phosphate buffer saline (PBS) containing α-amylase or lipase at 37 °C for 4 weeks. Fourier-transform infrared spectroscopy was used to analyze chemical bonds and their changes after degradation. Differential scanning calorimetry was applied to determine the crystallinity and recrystallization of samples before and after degradation. Mass loss and starch release were observed during degradation, and the porosity of samples was measured by the ethanol replacement method. Morphology was further determined using scanning electron microscopy. Finally, variations in compressive strength and modulus during degradation and pore formation were also measured. The porosity of samples reached 45% after 1 month of degradation, and mechanical properties were still appropriate for human bone tissue. Reduction in mechanical property after mass loss, starch release and pore formation was controlled by the hydrogen bonding and recrystallization effect of PCL after degradation. Results suggested that SPCL composite had potential to form porous scaffold with adequate mechanical properties in situ and is promising for bone tissue engineering applications.     

磷脂管的体外组装及其在生物与化学领域的研究进展

由磷脂组成的微管结构在有机体组织及器官中均有存在，在细胞间的物质传递及信息交流等方面起着重要作用。实现磷脂管在体外的简单快速组装是解析生命信息系统的良好途径。由于良好的生物相容性及支架结构特性，对磷脂管进行材料或结构修饰，是扩大其潜在应用的极佳手段。以磷脂管本身为载体以及以磷脂管为模板修饰构建的微纳米材料，在生物、材料及化学等方面的应用也取得了一系列成果。对磷脂管的体外组装及其在多个领域的应用研究进行了梳理归纳，重点对磷脂管的体外组装方式以及磷脂管在生物及化学等领域的应用等做了分类阐述与总结，并提出磷脂管在多功能纳米复合材料方面的未来发展及应用方向。     

Genipin‐crosslinked gelatin hydrogel incorporated with PLLA‐nanocylinders as a bone scaffold: Synthesis,characterization, and mechanical properties evaluation

Nowadays, despite remarkable progress in developing bone tissue engineering products, the fabrication of an ideal scaffold that could meet the main criteria, such as providing mechanical properties and suitable biostability as well as mimicking the bone extracellular matrix, still seems challenging. In this regard, utilizing combinatorial approaches seems more beneficial. Here, we aim to reinforce the mechanical characteristics of gelatin hydrogel via a combination of Genipin‐based chemical cross‐linking and incorporation of the poly l ‐lactic acid (PLLA) nanocylinders for application as bone scaffolds. Amine‐functionalized nanocylinders are prepared via the aminolysis procedure and incorporated in gelatin hydrogel. The nanocylinder content (0, 1, 2, 3, and 4 wt%) and cross‐linking density (0.1, 0.5, and 1 wt/vol%) are optimized to achieve suitable morphology, swelling ratio, degradation rate, and mechanical behaviors. The results indicate that hydrogel scaffold cross‐linking by 0.5 wt% of Genipin shows optimized morphological feathers with a pore size of around 300 to 500 μm as well as an average degradation rate (40.09% ± 3.08%) during 32 days. Besides, the incorporation of 3 wt% PLLA nanocylinders into the cross‐linked gelatin scaffold provides an optimized mechanical reinforcement as compressive modulus, and compressive strength show a 4‐ and 2.6‐fold increase, respectively. 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay indicates that the scaffold does not have any cytotoxicity effect. In conclusion, gelatin composite reinforced with 3 wt% PLLA nanocylinders cross‐linked via 0.5 wt/vol% Genipin is suggested as a potential scaffold for bone tissue engineering applications.     

与胶原特异性结合的BMP2模拟肽/PLGA 3D打印复合支架的制备及成骨诱导活性

将胶原绑定结构域(CBD)多肽序列与骨形态发生蛋白2模拟肽(BMP2-MP)序列连接制备具有胶原绑定能力的CBD-BMP2-MP, 再将CBD-BMP2-MP与聚丙交酯-乙交酯/胶原(PLGA/COL)3D打印支架相结合, 以支架表面的胶原成分为媒介, 将CBD-BMP2-MP更有效地固定于骨修复材料上, 达到对其进行改性的目的. 利用扫描电子显微镜(SEM)、 电子万能试验机和接触角测量仪对复合支架表面形貌、 力学强度和亲水性等材料学性能进行评价. 用荧光成像法评测 CBD-BMP2-MP及BMP2-MP与支架材料的结合能力. 在各组支架材料表面接种MC3T3-E1细胞进行体外培养, 采用CCK-8、 鬼笔环肽荧光染色、 茜素红染色及qPCR综合评价细胞在材料表面的黏附、 增殖和成骨分化等细胞行为, 研究CBD-BMP2-MP修饰的3D多孔PLGA/COL复合支架的生物学性能. 研究结果表明, 利用3D打印技术制备的多孔支架具有形貌可控的孔隙结构, 为细胞生长创造更有利的细胞微环境, 支架表面胶原成分的加入提高了支架材料的亲水性, 同时对支架材料本身的力学性能无任何影响, 提高了复合支架本身的生物相容性. 与普通BMP2-MP相比, CBD-BMP2-MP具有更好的胶原绑定能力, 与复合支架的结合更稳定, 提高了PLGA/COL复合支架对BMP2-MP的负载能力. 支架表面负载CBD-BMP2-MP后具有极强的促细胞成骨分化能力. MC3T3-E1细胞表现出更高的钙沉积能力, 并且成骨分化相关基因Runx2, ALP, COL-I及OPN等水平也有了明显提升. 表明CBD-BMP2-MP多孔复合支架具有良好的生物相容性和成骨诱导活性, 在骨组织修复领域具有良好的应用前景.     

Effect of the C/O ratio in graphene oxide materials on the reinforcement of epoxy-based nanocomposites

The effect of the C/O ratio of graphene oxide materials on the reinforcement and rheological percolation of epoxy-based nanocomposites has been studied. As-prepared graphene oxide (GO) and thermally-reduced graphene oxide (TRGO) with higher C/O ratios were incorporated into an epoxy resin matrix at loadings from 0.5 to 5 wt %. Tensile testing revealed good reinforcement of the polymer up to optimal loadings of 1 wt %, whereas agglomeration of the flakes at higher loadings caused the mechanical properties of the composites to deteriorate. The level of reduction (C/O) of the graphene oxide filler was found to influence the mechanical and rheological properties of the epoxy composites. Higher oxygen contents were found to lead to stronger interfaces between graphene and epoxy, giving rise to higher effective Young's moduli of the filler and thus to superior mechanical properties of the composite. The effective modulus of the GO in the nanocomposites was found to be up to 170 GPa. Furthermore, rheological analysis showed that highly oxidized graphene flakes did not raise the viscosity of the epoxy resin significantly, facilitating the processing considerably, of great importance for the development of these functional polymeric materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 281–291