聚(丙交酯-co-乙交酯)/β-磷酸三钙复合物的电纺研究

对生物可吸收聚(丙交酯-co-乙交酯)(poly(lactide-co-glycolide),PLGA)与β-磷酸三钙(-βTCP)复合物体系进行了电纺.研究了PLGA的浓度,-βTCP与PLGA比例,加料速度,电压,喷头与接收体之间的距离等因素对电纺过程的影响,制备出纳米纤维膜,并用扫描电镜(SEM)等对纤维膜进行表征.结果表明,电纺溶液浓度越高,或者加料速度越快,纳米纤维的直径越粗.力学实验显示,复合物中-βTCP的含量增加使纳米纤维膜的拉伸强度和杨氏模量下降.     

氨基官能化聚乳酸电纺纤维的制备、 表征和应用

通过聚乳酸(PLA)和氨基丙基三乙氧基硅烷(KH550)混合进行静电纺丝制备氨基官能化聚乳酸纳米纤维. 采用滴定法测定了纤维表面氨基含量, 证明当KH550的添加量为3%~13%(质量分数)时, 有19%~26%的氨基出现在纤维的表面. 利用场发射扫描电子显微镜、 差示扫描量热(DSC)仪、 接触角测试仪和电子拉伸机对纤维形貌、 PLA的玻璃化转变温度和熔点以及纤维膜的亲水性和力学性能进行了表征. 结果表明, KH550的加入可以在电纺纤维表面引入氨基, 同时使纤维直径变细, 使PLA的玻璃化转变温度上升, 熔点下降, 电纺纤维膜的亲水性略有增加, 力学性能有所下降. 通过吸附将金纳米粒子负载到氨基官能化聚乳酸电纺纤维膜上, 得到负载型催化剂, 对硼氢化钠还原对硝基苯酚的反应具有良好的催化活性和重复使用性.     

PVA/SiO2-TiO2杂化电纺纤维膜的形态与性能

以正硅酸乙酯(TEOS)、钛酸四丁酯(TBT)和聚乙烯醇(PVA)为原料, 用溶胶凝胶法制备了PVA/(SiO2-TiO2)杂化纺丝液, 将其电纺成纤维膜. 红外光谱结果证实, PVA的羟基与TEOS和TBT水解后的羟基发生了缩合反应, 杂化电纺纤维膜以网络结构形式相结合; X射线衍射分析表明, 杂化电纺纤维膜的结晶度比纯PVA电纺纤维膜小; 扫描电镜表明, 随杂化纤维膜中无机相含量的增加, 纤维的直径不断增加, 纤维出现一定的弯曲和扭曲, 并伴有少量带状结构的纤维; 紫外-可见光谱结果表明, TiO2的引入增加了纤维膜的抗紫外性; TGA热分析结果表明, 杂化纤维膜的耐热性能优于纯PVA电纺纤维膜的; 耐水性和稳定性测试表明, 杂化纤维膜的耐水性和稳定性优于纯PVA和PVA/SiO2电纺纤维膜的.     

原位交联明胶电纺纤维的制备工艺研究

提出一种原位交联工艺,用于一步制备交联明胶电纺纤维膜,克服目前该电纺膜交联工艺繁琐以及交联过程破坏纤维形态等缺点.通过一系列实验,找出明胶-三氟乙醇-戊二醛三元溶液体系的稳定电纺条件.所得的纤维直径在1μm左右,远大于单纺明胶的纤维直径.同时发现,在电纺过程中,由于纤维表面戊二醛迅速挥发,使得纤维形成"伪核壳"结构.利用流变仪对三元溶液交联速率进行分析,结果表明戊二醛加入明胶溶液后,体系黏度瞬间增大,10 min后维持稳定.最后,通过耐水性试验评价纤维膜交联效果,发现纤维膜有10%左右的溶解,但在水介质中仍可保持很好的纤维形态.     

溶剂性质对两亲性聚肽静电纺丝的影响

通过对聚(γ-苄基L-谷氨酸酯)(PBLG)的亲水改性制备了两亲性聚(γ-苄基L-谷氨酸酯-co-羟乙谷酰胺)无规共聚肽(PBHG)用于静电纺丝制备超细纤维.通过傅里叶变换红外光谱、核磁共振氢谱表征了聚合物结构.通过测定溶液表面张力、黏度、电导率及扫描电镜观察纤维形貌考察了不同溶剂及PBHG浓度对纺丝溶液性质及电纺纤维的影响.通过水浸实验及MTT法评价了电纺纤维膜的亲水性及细胞相容性.研究发现在三氯甲烷(TCM)和四氢呋喃(THF)中PBHG采取α-螺旋构象,刚性分子链自取向排列,可获得直径为微米或亚微米的电纺纤维.以TCM为溶剂时,因溶液表面张力大、导电率低导致纤维品质较差,而以THF为溶剂可获得表面光洁、尺寸均匀的电纺纤维.当溶剂为三氟乙酸(TFA)时,PBHG采取无规线团构象,柔性分子链彼此缠结,同时溶液表面张力小、黏度低、电导率高,可获得纳米电纺纤维.但因TFA挥发性相对较差,易造成纤维粘连.将TFA与TCM复配后作为溶剂可改善纤维粘连问题.与PBLG电纺纤维相比,改性后的PBHG电纺纤维的亲水性得到了改善,可在水中保持纤维骨架而无需交联,并表现出良好的细胞相容性,能促进细胞在电纺纤维膜上的增殖.     

钴卟啉功能化电纺纤维膜的制备及其苯胺检测应用研究

以四苯基钴卟啉为识别分子,可溶性聚酰亚胺为高分子载体,采用静电纺丝技术制备一种负载钴卟啉的聚酰亚胺电纺纤维膜,用于对微量苯胺蒸气的快速检测.结果表明,钴卟啉基团的引入并没有使纺丝条件和过程发生很大的改变,依旧可以得到直径均一、形貌良好的电纺纤维.制备的钴卟啉功能化聚酰亚胺电纺纤维膜卟啉单元负载量高、分布均匀,保持了钴卟啉的基本光谱特性.当置于苯胺蒸气中时,电纺纤维膜中的钴卟啉可与苯胺分子轴向配位,形成有效的能量转移复合物,引起电纺纤维膜的紫外光谱发生改变.并且随着苯胺蒸气浓度的增加,紫外光谱呈现规律性变化,从而达到对苯胺蒸气检测的目的.进一步由紫外光谱计算得到其检测限为7.82 mg/m3.经过5次连续的苯胺蒸气作用—氮气吹扫过程后,电纺纤维膜的紫外吸收光谱可基本回复至原有状态,显示了较好的重现性和优异的可重复使用性.     

纳米羟基磷灰石表面接枝聚合左旋丙交酯

为了改善HA纳米粒子与有机PLGA的相容性,分别采用六亚甲基二异氰酸酯加乙二醇、左旋乳酸改性纳米粒子表面后或直接原位接枝聚合左旋丙交酯等3种不同方法,制备了表面修饰聚乳酸的纳米羟基磷灰石(PLLA-g-HA).FTIR、XPS、TEM、TGA测试表明PLLA成功接枝到HA的表面.其中六亚甲基二异氰酸酯加乙二醇改性HA纳米粒子所获得的PLLA接枝率远高于其它两种方法达25%,调整有机相和无机相的比例对PLLA接枝率的影响较小,其在氯仿中可以稳定分散2天以上.共混电纺丝后的拉伸测试表明PLLA-g-HA/PLAG复合纤维膜的力学性能高于HA/PLGA膜,当两者之间的比例为5%拉伸性能达到最大值.     

PLGA/明胶共混体系的静电纺丝研究

采用静电纺丝技术制备了聚乳酸乙醇酸(PLGA)/明胶(Gt)的复合超细纤维, 考察了溶液浓度、电压及流速对纤维形貌的影响. 研究了不同明胶比例的纤维膜的微观形貌和干湿态的力学性能. 结果表明, 在溶液浓度0.12 g/mL, 电压7.5 kV, 流速0.8 mL/h条件下, 所得PLGA/Gt复合纤维直径较小, 粗细较均匀且缺陷少. 含有明胶的复合纤维直径远小于PLGA单纺纤维直径, 明胶的加入降低了膜的拉伸强度和断裂伸长率, 提高了膜的亲水性. 经PBS浸泡后, 复合膜的弹性得到加强. 明胶质量分数为5%和10%时, 纤维直径分布较窄, 当明胶的质量分数增加至15%时, 纤维的直径分布变宽.     

速溶电纺载药PVP纳米纤维膜制备与表征

采用电纺工艺制备载豆腐果苷聚乙烯基吡咯烷酮纳米纤维膜.通过偏光显微镜确定电纺条件,利用扫描电镜对纤维膜表面形态进行观察;采用X-射线晶体衍射(XRD)和差示扫描量热分析(DSC)检测纤维膜中药物的存在状态,通过红外光谱分析药物与纤维基材之间的相互作用.结果表明载药纤维直径分布均匀(400~600 nm)、表面光滑无药物颗粒,药物与聚合物之间通过氢键作用、具有良好的相容性,XRD和DSC结果表明药物以无定形态高度分散于纳米纤维中,纤维膜中药物以"聚合物控释"机制在13.7 s左右完全溶解.     

二氧化硅/聚乙烯醇杂化电纺纤维膜的制备与结构形态

用溶胶-凝胶(Sol-Gel)法制备了不同二氧化硅含量的PVA/SiO2杂化纺丝液,将其电纺成纤维膜.XRD结果表明,杂化电纺纤维膜的结晶度较纯PVA电纺纤维膜小;FTIR证实了PVA的羟基与正硅酸乙酯水解后的羟基发生了缩合反应,杂化电纺纤维膜是以网络结构形式相结合的;FESEM表明,PVA/SiO2质量比为4∶1时,纤维光滑,分散比较均匀.随着二氧化硅含量的增加,纤维直径变细,纺锤形珠节结构增多.加入金属盐NaCl和MgCl2后,纤维直径变细,圆形珠节增多.从理论上分析了纤维膜结构形态的形成机理.     

Morphological Characterization of Electrospun Nano-Fibrous Membranes of Biodegradable Poly(L-lactide) and Poly(lactide-co-glycolide)

Hydrophobic biodegradable polyesters, poly(L-lactide) (PLLA) and poly(lactide-co-glycolide) (PLGA), were electrospun on different types of collectors to induce morphological changes in the nanofibrous membrane. On the metal collector smooth nonwoven membranes were obtained for both PLLA and PLGA, while on the water reservoir the surface of the membranes became rough due to shrinkage and slow charge dissipation. When NaCl was added to water to enhance the conductivity, the roughness of the membrane surface was changed, yet the shrinkage remained relatively unchanged. The crystallization of PLLA electospun material on the metal plate was suppressed because of the rapid solvent evaporation, however, upon annealing above the glass transition temperature for 24 hr the PLLA membrane became crystallized. When electrospun on the water reservoir, the PLLA membrane remained amorphous. Crystalline PLLA was obtained by electrospinning on the methanol reservoir due to the swelling of nanofibers by methanol.     

A nanofibrous composite membrane of PLGA-chitosan/PVA prepared by electrospinning

Tissue engineering scaffolds produced by electrospinning feature a structural similarity to the natural extracellular matrix. In this study, poly(lactide-co-glycolide) (PLGA) and chitosan/poly(vinyl alcohol) (PVA) were simultaneously electrospun from two different syringes and mixed on the rotating drum to prepare the nanofibrous composite membrane. The composite membrane was crosslinked by glutaraldehyde vapor to maintain its mechanical properties and fiber morphology in wet stage. Morphology, shrinkage, absorption in phosphate buffered solution (PBS) and mechanical properties of the electrospun membranes were characterized. Fibroblast viability on electrospun membranes was discussed by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] assay and cell morphology after 7 days of culture. Results indicated that the PBS absorption of the composite membranes, no matter crosslinked or not, was higher than the electrospun PLGA membrane due to the introduction of hydrophilic components, chitosan and PVA. After crosslinking, the composite membrane had a little shrinkage after incubating in PBS. The crosslinked composite membrane also showed moderate tensile properties. Cell culture suggested that electrospun PLGA-chitosan/PVA membrane tended to promote fibroblast attachment and proliferation. It was assumed that the nanofibrous composite membrane of electrospun PLGA-chitosan/PVA could be potentially used for skin reconstruction.     

大豆分离蛋白/聚乙烯醇的电纺研究

对大豆分离蛋白(SPI)/聚乙烯醇(PVA)的电纺进行了研究, 讨论了溶液性质和甘油的加入对SPI/PVA电纺纤维形貌的影响, 并对SPI/PVA电纺膜进行了成分分析和力学性能表征. 结果表明, 加入甘油可以提高SPI/PVA的可电纺性, 同时使SPI/PVA电纺膜的拉伸强度从不含甘油的(5.17±0.62) MPa下降到含有甘油的(1.67±0.21) MPa, 而伸长率呈增加趋势.     

Superhydrophobicity of PHBV fibrous surface with bead-on-string structure

A poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibrous surface with various bead-on-string structures was fabricated by electrospinning. PHBV was electrospun at various concentrations and then CF4 plasma treatment was employed to further improve the hydrophobicity of the PHBV fiber surfaces. The surface morphology of the electrospun PHBV mats was observed by scanning electron microscopy (SEM). The surface properties were characterized by water contact angle (WCA) measurements and X-ray photoelectron spectroscopy (XPS). The surface morphology of the electrospun PHBV fibrous mats with the bead-son-string structure varied with the solution concentration. The WCA of all of the electrospun PHBV mats was higher than that of the PHBV film. In particular, a very rough fiber surface including porous beads was observed when PHBV was electrospun from the solution with a concentration of 26 wt%. Also, its WCA further increased from 141 degrees to 158 degrees after CF(4) plasma treatment for 150 s. PHBV can be rendered superhydrophobic by controlling the surface morphology and surface energy, which can be achieved by adjusting the electrospinning and plasma treatment conditions.     

CONTROL OF DIMENSIONAL STABILITY AND DEGRADATION RATE IN ELECTROSPUN COMPOSITE SCAFFOLDS COMPOSED OF POLY(D,L-LACTIDE-CO-GLYCOLIDE)AND POLY(Ε-CAPROLACTONE)

The purpose of this study is to investigate the effect of composition poly(D,L-lactide-co-glycolide)/poly(ε-caprolactone)(PLGA/PCL)blending on the morphology,shrinkage and degradation behaviors of the electrospun fibers.With the increase of PLGA content in the composite fibers,the average diameter of the electrospun fibers increased from 1.35 μm to 1.95μm.The serious shrinking of the electrospun PLGA meshes could be circumvented by adding 20% PCL in the fibers,resulting from the semi-crystalline nature of PCL.The degradation rate of the electrospun meshes could be modulated by PLGA/PCL composition.In addition,the electrospun meshes containing 20% PCL displayed stable dimensional morphology with degradation.     

Prevention of postoperative tendon adhesion by biodegradable electrospun membrane of poly(lactide-co-glycolide)

An electrospun poly(lactide-co-glycolide)(PLGA) membrane was prepared and used to perform the anti-adhesion of Achilles tendon. Throughout the experiments, the membrane showed an appropriate degradation rate, and the p H values of degradation media were maintained at around 7.4. Simultaneously, the excellent biocompatibility of the membrane in vitro and in vivo was confirmed by live/dead and histopathological analyses. Meanwhile, the membrane can reduce tendon adhesion significantly and promote functional recovery effectively. The encouraging results were further demonstrated by hematoxylin and eosin(HE), and Masson's trichrome stainings, and type I collagen immunohistochemical analysis. It was concluded that the model treated with the electrospun PLGA membrane was significantly better with respect to the adhesion prevention and tissue repair than that without treatment. Considering the results of degradation and adhesion prevention efficacy, the electrospun PLGA membrane would be a great candidate for the prevention of postoperative tendon adhesion.     

CONTROL OF DIMENSIONAL STABILITY AND DEGRADATION RATE IN ELECTROSPUN COMPOSITE SCAFFOLDS COMPOSED OF POLY(D,L-LACTIDE-co-GLYCOLIDE) AND POLY(ε-CAPROLACTONE)

The purpose of this study is to investigate the effect of composition poly(D,L-lactide-co-glycolide)/poly(ε- caprolactone)(PLGA/PCL)blending on the morphology,shrinkage and degradation behaviors of the electrospun fibers. With the increase of PLGA content in the composite fibers,the average diameter of the electrospun fibers increased from 1.35μm to 1.95μm.The serious shrinking of the electrospun PLGA meshes could be circumvented by adding 20% PCL in the fibers,resulting from the semi-crystalline nature ...     

Degradation behavior of electrospun microfibers of blends of poly(lactide-co-glycolide) and Pluronic F-108

Electrospun poly(dl-lactide-co-glycolide) (PLGA) microfibers have been explored as extra cellular matrix mimicking scaffolding systems for tissue engineering application. However, the hydrophobic nature of PLGA can be limiting in terms of protein adsorption. Hence, blending of PLGA with a hydrophilic polymer (Pluronic^®) prior to electrospinning has been explored as a potential strategy to impart hydrophilicity to PLGA microfibers. In this study, PLGA (85/15) was blended with small quantities (0.5-2% w/v) of Pluronic^® F-108 (PF-108) and electrospun into microfibers. Blending of PF-108 demonstrated a significant decrease in the surface hydrophilicity of microfibers as was evidenced by an increase in wetting tension. Surface analysis using XPS indicated the presence of PF-108 in the bulk of the fibers in addition to the surface of the fibers. The results of the water uptake studies indicated that the water uptake capacity and consequential fiber swelling was significantly increased in the presences of PF-108. The in vitro degradation studies demonstrated that the trend in molecular weight loss was not significantly influenced by the presence of small quantities of PF-108. Therefore, blending of PLGA with PF-108 could be an effective technique for surface modification of electrospun PLGA microfibers without compromising on the other advantages of PLGA.     

聚乳酸-乙醇酸/纳米氧化锌复合电纺纤维装载亲疏水药物的控释及体外细胞毒性

利用静电纺丝技术制备了负载亲水性药物阿霉素(DOX)以及疏水性药物喜树碱(CPT)的复合纳米纤维. 先用巯基封端的普朗尼克(F127)修饰纳米氧化锌(FZnO), 再将FZnO负载盐酸阿霉素(DOX@FZnO), 最后将DOX@FZnO与CPT一起纺入聚乳酸-乙醇酸(PLGA)纤维中. 体外药物释放结果表明, 复合纳米纤维能够减小亲水性药物的突释, 减缓药物释放速率, 延长药物释放时间. 体外细胞活性结果表明, 双载药复合纤维比单载药复合纤维具有更强的细胞毒性, 能够有效抑制癌细胞生长.