臭氧引发接枝制备聚偏氟乙烯亲水膜

利用臭氧的强氧化性,对溶解在N-甲基吡咯烷酮中的聚偏氟乙烯进行处理引入过氧基团,然后通过热引发接枝聚合亲水性聚乙二醇甲基丙烯酸酯(PEGMA),通过相转变法(phase inversion)制备具备亲水特性的PVDF分离膜.通过红外光谱、热重分析和接触角测试对接枝改性后的聚偏氟乙烯的结构和性能进行表征.红外光谱显示在1 734 cm-1处出现PEGMA的特征吸收峰,表明已成功接枝上PEGMA.接枝后的PVDF膜接触角降低到42°,表现出很好的亲水性;同时研究了接枝条件对改性膜亲水性的影响,随接枝单体浓度增加其亲水性增大;改性前后的聚偏氟乙烯膜的表面形貌通过扫描电子显微镜(SEM)分析表明,在相同成膜条件下改性后分离膜表面形貌发生很大变化,改性后制备的分离膜有较大的膜孔出现;水通量测试和牛血清蛋白吸附实验进一步表明,接枝改性可以明显改善PVDF分离膜的亲水性和抗污染性能.     

聚乙烯表面亲水化改性及其血液相容性改进

以过氧化苯甲酰（BPO）为引发剂,在聚乙烯（PE）膜表面接枝丙烯酸（AA）以改善其亲水性。系统地讨论了引发剂浓度、单体浓度、反应温度以及反应时间等各影响因素对接枝率的影响,并通过傅立叶变换红外（FT-IR）、表面水接触角等物理手段来表征接枝膜的表面结构、亲水性等性能。实验结果表明BPO能成功引发丙烯酸接枝PE膜,接枝改性后PE膜亲水性有了明显的提高。采用了3种比较直观的常规评价方法对PE膜接枝改性前后的血液相容性进行初步的评价。研究结果表明表面接枝AA后的PE膜与血细胞的相互作用较弱,对血细胞的破坏程度明显减小,其抗凝血性比未接枝改性膜有显著提高。     

聚偏氯乙烯超滤膜的辐照接枝改性研究

聚偏氟乙烯超滤膜经Ｃｏ－６０辐照，接枝乙烯基单体，再经磺化，成为磺化聚氟乙烯超滤膜。研究了辐照剂量、接枝时间对接枝率的影响和磺化反应的条件等。试验表明，改性后膜的亲水性和抗污染性增强。此外，还讨论了膜改性的机理。     

预光照聚四氟乙烯薄膜表面的无光引发剂气相光接枝聚合

研究了聚四氟乙烯（ＰＴＦＥ）薄膜的非极性表面光接枝改性，以赋予其在面一定的极性，改善表面的亲水性。采用预光照、不加光引发剂，用紫外光直接引发ＰＴＦＥ薄膜表面的丙烯酸接枝。改性后薄膜表面的水接触角由９８°降至６５°，染色程度明显提高。研究了反应条件对接枝结果的影响，并通过ＥＳＣＡ等分析手段，探讨了接枝反应机理。预先照可活化ＰＴＦＥ膜表面，使聚四氟乙烯的Ｃ－Ｆ键断裂产生自由基。光引发剂二苯甲酮不能引发ＰＴＦＥ膜，而能引发丙烯酸，便之一生均聚物，不加二苯甲酮可减小接枝阻力。     

聚苯乙烯溴代并接技聚二甲基硅氧烷

聚苯乙烯（PS）在苯溶液中与溴代丁二酰亚胺（NBS）反应，经分离提纯得到了固体溴代聚苯乙烯（PSB）。将所得PSB溶于苯并与低分子量的聚二甲基硅氧烷硅醇锂（PDMSOLi）反应，经分离提纯得到固体的溴代聚苯乙烯接枝聚二甲基硅氧烷（PSB－g-PDMSO),所得PSB-g-PDMSO的结构经^1H-NMR、IR及TEM表征。     

PVDF-g-PNIPAAm温敏抗污染膜的制备及性能研究

通过自由基共聚将聚(N-异丙基丙烯酰胺)(PNIPAAm)接枝到了碱处理聚偏氟乙烯(PVDF)粉末上,合成接枝共聚物PVDF-g-PNIPAAm。以此为原材料通过相转化法制备温敏抗污染分离膜。通过调控反应时间,达到不同的PNIPAAm接枝率,研究了不同接枝率对膜结构及性能的影响。结果表明,随着反应时间的延长,PNIPAAm的接枝率逐渐增加。成膜过程中发挥致孔作用明显致使膜表面的微孔数目逐渐增加。此外,PNIPAAm的接枝率越高膜的亲水性越强,且温敏性能提高。由于室温下PNIPAAm的亲水性,膜表面易形成水化层,从而提高改性膜的抗蛋白质污染性能。     

聚羟基烷酸酯表面接枝聚乙烯基吡咯烷酮的研究

采用紫外光接枝改性的方法将N-乙烯基吡咯烷酮(NVP)单体接枝到聚β-羟基丁酸酯和聚β-羟基戊酸酯的共聚物(PHBV)膜表面上,形成PHBV-g-PVP共聚物,从而提高其亲水性.并用接触角测定仪、傅立叶红外光谱仪和扫描电镜进行了分析表征.结果表明,经过改性后的PHBV膜表面的亲水性显著提高.     

电纺PLLA/PCL/PEG共混纤维膜的结构及性能

采用静电纺丝技术制备了聚乳酸（PLLA）/聚己内酯（PCL）/聚乙二醇（PEG）共混纤维膜,考察了溶剂体积比、共混物共混质量比、溶液浓度对电纺纤维形貌的影响,研究了共混纤维膜的热稳定性、结晶性、力学性能及亲水性。结果表明加入PEG有效提高了共混纤维膜的热稳定性和结晶性,提高了共混纤维膜的拉伸强度、弹性模量和亲水性能。     

聚两性电解质修饰聚偏氟乙烯膜的制备及抗污染性能

膜污染是膜分离技术广泛应用的瓶颈之一。文中通过自由基接枝聚合法将2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)接枝到聚偏氟乙烯(PVDF)膜上构建聚两性电解质化膜表面。研究了改性前后膜表面结构和抗污染性能的变化。随着单体投料量增加,聚两性电解质的接枝率逐渐增加;接枝聚两性电解质后,膜亲水性逐渐增强,膜表面孔尺寸减小。与纯PVDF膜相比,改性膜具有较低的蛋白质吸附量;在牛血清蛋白(BSA)溶液渗透过程中,膜的不可逆污染向可逆污染转化。由于可逆污染可通过简单的纯水清洗得到抑制,改性膜具有较高的通量恢复率。这个结果证明了聚两性电解质的引入赋予PVDF膜良好的抗污染性能。     

两性离子聚合物表面改性的聚偏氟乙烯抗污染膜的制备及性能

提高聚偏氟乙烯(PVDF)抗污染性能是改善PVDF应用效果的重要途径。文中通过自由基聚合的方法将抗污染材料——两性离子类化合物磺酸甜菜碱(DMAPS)接枝到碱处理过的PVDF膜表面。研究了接枝DMAPS后,PVDF膜表面的结构与性能变化,并初步探讨了改性后的PVDF膜对牛血清蛋白的吸附性能。结果表明,在PVDF膜表面接枝DMAPS后,膜表面孔洞减小,亲水性提高。虽然改性后的PVDF膜通量有所下降,但通过牛血清蛋白(BSA)的振荡吸附实验发现,两性离子改性膜表现出良好的抗蛋白质吸附性能。与PVDF原膜相比,改性膜在BSA溶液中通量下降率小,用水清洗后膜通量恢复率高。     

基于贻贝仿生化学改善聚己内酯纤维多孔支架的 细胞相容性

在组织工程领域,支架的表面化学性能对调控细胞的生长行为起着关键的作用。为进一步改善聚己内酯(PCL)纤维支架的细胞相容性,开发了一种基于贻贝仿生化学在PCL纤维支架表面接枝生物相容性大分子的方法。该方法主要包含多巴胺在PCL纤维的表面涂覆和自聚合,以及生物活性大分子精氨酸-甘氨酸-天冬氨酸(RGD)和肝素的引入。傅里叶变换红外光谱测试结果表明RGD和PDA被成功地引入到PCL纤维支架表面。扫描电镜形貌检测和水接触角测试结果表明该改性手段不仅增大了纤维支架的表面粗糙度并且改善了支架的表面润湿性能。血管内皮细胞在改性的支架表面表现出了良好的细胞黏附性和细胞存活性。这种不涉及任何有毒溶剂的改性方法在组织工程支架领域具有广阔的应用前景。     

Radiolabeled gelatin type B analogues can be used for non-invasive visualisation and quantification of protein coatings on 3D porous implants

This study covers the quantification of the covalent attachment of gelatin type B (GelB) and the subsequent adsorption of Fibronectin (Fn) on poly-ε-caprolactone (PCL) surfaces, functionalised with 2-aminoethyl methacrylate (AEMA) by means of post-plasma UV-irradiation grafting. As typical surface characterisation tools do not allow quantification of deposited amounts of GelB or Fn, radiolabeled analogues were used for direct measurement of the amount of immobilized material. Bolton-Hunter GelB (BHG) and Fn were radioiodinated with (131)I and (125)I respectively and S-Hynic GelB (SHG) was labeled with (99m)Tc. Immobilisation of (131)I-BHG or (99m)Tc-SHG on both PCL and PCL-AEMA scaffolds was performed in analogy with earlier work. SPECT images on scaffolds coated with (99m)Tc-SHG conjugates were acquired on a U-SPECT II camera. There was a clear difference in the amount of deposited (131)I-BHG between blanco and AEMA-grafted PCL on 2D samples. No significant differences in immobilization behaviour were observed between (99m)Tc-SHG and (131)I-BHG. Subsequent immobilisation of Fn was successful and depended on the amounts of deposited GelB. SPECT imaging on cylindrical 3D scaffolds confirmed these findings and showed that the amount of immobilized (99m)Tc-SHG was depth dependant. The architecture of the scaffolds strongly influences the distribution of GelB within these structures. Furthermore, there is a clear difference in the homogeneity of the protein coating when different GelB immobilization protocols were applied. This study shows that radiolabeled compounds are a rapid and accurate tool in the quantitative and qualitative evaluation of the biofunctionalisation of AEMA grafted PCL scaffolds.     

Double protein functionalized poly-ε-caprolactone surfaces: in depth ToF–SIMS and XPS characterization

In biomaterial research, great attention has focussed on the immobilization of biomolecules with the aim to increase cell-adhesive properties of materials. Many different strategies can be applied. In previously published work, our group focussed on the treatment of poly-ε-caprolactone (PCL) films by an Ar-plasma, followed by the grafting of 2-aminoethyl methacrylate (AEMA) under UV-irradiation. The functional groups introduced, enabled the subsequent covalent immobilisation of gelatin. The obtained coating was finally applied for the physisorption of fibronectin. The successful PCL surface functionalization was preliminary confirmed using XPS, wettability studies, AFM and SEM. In the present article, we report on an in-depth characterization of the materials developed using ToF–SIMS and XPS analysis. The homogeneous AEMA grafting and the subsequent protein coating steps could be confirmed by both XPS and ToF–SIMS. Using ToF–SIMS, it was possible to demonstrate the presence of polymethacrylates on the surface. From peak deconvoluted XPS results (C- and N-peak), the presence of proteins could be confirmed. Using ToF–SIMS, different positive ions, correlating to specific amino-acids could be identified. Importantly, the gelatin and the fibronectin coatings could be qualitatively distinguished. Interestingly for biomedical applications, ethylene oxide sterilization did not affect the surface chemical composition. This research clearly demonstrates the complementarities of XPS and ToF–SIMS in biomedical surface modification research.     

Fabrication and characterization of PCL/gelatin/chitosan ternary nanofibrous composite scaffold for tissue engineering applications

In the present study, we have fabricated a ternary composite nanofibrous scaffold from PCL/gelatin/chitosan, by electrospinning technique, using a solvent system—chloroform/methanol for polycaprolactone (PCL) and acetic acid for gelatin and chitosan, for tissue engineering applications. Field emission scanning electron microscopy (FE-SEM) was used to investigate the fiber morphology of the scaffold and it was found that the fiber morphology was influenced by the concentrations of PCL, gelatin, and chitosan in polymer solution during electrospinning. X-ray diffraction, Fourier transform infrared, and thermogravimetric (TG) analysis results showed some interactions among the molecules of PCL, gelatin, and chitosan within the scaffold. In-vitro cell culture studies were done by seeding L929 mouse fibroblasts on fabricated composite scaffold, which confirmed the cell viability, high cell proliferation rate, and cell adhesion on composite scaffold as indicated by MTT assay, DNA quantification, and FE-SEM analysis of cell-scaffold construct. Thus, the ternary composite scaffold made from the combination of PCL (synthetic polymer), gelatin, and chitosan (natural polymer) may find potential application in tissue engineering.     

Fabrication and characterization of PCL/gelatin composite nanofibrous scaffold for tissue engineering applications by electrospinning method

In the present study, composite nanofibrous tissue engineering-scaffold consisting of polycaprolactone and gelatin, was fabricated by electrospinning method, using a new cost-effective solvent mixture: chloroform/methanol for polycaprolactone (PCL) and acetic acid for gelatin. The morphology of the nanofibrous scaffold was investigated by using field emission scanning electron microscopy (FE-SEM) which clearly indicates that the morphology of nanofibers was influenced by the weight ratio of PCL to gelatin in the solution. Uniform fibers were produced only when the weight ratio of PCL/gelatin is sufficiently high (10:1). The scaffold was further characterized by Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric (TG) analysis, and X-ray diffraction (XRD). FT-IR and TG analysis indicated some interactions between PCL and gelatin molecules within the scaffold, while XRD results demonstrated crystalline nature of PCL/gelatin composite scaffold. Cytotoxicity effect of scaffold on L929 mouse fibroblast cells was evaluated by MTT assay and cell proliferation on the scaffold was confirmed by DNA quantification. Positive results of MTT assay and DNA quantification L929 mouse fibroblast cells indicated that the scaffold made from the combination of natural polymer (gelatin) and synthetic polymer (PCL) may serve as a good candidate for tissue engineering applications.     

Type I Collagen Immobilized Poly(caprolactone) Nanofibers: Characterization of Surface Modification and Growth of Fibroblasts

Poly(caprolactone) (PCL) electrospun nanofibers were modified by aminolysis and collagen was immobilized on the aminolysed PCL nanofibers. Considering low immunogenic response collagen elicits, immobilization of the same is anticipated to enhance the tissue engineering application of the PCL nanofibers. Amino groups were introduced into PCL nanofibers through aminolysis process. Aminolysis of PCL nanofibers was confirmed by electron dispersive X‐ray analysis (EDX). Collagen was immobilized on aminolysed PCL nanofibers using glutaraldehyde as crosslinker. The collagen crosslinking on to PCL nanofibers was established by attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy. The fiber morphologies of PCL nanofibers at different stages were characterized by scanning electron microscopy (SEM). The change in hydrophobicity of PCL nanofibers due to aminolysis and collagen immobilization was determined by water contact angle measurements. Aminolysis followed by collagen immobilization had reduced the intrinsic hydrophobicity of PCL nanofibers. NIH 3T3 fibroblasts were cultured for 2 days on PCL nanofibers, aminolysed PCL nanofibers, and aminolysed PCL nanofibers crosslinked with collagen. Cell attachment and growth were observed by MTT assay in each case. Collagen immobilization improved the biocompatibility of the PCL nanofibers. Thus the modified PCL nanofibers can be used as suitable broad spectrum scaffold for skin, cartilage, bone, cardiac constructs for efficient tissue engineering applications.     

Nanofibers prepared by needleless electrospinning technology as scaffolds for wound healing

Electrospun gelatin and poly-ε-caprolactone (PCL) nanofibers were prepared using needleless technology and their biocompatibility and therapeutic efficacy have been characterized in vitro in cell cultures and in an experimental model of a skin wound. Human dermal fibroblasts, keratinocytes and mesenchymal stem cells seeded on the nanofibers revealed that both nanofibers promoted cell adhesion and proliferation. The effect of nanofibers on wound healing was examined using a full thickness wound model in rats and compared with a standard control treatment with gauze. Significantly faster wound closure was found with gelatin after 5 and 10 days of treatment, but no enhancement with PCL nanofibers was observed. Histological analysis revealed enhanced epithelialisation, increased depth of granulation tissue and increased density of myofibroblasts in the wound area with gelatin nanofibers. The results show that gelatin nanofibers produced by needleless technology accelerate wound healing and may be suitable as a scaffold for cell transfer and skin regeneration.     

等离子体诱导接枝聚合法制备pH感应开关膜

利用等离子体诱导填孔接枝聚合法在聚偏氟乙烯多孔膜上接枝聚甲基丙烯酸pH感应型开关,系统研究了接枝率对膜的pH感应开关特性的影响.结果表明,开关膜的接枝率对膜的过滤通量、pH感应开关系数和膜孔径感应pH变化倍数都有重要的影响.接枝率≤5.98%时,pH感应开关系数和膜孔径感应pH变化倍数均随接枝率的增加而增加;而对于接枝率＞5.98%的膜,pH感应开关系数和膜孔径pH感应变化倍数随接枝率的增加而减少,直至膜开关系数和膜孔径pH感应变化倍数趋近于1.为了获得较好的开关性能,必须将膜的接枝率控制在适当的范围内.     

Relationship between the fibroblastic behaviour and surface properties of RGD-immobilized PCL membranes

In this study, poly-ε-caprolactone (PCL) membranes were modified with the cell adhesive peptide RGD by chemical immobilization technique. The roughness and hydrophilicity were increased after RGD immobilization and an improved cell attachment was observed.     

Enhancing growth and proliferation of human gingival fibroblasts on chitosan grafted poly (ε-caprolactone) films is influenced by nano-roughness chitosan surfaces

The bioactivity of poly (epsilon-caprolactone) (PCL) films is improved by grafting chitosan (CS) surfaces with various values of nano-roughness on PCL surfaces. To examine the effects of the design, growing human gingival fibroblasts (HGFs) on the films was conducted. Various values of nano-rough CS surfaces were cast using nano-rough PCL molds that had been fabricated using a solvent-etched technique. The features of nano-CS/PCL surfaces were characterized using an atomic force microscope (AFM) to observe the topography and to determine the value of centerline average roughness of a surface, R(a). The R(a) values of the nano-CS/PCL films were 36.8 +/- 1.6, 100.0 +/- 3.0, and 148 +/- 7.0 nm, while that of the smooth CS/PCL film was 12.5 +/- 1.6 nm. The growth and proliferation of HGFs on the films are elucidated by fluorescent staining and analyzed by MTT viability assay following three and 7 days of culture. The viability assay of the cells reveals that the growth rates of HGFs on both CS/PCL and nano-CS/PCL films significantly exceed (95% or more; P < 0.001) those of PCL on both days, demonstrating the improvement of the bioactivity of PCL films by grafting CS. Additionally, the growth rates and proliferations of HGFs on nano-CS/PCL films of roughness 100 and 148 nm markedly exceed (15% or more; P < 0.001) those on 36.8 nm nano-CS/PCL and CS/PCL films, after both periods of culturing, indicating that the high nano-roughness CS surfaces further enhance the growth rate of HGFs. In conclusion, markedly improving the bioactivity of PCL films by grafting CS is demonstrated. Moreover, high nano-roughness of nano-CS/PCL films can further accelerate the growth and proliferation of HGFs compared with those of CS/PCL films. This work presents a new concept for designing biomaterials in tissue engineering.