羟基磷灰石的表面改性及其对聚乳酸基多孔支架性能的影响

分别采用柠檬酸和硬脂酸对纳米羟基磷灰石（n-HA）进行表面处理,并利用TGA、FTIR、XPS等研究了不同改性剂的改性效果,发现柠檬酸和硬脂酸能够成功接枝在n-HA表面,但硬脂酸的接枝率更高。将柠檬酸改性的n-HA与聚乳酸（PLA）共混制备复合材料,通过SEM观察发现,制备的n-HA/PLA复合材料在n-HA粉体添加量不超过20wt%时,经处理后的n-HA粉体在基体中分散均匀,两相界面处结合紧密。同时研究了n-HA/PLA复合材料制备多孔骨支架的3D打印成型工艺,并测试了其力学性能,结果表明,采用熔融沉积3D打印技术制备的支架有良好的压缩模量,但达到10%形变时所承受的压缩强度与PLA相比仍然有一定差距。     

可生物降解纳米羟基磷灰石/聚酯型弹性体复合材料的制备及性能

通过熔融缩聚法制备了纳米羟基磷灰石(n-HA)/聚1,2-丙二醇-癸二酸-柠檬酸酯(1,2-PPSC) 生物弹性体复合材料。用红外光谱(FTIR)和固体核磁共振光谱(13C NMR) 对复合材料的化学结构进行表征,用扫描电子显微镜(SEM)和透射电镜 (TEM)对n-HA的形态及其在基体中的分散性进行表征。结果表明,n-HA与癸二酸没有发生化学反应,n-HA与1,2-PPSC基体无明显化学键生成,n-HA均匀分散在1,2-PPSC基体中。动态力学性能(DMA) 的测试结果表明,n-HA与1,2-PPSC基体之间生成了良好的界面结合。差示扫描量热(DSC)分析和DMA的测试结果表明,n-HA/1,2-PPSC复合材料玻璃化转变温度(T_g)随着n-HA质量分数的增加而降低,这是由于n-HA影响了聚合物酯化反应的进行,导致化学交联密度降低。n-HA的加入提高了复合材料的亲水性,降低了复合材料的吸水率,减缓了复合材料的降解速率。复合材料的力学性能与基体相比有明显的提高,当n-HA质量分数为20%时,复合材料的弹性模量提高11.4倍,拉伸强度提高8.2倍,且断裂伸长率基本不变。     

Preparation and characterization of nano-hydroxyapatite/poly(vinyl alcohol) hydrogel biocomposite

Nano-hydroxyapatite (n-HA) was used to make a new hydrogel biocomposite with poly(vinyl alcohol) (PVA) by a unique technique. Fourier transform infrared absorption spectra (IR), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TG) and burning test were used to test the physical and chemical characteristics of the composite. Chemical binding between inorganic n-HA and poly(vinyl alcohol) was investigated and discussed. The results showed that the composite had good thermal stability and homogeneity. The n-HA crystals were uniformly distributed in the polymer matrix. The improved n-HA/PVA hydrogel could be used as an artificial articular cartilage, showing a promoting prospect.     

Preparation and characterization of poly(vinyl alcohol)/poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone)/nano-hydroxyapatite composite membranes for tissue engineering

In this paper, the poly(vinyl alcohol)/poly(epsilon-caprolactone)-PEG-poly(epsilon-caprolactone)/nano-hydroxyapatite (PVA/PCEC/n-HA) composite membranes were prepared by solution casting and evaporation methods. The effect of n-HA content on the properties of the composite membranes was studied. The PVA/PCEC/n-HA composite membranes were analyzed by FTIR spectroscopy, X-ray diffraction, water content measurement, contact angle, mechanical test, scanning electron microscopy. The results showed that the surface roughness of the composite membranes increased with the increase of n-HA contents. The n-HA content had obvious influence on the swelling ratio, tensile strength and elongation rate of the composite membranes. With the increase of n-HA contents, the swelling ratio increased at first, and then decreased; tensile strength and elongation rate decreased gradually. The PVA/PCEC/n-HA composite membranes may be applied in the field of tissue engineering.     

Development of poly(lactic acid) nanostructured membranes for the controlled delivery of progesterone to livestock animals

Solution blow spinning (SBS) is a novel technology feasible to produce nanostructured polymeric membranes loaded with active agents. In the present study, nanofibrous mats of poly(lactic acid) (PLA) loaded with progesterone (P4) were produced by SBS at different P4 concentrations. The spun membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). The in vitro releasing of P4 was evaluated using high-performance liquid chromatography (HPLC). Interactions between progesterone and PLA were confirmed by rheological measurements of the PLA/P4 solutions and in the spun mats by microscopy (SEM), thermal (DSC) and spectral (FTIR) analyses. SEM micrographs provided evidences of a smooth and homogeneous structure for nanostructured membranes without progesterone crystals on fiber surface. FTIR spectroscopy indicated miscibility and interaction between the ester of PLA and the ketone groups of the P4 in the nanofibers. X-ray analysis indicated that the size of PLA crystallites increased with progesterone content. Finally, by in vitro release experiments it was possible to observe that the progesterone releasing follows nearly first-order kinetics, probably due to the diffusion of hormone into PLA nanofibers.     

Preparation and characterization of collagen-modified polylactide microparticles

To improve cytocompatibility of polylactide (PLA) and to obtain an injectable scaffold for tissue engineering, collagen-modified PLA (CPLA) microparticles were prepared. Poly-(α-methacrylic acid)-grafted PLA (PMAA-PLA) was obtained by photooxidization and UV induced polymerization. Suspension of PMAA-PLA microspheres with an average size of 172.8 ± 3.6 nm was prepared with solvent evaporation technique. CPLA microparticles were prepared by adding collagen acetic acid solution into PMAA-PLA microsphere suspension prepared above. FTIR spectrum of PMAA-PLA confirmed that PMAA had been grafted on PLA surface. Analytical results of FTIR, XPS, SEM, hematoxylin and eosin (HE) stained and zeta potential measurement showed that the CPLA microparticles obtained by modifying PMAA-PLA microspheres with collagen molecules uniformly have a microporous structure and a particle size of less than 100 μm. The CPLA microparticles were expected to be used as an injectable scaffold for tissue 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.     

Roles and evidence of wood flour as an antibacterial promoter for triclosan-filled poly(lactic acid)

Mechanical and antibacterial performances of poly(lactic acid) (PLA) were assessed as a function of triclosan and wood fillers under a wide range of contact times using Gram-negative Escherichia coli (E. coli, ATCC 25922) as testing bacteria. Water contact angle (WCA) measurement, Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) were performed to characterize the PLA, its blend with triclosan, and its composite with wood filler, and used to substantiate the antibacterial performance results. The experimental results suggested that introduction of wood flour changed the mechanical properties of PLA, whereas triclosan had no definite effect on the mechanical properties. E. coli growth appeared to increase with contact time for PLA, but to decrease with contact time for the wood/PLA composites. Based on the results and quantitative evidence, it was proposed that the wood flour acted as an “antibacterial promoter” for triclosan blended wood/PLA composites, which facilitated triclosan migration onto the wood/PLA composite surfaces to kill the bacteria. The molecular interactions between PLA, triclosan and wood were quantitatively characterized experimentally by CAM, DSC and FTIR. The change in hydrophilicity by the presence of wood filler was found to be the main reason for the improved antibacterial activity of triclosan in the wood/PLA composites.     

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。      

Preparation and characterization of Ni-nitrilotriacetic acid bearing poly(methacrylic acid) coated superparamagnetic magnetite nanoparticles

Stable superparamagnetic magnetite (Fe3O4) nanoparticles were synthesized via co-precipitation in the presence of poly(methacrylic acid) (PMAA) in aqueous solution. The polymer coated Fe3O4 nanoparticles were characterized using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, thermal analysis, and vibrating sample magnetometry (VSM) techniques. These measurements reveal the presence of magnetite nanoparticles with a size of approximately 8 nm inside the PMAA matrix. The magnetization value of these superparamagnetic nanoparticles at room temperarure and 7 T was measured as about 40 emu/g. PMAA-coated Fe3O4 nanoparticles were further assembled with Ni-chelate through a reaction between a primary amine-bearing NTA (nitrilotriacetic acid) ligand and carboxy-functional groups of PMAA. NTA-PMAA-coated magnetite nanoparticles were then loaded with nickel ions and characterized using FTIR. The average amount of binded Ni on the surface of the NTA-modified PMAA coated Fe3O4 was calculated as 1.65 +/- 0.3 x 10(-6) mol nickel(II) ions per g of the magnetic particles from the inductively coupled plasma optical emission spectroscopy (ICP-OES) measurements.     

PLA-PEG-PLA copolymer-based polymersomes as nanocarriers for delivery of hydrophilic and hydrophobic drugs: preparation and evaluation with atorvastatin and lisinopril

Tri-block poly(lactide)–poly(ethylene glycol)–poly(lactide) (PLA–PEG–PLA) copolymers were synthesized and used to prepare polymersomes loaded separately by the hydrophobic and hydrophilic model drugs, atorvastatin and lisinopril, respectively. The resulting nanostructures were characterized by various techniques such as FTIR, DSC, PCS and AFM. The polymersomes exhibited high encapsulation efficiencies of almost 78% and 70.8% for atorvastatin and lisinopril, respectively. Investigation on FTIR and DSC results revealed that such a high encapsulation efficiency is due to strong interaction between atorvastatin and the copolymer. The impact of drug/copolymer ratio and copolymer composition on drug-loading efficiency and drug release behavior were also studied. The results showed that in case of lisinopril, polymersomes exhibited a triphasic drug release, while for atorvastatin a biphasic release profile was obtained. Overall, the results indicated that PLA–PEG–PLA polymersomes can be considered as a promising carrier for both hydrophilic and hydrophobic drugs.     

纳米羟基磷灰石丝素蛋白仿生矿化材料的制备研究

以Ca(NO₃)₂与Na₃PO₄为无机相的前驱体,将丝素蛋白直接溶于Ca(NO₃)₂溶液中,不经过脱盐处理,直接滴入Na₃PO₄溶液中反应,在37℃下丝素蛋白和羟基磷灰石晶体之间相互作用,仿生合成了纳米羟基磷灰石(n-HA)丝素蛋白(SF)生物矿化材料.用FTIR、XRD、XPS和SEM进行表征.结果表明,羟基磷灰石和丝素蛋白两相间具有较强的化学键合,矿化材料中无机相包含少量碳酸根,为缺钙类骨羟基磷灰石并且呈现一定的长轴取向性,说明丝素蛋白大分子对羟基磷灰石晶体的成核和生长起着模板和调控作用.矿化物颗粒尺寸在50~200nm之间,其抗压强度为32.21MPa,可作为非承重部位骨组织缺损修复材料.     

纳米羟基磷灰石/聚酰胺66复合材料在模拟体液(SBF)中的表面生物活性研究

通过纳米羟基磷灰石／聚酰胺66(n—HA／PA66)复合材料体外模拟体液(SBF)浸泡实验，以聚酰胺66(PA66)为对照，用IR、XRD、SEM和ICP等手段对材料的表面组成和形貌变化进行了分析，比较了PA66和n-HA／PA66复合材料的表面生物活性。结果表明，n-HA／PA66复合材料在SBF中其表面形成的HA沉积物为部分碳酸基团取代的磷灰石，而PA66在浸泡过程中Ca、P不在聚合物表面沉积；n-HA／PA66复合材料具有良好的生物活性，作为骨组织修复或替代材料具有较高的研究和应用价值。     

PLA/PBAT/PLA-g-MAH可生物降解复合材料的形态结构与性能分析

通过熔融共混法制备马来酸酐接枝聚乳酸(PLA-g-MAH)用于改善聚乳酸/聚己二酸-对苯二甲酸丁二酯共混物(PLA/PBAT)的相容性,并对复合材料的形态结构、力学性能和生物降解性能进行研究。SEM结果显示,添加增容剂PLA-g-MAH后,PLA/PBAT共混物两相间的界面明显变得模糊,说明PLA-g-MAH对共混物有一定的增容作用;增容剂PLA-g-MAH的加入,使复合材料的拉伸强度和弯曲强度相比于纯PLA略有下降,但其冲击强度有一定程度的提高,断裂伸长率有显著提高,比纯PLA的断裂伸长率提高了约17倍,表现出良好的力学性能;另外,PLA-g-MAH的加入提高了共混物的生物降解性能。     

Morphology,hydrogen-bonding and crystallinity of nano-hydroxyapatite/polyamide 66 biocomposites

Nano-composites for load-bearing bone repair consisting of nano-hydroxyapatite (n-HA) and polyamide 66 were prepared by co-precipitation in ethanol. The relationships between structure and property of the composites were studied. Infrared spectrum results showed that n-HA and PA66 were mainly linked by hydrogen-bonding, which mainly existed between OH of n-HA and amide of PA66. The X-ray diffraction results revealed that the introduction of n-HA to polymeric matrix would weaken the crystallinity of α2 crystals in PA66, and most of the PA66 crystals in the composite were α1 crystals. A differential scanning calorimetry pattern showed that the hydrogen-bonding between organic and inorganic phases in the composite enhanced nucleation spots and played the role of nucleating agent, which resulted in the increase of nucleating speed of PA66 in the composite. However, the relative crystalline degree of PA66 in the composite decreased with the increase of the content of n-HA (the degrees of crystallinity were 27.67% for pure PA66, 23.44% for 30 wt% n-HA/PA66 and 22.98% for 40 wt% n-HA/PA66) because of the high viscosity of the system caused by the addition of n-HA and the hydrogen-bonding between n-HA and PA66.     

纳米羟基磷灰石的预处理及在聚醚醚酮中的分散性

对纳米羟基磷灰石(n-HA)浆料进行了分析和纯化处理,研究了纯化处理后的n-HA在聚醚醚酮(PEEK)中的分散性,进而采用溶液共混法制备了一系列n-HA/PEEK复合材料。结果表明,n-HA原料(浆料)中含有的Ca、Na元素以及碳酸根可通过洗涤除去。XRD、FT-IR以及SEM等分析表明,添加硅烷偶联剂,以聚乙二醇作为分散剂,并采用超声振荡的方法能使n-HA均匀分散在聚醚醚酮(PEEK)中,其中的硅烷偶联剂与n-HA形成了新的键。     

纳米类骨磷灰石晶体合成

采用硝酸钙和磷酸钠水溶液以不同滴定顺序,于70℃下合成了纳米羟基磷灰石(n-HA)沉积物.结果表明,不同的滴定顺序得到的产物都是n-HA晶体,合成的n-HA具有与骨磷灰石晶体十分类似的组成成分、尺寸、结晶度和形貌,因此,合成的n-HA可称为类骨磷灰石晶体.考察了不同滴定顺序对n-HA形貌、结晶度和尺寸的影响;发现相同温度下,磷酸钠滴定硝酸钙得到的磷灰石呈现相对规整的针状晶体,结晶度高,杂质离子少.     

接枝细菌纤维素改性聚乳酸复合材料的制备与性能

聚乳酸(PLA)作为新型的绿色友好材料有非常广阔的应用前景。为有效解决PLA韧性差、结晶速率低等问题,本文提出了以纤维素改性PLA的方法。首先以细菌纤维素(BC)为底物,使L-丙交酯(LLA)在其表面进行原位开环聚合,得到了BC-g-PLA接枝产物;然后将该接枝产物作为增韧剂添加到PLA中,采用溶液浇筑的方法制备得到复合薄膜材料。结果表明：溶液接枝法的反应效率比熔融接枝法更高,接枝率可达到76.60%;通过FTIR、核磁共振波谱仪与XRD对接枝产物进行结构测试,证实了PLA成功接枝到BC表面;通过偏光显微镜观察复合薄膜材料晶体形貌发现BC-g-PLA作为异相成核剂,添加量为0.6%时,对球晶的均匀细化程度最高;通过力学性能测试发现,PLA薄膜增韧改性后断裂伸长率可提高175%,拉伸强度可提高22.7%;通过差示扫描量热仪测试复合薄膜材料的结晶性能,结晶度从未改性的2.53%提高到13.26%,结晶速率也有所增加。     

Electrospun PCL/PLA/HA based nanofibers as scaffold for osteoblast-like cells

Polycaprolactone (PCL), poly (lactic acid) (PLA) and hydroxyapatite (HA) are frequently used as materials for tissue engineering. In this study, PCL/PLA/HA nanofiber mats with different weight ratio were prepared using electrospinning. Their structure and morphology were studied by FTIR and FESEM. FTIR results demonstrated that the HA particles were successfully incorporated into the PCL/PLA nanofibers. The FESEM images showed that the surface of fibers became coarser with the introduction of HA nanoparticles into PCL/PLA system. Furthermore, the addition of HA led to the decreasing of fiber diameter. The average diameters of PCL/PLA/HA nanofiber were in the range of 300-600 nm, while that of PCL/PLA was 776 +/- 15.4 nm. The effect of nanofiber composition on the osteoblast-like MC3T3-E1 cell adhesion and proliferation were investigated as the preliminary biological evaluation of the scaffold. The MC3T3-E1 cell could be attached actively on all the scaffolds. The MTT assay revealed that PCL/PLA/HA scaffold shows significantly higher cell proliferation than PCL/PLA scaffolds. After 15 days of culture, mineral particles on the surface of the cells was appeared on PCL/PLA/HA nanofibers while normal cell spreading morphology on PCL/PLA nanofibers. These results manifested that electrospun PCL/PLA/HA scaffolds could enhance bone regeneration, showing their marvelous prospect as scaffolds for bone tissue engineering.     

The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion

The main aims of this work were to study the effect of surface modifications on sisal fiber properties as well as on fiber/poly (lactic acid) (PLA) interface adhesion. For this purpose, alkali, silane and combination of both treatments were applied to sisal fiber. The effects of treatments on fiber thermal stability, fiber wettability, morphology, tensile properties and on fiber/PLA interfacial shear strength (IFSS) were studied. After treatments IFSS values improved at least 120%, however, tensile strength of sisal fibers decreased. Alkali treatment removed some non-cellulosic components (hemicelluloses, lignin) as confirmed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The removal of non-cellulosic materials led to fibrillated and rough morphology as observed by optical microscopy (OM). FTIR spectrum of silane treated fibers showed a band related to silane amino group and contact angle measurements confirmed that fibers became more hydrophobic. All treatments used improved fiber/PLA adhesion.