新型改性的n-HA与PLGA复合材料的制备及性能研究

采用硅烷偶联剂(KH550)和L-丙交酯LLA联合接枝处理的新方法对纳米羟基磷灰石(n–HA)进行表面改性, 然后将其与聚乳酸-羟基乙酸(PLGA)作不同比例复合(n-HA为3wt%、10wt%、20wt%及30wt%), 得到改性n-HA/PLGA复合材料(g-n-HA/PLGA)。将其与未改性n-HA及未改性n-HA/PLGA复合材料作对比检测。结果表明, 该联合处理方法是n-HA进行表面接枝改性的新型有效方法。且改性处理后的n-HA与未改性处理的n-HA相比, 能更好地在PLGA基体中分散均匀, 并能提高PLGA结晶能力和PLGA的力学性能。当改性处理后的n-HA添加量为10wt%时, 其复合材料抗弯强度和拉伸强度分别比未改性n-HA/PLGA提高14.4%和11.3%。该新型g-n-HA/PLGA复合材料有望用作骨折固定材料。     

组织工程用PEGDA水凝胶材料低温等离子体接枝聚合

采用自由基聚合法合成了聚乙二醇双丙烯酸酯(PEGDA)/甲基丙烯酸β-羟乙酯(HEMA)共聚物水凝胶,材料表面在非反应性气体氩气气氛下进行等离子体表面处理,并在紫外光辐照条件下进行丙烯酰胺接枝共聚。红外谱图证明PEGDA/HEMA共聚物水凝胶上接枝了酰胺基团,材料的亲水性提高,等离子体表面处理后,材料表面形成含氧基团,氮原子含量增加。     

低温等离子体液相接枝处理电纺PET膜的制备与研究

采用氮气(N2)低温等离子体引发苯二甲酸乙二醇酯(PET)纳米纤维薄膜表面接枝,液相低温等离子体处理接枝丙烯酸单体,通过电镜照片、水接触角测试、FTIR测试及力学测试,讨论了液相接枝处理后,薄膜的形态及性能的变化。实验中接枝处理的工艺条件是,丙烯酸接枝溶液体积浓度10%,接枝温度60℃,接枝时间2h。液相低温等离子体接枝处理后,薄膜的表面亲水性得到了有效的提高。     

等离子体表面接枝改性聚对苯二甲酸乙二醇酯的血液相容性研究

利用等离子体表面接枝改性方法在聚对苯二甲酸乙二醇酯(polyethylene terephthalate，PET)材料表面接枝不同分子量的聚乙二醇(PEG)，体外血液相容性实验表明．接枝了PEG的PET材料的血液相容性与PEG的分子量有关；当接枝的PEG分子量达到6000时，材料的血液相容性最好。     

磷酰胆碱类似物在有机硅材料表面的常压等离子体引发接枝改性研究

采用He常压辉光放电等离子体(APGDP)处理有机硅薄膜材料表面并引发2-甲基丙烯酰氧乙基磷酰胆碱(MPC)在其表面接枝聚合.通过ATR-FTIR对接枝前后膜表面的结构进行表征分析,确定MPC共价接枝到材料表面.改性后膜表面的接触角由101°下降到54°,在室温下保存15天后仍维持在58°左右,表明接枝MPC后有机硅材料获得高亲水性的表面,并能使这一性质较好地保持.接枝前后膜的力学性质变化不大.体外血小板粘附实验表明,接枝MPC后的材料表面能够显著抑制血小板的粘附和聚集,具有优良的血液相容性,可以作为一种新型医用生物弹性体.     

大气压辉光放电液相沉积装置在表面改性中的应用

用高频高压电源、介质阻挡放电装置及惰性气体氦(He)产生大气压辉光放电等离子体,超声喷嘴喷射雾状液滴直接送入等离子体区域,喷洒在处理物表面上,进行等离子体接枝聚合.应用这套装置对PE纤维进行处理,选择甲基丙烯酸十二氟庚酯DFMA(C11H8F12O2)作为液相单体,对不同处理参数下PE纤维表面的接触角和接枝率变化进行了规律性和原理分析,用IR、SEM和EDS分析了处理前后PE纤维表面的变化.实验结果表明,在PE纤维表面成功引入了疏水性基团,提高了其疏水性.     

用低温等离子体对高分子材料进行表面加工

用等离子体对高分子材料进行表面处理.改变其表面性质是一个值得推广的方法.在第一部分介绍了高温等离子体和低温等离子体的特性;在第二部分介绍了荷电粒子与高分子材料表面的相互作用;第三部分介绍了低温等离子体在改善纺织品表面性能中的应用.其中的一类主要是表面变性.即改善纺织品的亲水性或润湿性.提高表面染色粘附性:另一类主要的表面处理是乙烯系不饱和单体.不饱和聚合物、丙睛、丙烯酸等的接枝.可以根据不同的单体与要达到的目的来确定使用什么单体和什么工艺.经过接枝处理的纤维性能将会发生较大的改变.     

聚乳酸-羟基乙酸/改性纳米羟基磷灰石复合多孔支架材料的研制

聚乳酸-羟基乙酸(PLGA)/改性纳米羟基磷灰石(MHA)复合多孔组织工程支架材料的制备主要包含以下步骤:首先通过室温化学共沉淀法制备纳米羟基磷灰石,然后通过L-丙交酯在二甲苯溶液中聚合接枝纳米羟基磷灰石得到改性的纳米羟基磷灰石;最后通过改进的热致相分离两步初化法制备PLGA/MHA复合多孔支架.X射线衍射仪(XRD)显示纳米羟基磷灰石合成成功,透射电子显微镜(TEM)结果显示其为半径为30～50nm的球形,红外光谱显示聚乳酸成功的接枝到纳米羟基磷灰石表面;扫描电子显微镜(SEM)结果表明改进的热致相分离两步初化法制备的PLGA/MHA复合多孔支架的孔径在100～450μm.     

丝素改性胶原膜的低温等离子体改性及体外抗凝血性研究

选用SO2、NH3、CO2三种工作气体，采用低温等离子体技术对丝素改性胶原膜进行了表面改性。运用X光电子能谱分析了材料的表面性质。材料的体外抗凝血性能由体外凝血时间——凝血酶原时间(PT)、部分凝血活酶时间(APTT)、凝血酶时间(TT)作为评价标准。结果表明，SO2、CO2等离子体处理可分别在材料表面引入磺酸和酸酸基团，材料的体外抗凝血性得到很大的改善。NH3等离子体处理可以增加材料表面的氨基的数目，它对材料的抗凝血性没有贡献。     

低温等离子体表面处理PEGDA/HEMA水凝胶的时效性及亲水性

采用低温等离子体工艺对聚乙二醇双丙烯酸酯(PEGDA)/甲基丙烯酸-2-羟基乙酯(HEMA)共聚物凝胶膜进行表面改性,研究了等离子处理的时效性,通过紫外接枝法在等离子处理材料表面接枝丙烯酰胺(AAm),并探讨了时效性对丙烯酰胺接枝率的影响和表面改性后材料的亲水性。研究结果表明,氩等离子处理凝胶材料具有一定的时效性,随着放置时间的延长,AAm的接枝率降低,接枝后PEGDA/HEMA材料的亲水性得到改善,材料的亲水性随着AAm的浓度的增大而增大。     

Transfer of collagen coating from porogen to scaffold: Collagen coating within poly(dl-lactic-co-glycolic acid) scaffold

Using paraffin micro-spheres as porogen, this paper addressed a novel method to coat collagen onto the internal pore surface within poly(dl-lactic-co-glycolic acid) (PLGA) scaffold with controlled pore size. The paraffin micro-spheres with desirable size were mixed with collagen solution (0.5–1.0% w/v), molded to form a paraffin micro-sphere scaffold, and dried. The collagen was left on the surface of the paraffin micro-spheres and even among the paraffin micro-spheres. PLGA solution was then cast into the interspace of the paraffin/collagen scaffold and dried. After the paraffin micro-spheres were dissolved and removed, PLGA scaffold with controlled pore size, good interconnectivity and high porosity was obtained. Collagen was transferred from the paraffin micro-spheres to the surfaces of the pore wall. Observation of scanning electron microscopy (SEM) showed that collagen was coated on the paraffin micro-spheres and was on the surfaces of pore wall within PLGA scaffold. Fourier transform infrared spectroscopy (FTIR) also detected the presence of collagen in the PLGA scaffold so formed; and there was no apparent change on the molecular components of collagen during the experimental procedure.     

Mineralization of Collagen‐Coated Electrospun Poly(lactide‐co‐glycolide) Nanofibrous Mesh to Enhance Growth and Differentiation of Osteoblasts and Bone Marrow Mesenchymal Stem Cells

To obtain the biomimetic scaffolding materials for bone tissue engineering, poly(lactide‐co‐glycolide) (PLGA) nanofibrous mesh (NFM) was mineralized in a 5× simulated body fluid (SBF) for different time after it was treated by air plasma for 15 min and subsequent collagen coating. The apatite particles were nucleated on the surface of individual nanofibers, gradually grew up, and finally covered the whole NFM surface. The mineral aggregates were mainly composed of tiny hydroxyapatite (HA) nanoparticles, whose content reached a constant value of 54 µg · cm^?2 after 9 days. The collagen coating and apatite deposition enhanced the NFM strength pronouncedly too. In vitro cell culture demonstrated that the non‐ or less mineralized NFMs were more beneficial of cell spreading and proliferation than those highly mineralized NFMs, but the latter ones could strongly promote secretion of alkaline phosphatase (ALP) by osteoblasts after cultured for 14 days. Moreover, the highly mineralized NFMs also could significantly up‐regulated ALP activity and calcium synthesis of bone marrow mesenchymal stem cells (BMSCs), demonstrating that these NFMs are more favorable of the osteoblast phenotype expression and osteogenic induction. Therefore, the biomimetic apatite deposited PLGA/collagen NFM could be a promising candidate scaffold for bone tissue engineering.     

低温等离子体对天然胶原材料表面改性的研究

采用牛腱中提取的胶原蛋白为原料，制成薄膜试样，在Ｏ２和Ａｒ条件下，用低温等离子体处理天然胶原薄膜的表面．处理后的试样通过电子光谱（ＥＳＣＡ），红外光谱（ＩＲ），Ｘ射线衍射和接触角测量来研究其结构和性能的变化．实验表明：处理后胶原材料的表面、内部结构及化学成分都发生了明显的变化；它与水和二碘甲烷的接触角明显小于等离子处理前的可见低温等离子体方法能用于胶原材料的改性．     

Effect of solid freeform fabrication-based polycaprolactone/poly(lactic-co-glycolic acid)/collagen scaffolds on cellular activities of human adipose-derived stem cells and rat primary hepatocytes

Highly biocompatible polycaprolactone (PCL)/poly(lactic-co-glycolic acid) (PLGA)/collagen scaffolds in which the PCL/PLGA collagen solution was selectively dispensed into every other space between the struts were fabricated using solid freeform fabrication (SFF) technology, as we described previously. The objective of this study was to evaluate and compare the PCL/PLGA/collagen scaffolds (group 3) with PCL/PLGA-only scaffolds (group 1) and PCL/PLGA scaffolds with collagen by the dip-coating method (group 2) using human adipose-derived stem cells (hASCs) and rat primary hepatocytes. The selectively dispensed collagen formed a three-dimensional (3D) network of nanofibers in group 3, as observed by scanning electron microscopy. The compressive strength and modulus of group 3 were approximately 140 and 510 times higher, respectively, than those of a sponge-type collagen scaffold whose weak mechanical properties were regarded as a critical drawback. Proliferation and osteogenic differentiation of hASCs were promoted significantly in group 3 compared to groups 1 and 2. In addition, we found that the viability and albumin secretion ability of rat primary hepatocytes were highly retained for 10 days in group 3 but not group 1. Interestingly, hepatocyte aggregation, which enhances hepatic function through cell–cell interactions, was observed particularly in group 3. In conclusion, group 3, in which the collagen was selectively dispensed in the 3D space of the porous PCL/PLGA framework, will be a promising 3D scaffold for culturing various cell types.     

Preparation of a biphasic scaffold for osteochondral tissue engineering

Tissue engineering has been developed as a prospective approach for the repair of articular cartilage defects. Engineered osteochondral implants can facilitate the fixation and integration with host tissue, and therefore promote the regeneration of osteochondral defects. A biphasic scaffold with a stratified two-layer structure for osteochondral tissue engineering was developed from biodegradable synthetic and naturally derived polymers. The upper layer of the scaffold for cartilage engineering was collagen sponge; the lower layer for bone engineering was a composite sponge of poly(DL-lactic-co-glycolic acid) (PLGA) and naturally derived collagen. The PLGA–collagen composite sponge layer had a composite structure with collagen microsponge formed in the pores of a skeleton PLGA sponge. The collagen sponge in the two respective layers was connected. Observation of the collagen/PLGA–collagen biphasic scaffold by scanning electron microscopy (SEM) demonstrated the connected stratified structure. The biphasic scaffold was used for culture of canine bone-marrow-derived mesenchymal stem cells. The cell/scaffold construct was implanted in an osteochondral defect in the knee of a one-year old beagle. Osteochondral tissue was regenerated four months after implantation. Cartilage- and bone-like tissues were formed in the respective layers. The collagen/PLGA–collagen biphasic scaffold will be useful for osteochondral tissue engineering.     

Development and in vitro evaluation of surface modified poly(lactide-co-glycolide) nanoparticles with chitosan-4-thiobutylamidine

The objective of this study was to develop a nanoparticulate drug delivery system based on the surface modification of poly(lactide-co-glycolide) (PLGA) nanoparticles with a thiolated chitosan. PLGA nanoparticles were prepared by the emulsification-solvent evaporation method. Immobilization of chitosan to the surface of PLGA nanoparticles via amide bonds was mediated by a carbodiimide. Thiol groups were covalently bound to the chitosan surface of particles by reaction with 2-iminothiolane. Obtained nanoparticles were characterized in vitro regarding size, zeta potential, thiol group content, stability at different pH values, mucoadhesion, and drug release. Results demonstrated that the surface modification of PLGA nanoparticles with thiolated chitosan (chitosan-TBA) leads to nanoparticles of a mean diameter of 889.5 ± 72 nm and positive zeta potential of + 24.74 mV. The modified nanoparticles contained 7.32 ± 0.24 μmol thiol groups per gram nanoparticles. The size of nanoparticles was strongly influenced by the pH of the surrounding medium, being 925.0 ± 76.3 nm at pH 2 and 577.8 ± 66.7 nm at pH 7.4. Thiolated nanoparticles showed a 3.3-fold prolonged residence time on the mucosa and an unchanged release profile in comparison to unmodified PLGA nanoparticles. These data suggest that surface modified chitosan-TBA conjugate PLGA nanoparticles have the potential to be used as mucoadhesive drug delivery system.     

Development and In Vitro Evaluation of Surface Modified Poly(lactide-co-glycolide) Nanoparticles with Chitosan-4-Thiobutylamidine

ABSTRACT

The objective of this study was to develop a nanoparticulate drug delivery system based on the surface modification of poly(lactide-co-glycolide) (PLGA) nanoparticles with a thiolated chitosan. PLGA nanoparticles were prepared by the emulsification-solvent evaporation method. Immobilization of chitosan to the surface of PLGA nanoparticles via amide bonds was mediated by a carbodiimide. Thiol groups were covalently bound to the chitosan surface of particles by reaction with 2-iminothiolane. Obtained nanoparticles were characterized in vitro regarding size, zeta potential, thiol group content, stability at different pH values, mucoadhesion, and drug release. Results demonstrated that the surface modification of PLGA nanoparticles with thiolated chitosan (chitosan-TBA) leads to nanoparticles of a mean diameter of 889.5 ± 72 nm and positive zeta potential of + 24.74 mV. The modified nanoparticles contained 7.32 ± 0.24 μmol thiol groups per gram nanoparticles. The size of nanoparticles was strongly influenced by the pH of the surrounding medium, being 925.0 ± 76.3 nm at pH 2 and 577.8 ± 66.7 nm at pH 7.4. Thiolated nanoparticles showed a 3.3-fold prolonged residence time on the mucosa and an unchanged release profile in comparison to unmodified PLGA nanoparticles. These data suggest that surface modified chitosan-TBA conjugate PLGA nanoparticles have the potential to be used as mucoadhesive drug delivery system.     

Collagen immobilization on polyethylene terephthalate surface after helium plasma treatment

An attractive alternative to add new functionalities such as biocompatibility due to the micro- and nano-scaled modification of polymer surfaces is offered by plasma processing. Many vital processes of tissue repair and growth following injuries depend on the rate of adsorption and self-assembling of the collagen molecules at the interfaces. Consequently, besides the amount of protein, it is necessary to investigate the form in which the collagen molecules are organizing on the polymer surface. In this study, direct current (DC) helium plasma treatment was used in order to obtain poly(ethylene terephthalate) (PET) films with different amounts of collagen and different shapes of aggregates formed from the collagen molecules. The immobilization of collagen on PET surface was confirmed by XPS measurements, an increase of the nitrogen content by increasing the plasma exposure time being recorded. The SEM and AFM measurements revealed the presence of grains and dendrites of collagen formed on the polymer surface. At 15 min plasma treatment time, the polymer surface after collagen immobilization has a homogenous topography. Usually, one can find fibrils, coil or dendrimers of collagen formed in buffer solutions and immobilized on different polymer surfaces. On the other hand, in this particular configuration, the combination of DC plasma and helium gas as a PET functionalization tool is an original one. As the collagen is not covalently immobilized on the surfaces, it may interact with the cell culture medium proteins, part of the collagen might being replaced by other serum proteins.     

Increased osteoblast functions on nanophase titania dispersed in poly-lactic-co-glycolic acid composites

The design of nanophase titania/poly-lactic-co-glycolic acid (PLGA) composites offers an exciting approach to combine the advantages of a degradable polymer with nano-size ceramic grains to optimize physical and biological properties for bone regeneration. Importantly, nanophase titania mimics the size scale of constituent components of bone since it is a nanostructured composite composed of nanometre dimensioned hydroxyapatite well dispersed in a mostly collagen matrix. For these reasons, the objective of the present in vitro study was to investigate osteoblast (bone-forming cell) adhesion and long-term functions on nanophase titania/PLGA composites. Since nanophase titania tended to significantly agglomerate when added to polymers, different sonication output powers were applied in this study to improve titania dispersion. Results demonstrated that the dispersion of titania in PLGA was enhanced by increasing the intensity of sonication and that greater osteoblast adhesion correlated with improved nanophase titania dispersion in PLGA. Moreover, results correlated better osteoblast long-term functions, such as alkaline phosphatase activity and calcium-containing mineral deposition, on nanophase titania/PLGA composites compared to plain PLGA. In fact, the greatest collagen production by osteoblasts occurred when cultured on nanophase titania sonicated in PLGA at the highest powers. In this manner, the present study demonstrates that PLGA composites with well dispersed nanophase titania can enhance osteoblast functions necessary for improved bone tissue engineering applications.     

Stimulation of healing within a rabbit calvarial defect by a PCL/PLGA scaffold blended with TCP using solid freeform fabrication technology

The purpose of this study was to investigate the healing capacity within an 8-mm rabbit calvarial defect using a polycaprolactone (PCL)/poly(lactic-co-glycolic acid) (PLGA) scaffold blended with tri-calcium phosphate (TCP) that was constructed using solid freeform fabrication (SFF) technology. The PCL/PLGA/TCP scaffold showed a 37?% higher compressive strength and rougher surface than the PCL/PLGA scaffold. In animal experiments, new bone formation was analyzed using microcomputed tomography (micro-CT) and histological and histometric analyses. The PCL/PLGA/TCP groups had significantly greater neo-tissue areas as compared with the control groups at 4 and 8 weeks (P?<?0.05). The PCL/PLGA/TCP group had significantly greater bone density as compared with the control and PCL/PLGA groups at 4 and 8 weeks (P?<?0.005). The results of this study suggest that the PCL/PLGA/TCP scaffold fabricated using SFF technology is useful for recovering and enhancing new bone formation in bony defects in rabbits.