PVA /HA复合水凝胶力学性能分析及有限元模拟

目的通过实验与有限元模拟对羟基磷灰石(HA)改变聚乙烯醇/羟基磷灰石(PVA/HA)复合水凝胶的力学性能本质及其承载特性进行研究。方法在UMT试验机上进行PVA/HA复合水凝胶的压缩及应力松弛实验。通过模拟与实验结果相结合,研究PVA/HA复合水凝胶的承载特性及HA对其性能的影响。结果随着HA含量的增加,PVA/HA复合水凝胶的压缩模量先增大后减小,而渗透系数先减小后增大;HA含量为3%的PVA/HA复合水凝胶压缩模量最大、渗透系数最小,分别为1.25 MPa和1.59×10-3 mm4.N-1.s-1。PVA/HA复合水凝胶的液体承载比例随着施载时间的增加呈现先增加后减小的非线性变化,加入HA的PVA/HA复合水凝胶的液体承载比例明显增加。应力松弛速率随着HA含量增加呈先上升后下降趋势,下压相同位移HA,含量为3%时,PVA/HA复合水凝胶所能分散的应力更多。结论 PVA/HA复合水凝胶内部的承载特性影响着其力学性能,HA含量为3%时的PVA/HA复合水凝胶力学性能最优,更接近于天然关节软骨的力学性能。     

多孔生物陶瓷与PVA水凝胶复合材料的制备与力学性能分析

目的将多孔生物陶瓷和聚乙烯醇(PVA)水凝胶交联成为一个仿生软骨-硬关节双层结构,并对该结构的微观形貌和力学性能进行分析。方法以羟基磷灰石(HA)为基体,采用添加碳酸氢铵(NH4HCO3)晶粒造孔的方式制备不同孔隙率的多孔羟基磷灰石生物陶瓷,以聚乙烯醇(PVA)为主要原料,环氧丙烷为交联剂,在多孔生物陶瓷表面及基体内交联制备出PVA水凝胶形成双层结构,对试样的断口形貌进行表征,对试样的拉伸强度和剪切强度等性能进行测试分析。结果交联的PVA水凝胶可以渗入到生物陶瓷基体表层以下的孔隙中,并且陶瓷基体和PVA水凝胶有很好的结合。随着多孔生物陶瓷孔隙率的增大,试样的最大拉伸和剪切负载均增大,平均孔隙率为70%试样的最大拉伸和剪切负载分别为153.61 N和64.46 N;而相应的拉伸和剪切强度略有下降,平均孔隙率为30%试样对应的最大拉伸和剪切强度分别为2.12 MPa和1.13 MPa。两者的失效形式均是因为裂纹的扩展,断口的微观形貌表明,断裂面存在明显的裂纹和内部缺陷,同时可观察出裂纹源和扩展方向。结论考虑到多孔生物陶瓷基体的强度,平均孔隙率为50%的多孔生物陶瓷的渗入效果适中,试样的拉伸强度和剪切强度、多孔生物陶瓷基体的压缩强度也有一定的保证,选择孔隙率为50%的试样较为合适。     

胶原-PVA复合水凝胶的制备

目的通过反复冻融法制备胶原-聚乙烯醇(PVA)复合水凝胶材料。方法制备组分比例(胶原固含量为0%、5%、10%、15%、20%)不同的5组胶原-PVA复合水凝胶试样,对其进行一些物理和化学性能的表征,选出性能最优的胶原/PVA配比。将最优配比制备出的胶原-PVA复合水凝胶进行细胞毒性实验的生物学评价。结果实验制备所得胶原-PVA复合水凝胶的红外图谱可见明显的酰胺谱带;差动扫描式热量法(DSC)图出现2个热吸收峰,峰值温度分别为65℃～72℃、222℃～225℃;扫描电子显微镜显示材料为多孔结构;X射线衍射(XRD)峰值为20°;溶胀值最高为24 g/g;透水气性最高的达1 400 g/(m2.24 h);降解性能良好,15 d内大部分降解率达80%;细胞毒性为0～1级。结论胶原-PVA复合水凝胶作为体表创伤敷料具有良好的应用前景,但尚需对其进行体表创伤修复效果及其他生物相容性的评价。     

细菌纤维素/聚乙烯醇/聚丙烯酰胺复合水凝胶的性能表征北大核心

背景:随着高分子水凝胶材料应用领域的扩展而对其性能提出了更高要求,研制和开发性能更为优良的高分子水凝胶材料已成为目前的研究热点。目的:比较细菌纤维素改性前后的聚乙烯醇/聚丙烯酰胺水凝胶的力学性能,为其用于伤口敷料提供理论依据。方法:实验利用细菌纤维素为增强材料,采用冷冻-熔融法,在细菌纤维素网络中引入聚乙烯醇/聚丙烯酰胺水凝胶,制备了细菌纤维素/聚乙烯醇/聚丙烯酰胺复合水凝胶,采用红外光谱、扫描电镜、热重分析、力学性能测试等手段对凝胶的结构和性能进行表征。结果与结论:①通过扫描电镜和红外光谱图可以看到聚乙烯醇和聚丙烯酰胺结合到了细菌纤维素上,说明制备出了细菌纤维素/聚乙烯醇/聚丙烯酰胺复合水凝胶;②细菌纤维素增强复合凝胶的热稳定性、拉伸强度明显提高,而断裂伸长率较细菌纤维素增强前下降;③聚丙烯酰胺浓度为1.0%时,复合水凝胶的拉伸强度和断裂伸长率最大分别为331.79 kPa和105.33%,聚乙烯醇浓度为3.5%时,复合水凝胶的断裂伸长率最大为46.25%,而拉伸强度随聚乙烯醇浓度的增加而增加;④结果表明,细菌纤维素的引入明显提高了水凝胶材料的力学性能,增强了其稳定性,该复合水凝胶有望用作伤口敷料。     

CRG/PVA复合水凝胶的3D打印工艺研究

利用生物高分子材料聚乙烯醇（PVA）、卡拉胶（CRG）的物理、生物学性能及其特殊的交联特性,制备一种可用于3D打印的CRG/PVA复合水凝胶生物墨水材料,为后期的工艺研究提供材料基础。构建了一套适合CRG/PVA复合水凝胶挤出打印的3D打印系统,并在此基础上研究和分析了活塞挤出速度、喷头移动速度、打印高度、线间距等工艺参数对水凝胶尺寸精度的影响。当挤出速度为0.3~0.6 mm/s、喷头移动速度为15~20 mm/s、打印高度为0.3~0.6 mm、线间距大于1.4 mm时,CRG/PVA复合水凝胶有很好的打印效果。水凝胶的临界坍塌角度实验显示对三维打印结构设计支撑结构能增大水凝胶的临界坍塌角度,使得大倾斜角度结构能够成功打印。     

用磁控溅射技术制备钛合金表面HA生物涂层

目的 探讨磁控溅射法制备的HA生物涂层组织结构以及涂层与基体的界面结合性能。方法 利用射频磁控溅射技术在Ti-6Al-4v基体表面制备HA生物涂层，利用扫描电镜(SEM)观察HA生物涂层表面形貌和断面形貌，利用X射线衍射仪(XRD)分析涂层的相结构，利用能量分散谱仪(EDS)分析涂层的Ca／P比，采用环氧树脂E-7对接法测定HA涂层与基体的界面结合强度。结果 溅射HA生物涂层的Ca／P比为1．7，后处理生物涂层中不存在其它钙磷杂质相，HA的晶化程度高，HA涂层与基体的界面结合强度为51．2MPa。结论 射频磁控溅射技术制备的HA生物涂层，表面形貌良好，涂层与基体的界面结合强度较高。     

壳聚糖/液晶复合水凝胶的制备及细胞相容性研究

 目的：基于仿生理念构建壳聚糖/液晶(CS/LC)复合水凝胶体系,通过观察复合水凝胶表面形貌和相分离结构、评价细胞相容性,探讨复合水凝胶体系中液晶微区结构形态对细胞行为的影响。方法：以CS为基底材料,复合具有一定流动和取向的羟丙基纤维素酯类LC,制备具有类生物膜结构的CS/LC复合基质,采用扫描电镜、X射线衍射等手段对复合材料进行表征分析,并进一步观察复合水凝胶对成纤维细胞活性的影响。结果：CS/LC复合水凝胶主要呈现非晶态,LC相以“岛屿”状态均匀分布于CS水凝胶基材中,与CS构成两相分离结构;细胞相容性实验表明复合水凝胶中嵌有连续分布的流动性LC畴有利于细胞的初始黏附与生长。结论：复合水凝胶的仿生结构及类组织黏弹性使其表现出良好的细胞相容性。     

羟基磷灰石/聚乙烯醇水凝胶的制备与生物活性评价

背景:先前的研究表明,羟基磷灰石/聚乙烯醇水凝胶复合水凝胶(hydroxyapatite/polyvinylalcoholhydrogel,HA/PVA-H)具有较好的机械性能和耐摩擦磨损性能,这说明HA/PVA-H复合材料具有早期承载能力和较好的生物活性。那么HA/PVA-H复合材料能否通过羟基磷灰石粒子与周围骨组织较快地形成活性结合呢?目的:制备羟基磷灰石/聚乙烯醇水凝胶,并对其进行生物学评价。方法:将Ca(OH)2研磨过筛后,配制成一定浓度的悬浮分散液;加入质量分数15%的PVA水溶液中,添加二甲亚砜,最后按Ca/P比1.67:1加入H3PO4的乙醇溶液,制备HA/PVA-H。对试样进行体外模拟体液培养实验,测试浸泡前后SBF浸泡液的变化,并利用扫描电镜、FTIR、XRD对材料的结构进行了表征和分析。结果与结论:扫描电镜观察可知羟基磷灰石/聚乙烯醇水凝胶表面有结晶体形成,经XRD分析确认为弱结晶的羟基磷灰石晶体;浸泡之后浸泡液的pH值与Ca、P离子浓度下降,同时FTIR结果显示试样中的PO43-特征峰得到增强,且有CO32-的特征峰形成。结果提示,羟基磷灰石/聚乙烯醇水凝胶复合材料具有较好的生物活性。     

缓释血管内皮生长因子的透明质酸水凝胶对大鼠脑损伤的修复作用

目的:探讨缓释血管内皮生长因子(VEGF)的透明质酸(HA)水凝胶对脑损伤大鼠的修复效果。方法:制备HA水凝胶并在其中添加包封VEGF的聚乳酸聚乙醇酸共聚物(PLGA)微球,形成可缓释VEGF的HA水凝胶复合支架。选用成年SD大鼠制备脑损伤模型,随机分为3组:将HA复合支架植入大鼠脑损伤区作为实验组(HA+PLGA组);单纯模型组;不添加PLGA微球的HA水凝胶植入作为HA对照组(HA组)。结果:HA水凝胶复合支架呈疏松多孔网状结构,可缓慢释放VEGF至少2周;术后8周大体观察可见HA水凝胶和脑组织整合良好,表面光滑; Nissl染色显示支架材料内有大量神经细胞;免疫荧光染色显示单纯HA支架可减轻脑损伤区胶质瘢痕的形成,缓释VEGF的HA复合支架对胶质瘢痕有更强的抑制作用;半薄切片组织学染色可见复合支架植入区有大量新生的血管,有大量细胞,血管周围可见神经纤维,而在单纯HA移植区血管和细胞较少。结论:缓释VEGF的HA水凝胶可与脑组织较好的整合,抑制胶质瘢痕的形成,诱导血管再生,进而促进大鼠脑损伤后的组织修复。     

直接心辅装置CRG/PVA复合水凝胶隔离层的制备与性能研究

基于气动肌肉的直接心辅装置近年来成为研究热点,针对该装置,提出一种水凝胶生物材料隔离层,用于避免气动肌肉与心脏直接接触,减小摩擦力与排异反应。首先选取聚乙烯醇(PVA)作为水凝胶隔离层3D打印的前驱体材料,并进行PVA水凝胶的制备;然后针对水凝胶固化时间长无法应用于3D打印的问题,加入卡拉胶(CRG)进行优化,并进行力学以及溶胀性能探究;最后将3D成型技术运用到隔离层的成型过程,并对水凝胶隔离层的摩擦磨损性能进行研究。结果表明,CRG/PVA复合水凝胶材料拉伸断裂应变及应力分别为280%、0.84 MPa,力学性能良好;CRG不仅能缩短水凝胶固化时间,且其含量从1%增加至5%,水凝胶溶胀度提高到3.70;水凝胶隔离层在120个工作周期后表面仅轻微损伤,进一步验证该结构能改善心脏摩擦环境。     

Preparation, characterization, and evaluation of radiopaque hydrogel filaments for endovascular embolization

Radiopaque hydrogel filaments were prepared, characterized, and evaluated for potential use as implants for endovascular embolization of vascular defects. Three hydrogel formulations were prepared by free radical polymerization: (i) poly(ethylene glycol) diacrylate with 2,4,6-triiodophenyl penta-4-enoate (PEG-I), (ii) poly(ethylene glycol) diacrylamide with barium sulfate (PEG-B), and (iii) poly(propylene glycol) diacrylate with barium sulfate (PPG-B). The PEG-B and PPG-B hydrogels exhibited radiopacity comparable with clinically used platinum coils, whereas the PEG-I hydrogel did not. In the dry state, the average ultimate tensile strength and strain of the hydrogels ranged from 37 to 128 gf and 21% to 72%, respectively. The PEG-B hydrogel had significantly higher tensile strength compared with the PEG-I hydrogel. In the hydrated state, the average ultimate tensile strength and strain ranged from 5 to 15 gf and 7% to 30%, respectively. Statistically significant differences in tensile strength were not present when hydrated. Compared with poly(ethylene) after 4-week implantation into the subcutaneous space of rabbits, the PEG-I hydrogel elicited slightly more inflammation, whereas the PEG-B and PPG-B hydrogels elicited less inflammation. All three hydrogel formulations elicited less fibrous encapsulation than poly(ethylene). With further development, these materials have potential as embolization devices.     

Crosslinking characteristics of and cell adhesion to an injectable poly(propylene fumarate-co-ethylene glycol) hydrogel using a water-soluble crosslinking system

The crosslinking characteristics of an injectable poly(propylene fumarate-co-ethylene glycol) [P(PF-co-EG)]-based hydrogel were investigated. A water-soluble crosslinking system was used, consisting of poly(ethylene glycol) diacrylate (PEG-DA), ammonium persulfate (APS), and ascorbic acid (AA). The effects of PEG block length of the P(PF-co-EG), APS concentration, AA concentration, and PEG-DA concentration on equilibrium water content, sol fraction, onset of gelation, mechanical properties, and endothelial cell adhesion were studied. The equilibrium water content of the hydrogels ranged from 57.1 +/- 0.3 to 79.7 +/- 0.2% whereas the sol fraction ranged from 2.5 +/- 0.0 to 3.33 +/- 5.4%. The onset of gelation times varied from 1.1 +/- 0.1 to 4.3 +/- 0.2 min. For all hydrogel formulations, the tensile strength fell between 61.7 +/- 18.2 and 401.3 +/- 67.5 kPa and tensile moduli ranged from 0.4 +/- 0.0 to 3.3 +/- 0.3 MPa. Endothelial cells attached to the hydrogels in a range of 3.9 +/- 1.4 to 31.1 +/- 14.1% of cells seeded. These findings suggest that injectable poly(propylene fumarate-co-ethylene glycol) hydrogel formulations in conjunction with a novel water-soluble crosslinking system may be useful for in situ crosslinkable tissue-engineering applications.     

In Vivo and Cytotoxic Assays of a Poly(vinyl alcohol)/Clay Nanocomposite Hydrogel Wound Dressing

In the present work, a nanocomposite hydrogel wound dressing was prepared on the basis of poly(vinyl alcohol) using organically-modified montmorillonite as nanoclay by the freezing–thawing cyclic method. In vivo assays were performed to evaluate its performance as an applicable wound dressing on animals. It showed an improved healing process for wounds covered by the prepared nanocomposite hydrogel compared with control wounds covered by sterile gauze. Significant improvements, such as better creation of moist surfaces on the wound with less scar formation, shorter duration of healing operation and better closing of the wound edges with enhanced tensile properties of the healed wound, i.e., tensile strength and elongation-at-break, were observed using the prepared nanocomposite hydrogel in comparison to the sterile gauze. An in vitro cytotoxic assay was also utilized to determine the biocompatibility of the prepared nanocomposite hydrogel. It showed that the prepared nanocomposite hydrogel is non-toxic and can be used as a biocompatible wound dressing in practical wound management.     

In vitro studies of plasma-sprayed hydroxyapatite/Ti-6Al-4V composite coatings in simulated body fluid (SBF)

The bioactivity of plasma-sprayed hydroxyapatite (HA)/Ti-6Al-4V composite coatings was studied by soaking the coatings in simulated body fluid (SBF) for up to 8 weeks. This investigation was aimed at elucidating the biological behaviour of plasma-sprayed HA/Ti-6Al-4V composite coatings by analyzing the changes in chemistry, and crystallinity of the composite coating in a body-analogous solution. Phase composition, microstructure and calcium ion concentration were analyzed before, and after immersion. The mechanical properties, such as tensile bond strength, microhardness and Young's modulus were appropriately measured. Results demonstrated that the tensile bond strength of the composite coating was significantly higher than that of pure HA coatings even after soaking in the SBF solution over an 8-weeks period. Dissolution of Ca-P phases in SBF was evident after 24h of soaking, and, a layer of carbonate-apatite covered the coating surface after 2 weeks of immersion. The mechanical properties were found to diminish with soaking duration. However, slight variation in mechanical properties was found after supersaturation of the calcium ions was attained with the precipitation of the calcium phosphate layers.     

Fabrication and characterization of phlorotannins/poly (vinyl alcohol) hydrogel for wound healing application

Abstract

Phlorotannins (PH) derived from brown algae have been shown to have biological effects. However, the application of PH in biomedical materials has not been investigated. Here, we investigated the effects of PH on normal human dermal fibroblast (NHDF) proliferation and fabricated a composite hydrogel consisting PH and poly (vinyl alcohol) (PVA) (PVA/PH) by a freezing-thawing method for wound healing applications. Cell proliferation was significantly higher in the PH-treated (0.01 and 0.02%) cells than in non-treated cells. Based on the mechanical properties, the PVA/PH hydrogel had a significantly increased swelling ratio and ultimate strain compared to the PVA hydrogel, but the ultimate tensile strength and tensile modulus were decreased. Additionally, cell attachment and proliferation on the composites were evaluated using NHDFs. The results showed that after 1 and 5 days, cell attachment and proliferation were significantly increased on the PVA/PH hydrogel compared with that on the PVA hydrogel. The findings from this study suggest that the PVA/PH hydrogel may be a candidate biomedical material for wound healing applications.     

医用细菌纤维素的性能研究

木醋杆菌静态培养得到的细菌纤维素(BC),化学处理后以进口细菌纤维素敷料(XBC)产品为对照样品,采用扫描电镜、傅立叶红外光谱、广角X射线衍射和力学拉伸测试分析二者的形态、结构与性能。结果表明:两种样品都是由高结晶指数纳米级纤维素纤维组成,其中BC的纤维直径为(22±9)nm,结晶指数为89.71%;测试样品BC的拉伸强度和弹性模量在湿态、干态下均显著高于对照样品XBC。细胞内毒性、豚鼠迟发型接触致敏实验和皮肤刺激等生物相容性测试结果表明:测试样品BC具有与对照样品XBC相似的生物相容性,能够安全应用于生物医用领域。     

Synthesis and Characterization of High-Transparent Poly(vinyl alcohol)/Poly(vinyl pyrrolidone)(PVA/PVP) Hydrogels

In this paper, transparent poly(vinyl alcohol)/poly(vinyl pyrrolidone)(PVA/PVP) hydrogels were prepared by using the solvent of dimethyl sulfoxide(DMSO) aqueous solution and the method of freeze/thawing. The effect of PVP interaction, mechanical property and transparence of PVA/PVP hydrogel was investigated and evaluated by FT-IR analysis, mechanical test machine and UV spectrophotometer. The results showed that when the content of PVP was 8% in the DMSO aqueous solution, the highest transparence of PVA/PVP hydrogel was obtained, with excellent tensile strength values higher than 3.5 MPa. Therefore, the PVA/PVP hydrogel composite has a potential to be used as the transparent core of a novel artificial cornea.     

聚甲基丙烯酸羟乙酯水凝胶人工晶状体材料的合成与性能

以甲基丙烯酸羟乙酯为原料,过硫酸铵/偏重亚硫酸钠为引发体系,二甲基丙烯酸三乙二醇酯为交联剂,采用溶液聚合法制备了聚甲基丙烯酸羟乙酯水凝胶(PHEMA)人工晶状体材料。系统考察了聚合反应时间、温度及引发剂和交联剂的用量等对该水凝胶材料机械强度、平衡水含量(EWC)的影响,并对PHEMA水凝胶的结构和光学性能进行了表征。实验结果表明,PHEMA水凝胶的最佳合成条件为:引发剂0.5wt%,交联剂1.0wt%,反应温度40℃,反应时间36h。在此条件下制备的PHEMA水凝胶的拉伸强度达到0.57MPa,邵氏A硬度为23.0,平衡含水量超过40%,透光率≥97%。     

Mechanisms of decrease in fatigue crack propagation resistance in irradiated and melted UHMWPE

Adhesive/abrasive wear in ultra-high molecular weight polyethylene (UHMWPE) has been minimized by radiation cross-linking. Irradiation is typically followed by melting to eliminate residual free radicals that cause oxidative embrittlement. Irradiation and subsequent melting reduce the strength and fatigue resistance of the polymer. We determined the radiation dose dependence and decoupled the effects of post-irradiation melting on the crystallinity, mechanical properties and fatigue crack propagation resistance of room temperature irradiated UHMWPE from those of irradiation alone. Stiffness and yield strength, were largely not affected by increasing radiation dose but were affected by changes in crystallinity, whereas plastic properties, ultimate tensile strength and elongation at break, were dominated at different radiation dose ranges by changes in radiation dose or crystallinity. Fatigue crack propagation resistance was shown to decrease with increase in radiation dose and with decrease in crystalline content. Morphology of fracture surfaces revealed loss of ductility with increase in radiation dose and more detrimental effects on ductility at lower radiation doses after post-irradiation melting.     

Development of antibiotic and debriding enzyme-loaded PLGA microspheres entrapped in PVA-gelatin hydrogel for complete wound management

Abstract A biocompatible moist system was developed for effective and complete wound healing. Optimized PLGA microspheres of gentamicin (GM) and serratiopeptidase (STP) were incorporated into PVA-gelatin slurry and casted into films to prepare multiphase hydrogel. The prepared system was characterized by in vitro and in vivo studies. Results revealed the uniform dispersion of microspheres in three-dimensional matrix of the hydrogel. The in vitro release data showed a typical biphasic release pattern. All parameters such as wound contraction, tensile strength, histopathological and biochemical parameters were observed significant (p 相似文献