Graphite/poly (vinyl alcohol) hydrogel composite as porous ringy skirt for artificial cornea

Graphite/poly (vinyl alcohol) (PVA) hydrogel composites, which were designed as the porous ringy skirt surrounding the transparent core of a novel artificial cornea, were prepared by using the freeze/thawing process and the particle-leaching technique. The properties of the composites, including the water content, the mechanical strength, the porous architecture and the interactions between the graphite and PVA, were investigated. The tissue responses to the composite and pure PVA hydrogel were studied by in vivo implantation in the dorsal muscles of mice. The results showed that chemical interactions were present between the graphite and PVA in the composite, which benefited the combination of the two phases and enhanced the uniform distribution of graphite particles in the PVA matrix. However, the present of graphites in the PVA hydrogels reduced the tensile strength, elongation at break and water content of the composite. Moreover, the porous graphite/PVA hydrogel composite had interconnective pore structure with high porosity and enough mechanical strength. According to the histological analysis of 1 week and 12 weeks post-implantation, the graphite/PVA hydrogel composites showed less inflammatory reactions than the PVA hydrogels at the 1 week post-implantation. Moreover, compared to pure PVA hydrogel, the graphite/PVA hydrogel composite exhibited enhanced migration and infiltration of cells, and more neovascularization and tissue ingrowth. These in vivo characteristics will be beneficial for the long-term biofixation of artificial cornea. Therefore, the porous graphite/PVA hydrogel composite has a potential to be used as novel artificial cornea skirt.     

纳米羟基磷灰石/聚乙烯醇复合人工角膜材料

用纳米HA 与聚乙烯醇(PVA) 制备了一种新型人工角膜, 光学中心采用柔韧透明的PVA 水凝胶, 周边支架采用纳米HA 与PVA 复合的多孔水凝胶, 该设计有利于提高人工角膜支架与宿主角膜组织的生物性结合, 同时从工艺上解决了光学中心与周边支架的结合问题。研究结果表明, 复合材料中纳米HA 与PVA 具有相互作用;纳米HA 在复合材料中均匀分散;多孔复合水凝胶具有良好的显微结构。用光学显微镜对该人工角膜光学中心和支架结合部观察, 表明二者通过互穿网络结构形成了紧密结合。动物实验术后进行裂隙灯和组织学观察表明该复合人工角膜的生物相容性好, 人工角膜支架与宿主角膜组织可生物性愈合, 该人工角膜具有很好的临床应用前景。     

Preparation and in vivo investigation of artificial cornea made of nano-hydroxyapatite/poly (vinyl alcohol) hydrogel composite

An artificial cornea consisted of a porous nano-hydroxyapatite/poly (vinyl alcohol) hydrogel (n-HA/PVA-H) skirt and a transparent center poly (vinyl alcohol) hydrogel (PVA-H) were prepared. The n-HA/PVA-H skirt was homogeneously porous and these pores were interconnected. Inter-penetrating network was observed along the interface between the core and the skirt. Artificial corneas were implanted in eyes of rabbit. The corneal tissues were evaluated histological. The results displayed that a good biocompatibility and interlocking had happened between artificial cornea and host tissues. This novel cornea prepared here is potential to be used clinically.     

Preparation and in vitro characterization of BC/PVA hydrogel composite for its potential use as artificial cornea biomaterial

In order to investigate the potential use for bacterial cellulose (BC) as a novel artificial cornea replacement, BC/poly(vinyl alcohol) (BC/PVA) hydrogel composites were synthesized by freezing-thaw method. The BC/PVA composites were characterized by UV–Vis spectrophotometer (UV–Vis), X-ray diffraction (XRD), thermogravimetric (TG) analysis, mechanical property tests and scanning electron microscope (SEM) analyses. Our results showed that the resultant BC/PVA composites exhibited desirable properties as artificial cornea replacement biomaterial including high water content, high visible light transmittance and suitable UV absorbance, increased mechanical strength and appropriate thermal properties. Results of this work revealed that the BC/PVA composites exhibited some promising characteristics as artificial cornea composite material and may be improved further for its realistic applications.     

Novel PVP/PVA hydrogels for articular cartilage replacement

Poly(vinyl alcohol) (PVA) hydrogel has been considered as a very interesting and promising material for articular cartilage replacement. The most vital shortcoming of PVA hydrogels is that their mechanical properties are difficult to meet the requirements of articular cartilage. In the present work, blend hydrogels based on PVA and poly (vinyl pyrrolidone) (PVP) were prepared by repeated freezing and thawing method. Such hydrogel had similar internal three-dimensional structure and water content (approximately 75%) as nature articular cartilage. The mechanical and tribological properties were investigated to find out that change of mechanical and tribological properties of PVP/PVA hydrogels were significantly dependent on PVP content and freezing–thawing cycles. The blend hydrogel with 1 wt.% PVP had the best mechanical properties and the friction system consisting of such blend hydrogel and stainless steel ball exhibited a mixed lubrication regime especially under bovine serum lubrication. The results established that such hydrogel would be a novel attractive material for articular cartilage replacement.     

微波原位合成2D Ni-Fe MOF/硅藻土复合材料及其改性聚乙烯醇水凝胶不锈钢筛网油水分离性能

如何高效处理含油污水的问题,是如今世界科研人员共同关注的问题。聚乙烯醇(PVA)水凝胶作为高含水量及具有三维亲水网络的软材料在油水分离领域引起了广泛的关注。但是,和大多数具有超润湿性质的水凝胶一样,PVA水凝胶类油水分离材料不仅力学性能差,同时也存在化学稳定性差的问题。基于此,通过微波法制备了2D Ni-Fe金属-有机框架材料(MOF)-硅藻土(Dia)纳米材料及其PVA复合水凝胶。同时,不锈钢网经过浸泡2D Ni-Fe MOF-Dia/PVA水凝胶溶液得到2D Ni-Fe MOF-Dia/PVA水凝胶不锈钢筛网,表现出超亲水-水下超疏油性质。利用SEM、XPS分析2D Ni-Fe MOF-Dia及其复合水凝胶的化学组成和表面形貌。研究了2D Ni-Fe MOF-Dia/PVA复合水凝胶的力学性能及2D Ni-Fe MOF-Dia/PVA复合水凝胶不锈钢筛网的油水分离与乳液分离的分离效率及水通量,并对其耐盐性、耐酸耐碱性油水分离性能进行了测试。结果表明:2D Ni-Fe MOF-Dia/PVA复合水凝胶具有优异的力学性能,拉伸与压缩强度分别达到1.49 MPa及0.58 MPa,同时表现出超亲水-水下超疏油性质,2D Ni-Fe MOF-Dia/PVA不锈钢筛网的油水分离与乳液分离效率与通量分别可达99.2%和742.7 L·m?2·h?1。在酸性、碱性、盐性环境下均保持优异的分离效率与通量,并且在5次循环后,依旧保持稳定的分离效率与通量。      

微晶和氢键双增强水凝胶AG/PVA/CB[7]的制备和性能

以天然高分子琼脂糖(AG)为第一物理交联网络、聚乙烯醇(PVA)为第二物理交联网络、七元瓜环(CB[7])为交联剂,制备了双网络AG/PVA/CB[7]水凝胶。使用SEM、FT-IR和XRD等手段表征AG/PVA/CB[7]水凝胶的形貌、结构以及交联方式,研究了这种水凝胶的力学性能、溶胀性能和宏观自愈性能。结果表明：这种凝胶具有高强度和自愈性,高分子链之间通过氢键和微晶共同交联使其机械性能提高;该凝胶的力学性能随着冷冻-解冻次数的增加而提高,交联剂CB[7]的加入也使其力学性能提高,循环5次后其拉伸强度为0.37 MPa,杨氏模量为 0.23 MPa,平衡溶胀率为140%。     

Hydrophilic sponges based on 2-hydroxyethyl methacrylate Part VII: Modulation of sponge characteristics by changes in reactivity and hydrophilicity of crosslinking agents

Despite previous unsuccessful attempts to use hydrated poly(2-hydroxyethyl methacrylate) sponges as implantable biomaterials, recently these materials became important as peripheral components in an artificial cornea of the core-and-skirt design. The low mechanical strength of sponges prompted this study on possible improvement of tensile properties by the use of a variety of crosslinking agents. Three vinylic (dimethacrylates) and two allylic compounds were used at different concentrations (0.1 to 2% (mol)) as crosslinking agents in the production of sponges. Their influence on the mechanical properties, porous morphology and swelling behavior of resulting sponges was evaluated. The onset of phase separation during polymerization was also measured by visible spectrophotometry. The results suggested an inherent heterogeneity of sponges, i.e. pores of non-uniform size and structural inhomogeneities. While the effects of changes in the nature and concentration of crosslinking agents on the equilibrium water content of sponges were ambiguous, some of the mechanical properties, such as toughness and elasticity, were improved by crosslinking with allylic agents. Scanning electron microscopic examination suggested that the mechanical effect is related to the variation of size of the polymer particles constituting the sponge structure, which was proved to be dependent upon the onset of phase separation during polymerization. ©2000 Kluwer Academic Publishers     

聚乙烯醇水凝胶的制备及性能

利用冷冻-解冻法制备聚乙烯醇(PVA)水凝胶,研究了不同因素对PVA水凝胶力学性能和溶胀特性的影响。结果表明,PVA水凝胶是一种典型的粘弹性材料,在一定应变区内,材料的拉伸模量随应变的增加而增大;拉伸强度和平均拉伸模量随PVA水溶液的浓度和冷冻-解冻循环次数的增加而增强,凝胶的最大拉伸强度和拉伸模量分别为2.27 MPa和0.95 MPa。溶胀特性研究显示,PVA水凝胶在生理盐水中的平衡溶胀比小于其在蒸馏水中的平衡溶胀比;凝胶的平衡溶胀比随浓度和冷冻-解冻次数的增加而下降,其下降趋势满足幂函数的变化规律;水凝胶的溶胀过程符合溶胀动力学方程。     

Highly antifouling double network hydrogel based on poly(sulfobetaine methacrylate)and sodium alginate with great toughness

Hydrogels with good antifouling and mechanical properties as well as biocompatibility have great appli-cation potential in the field of biomedicine.In this paper,a newly double network(DN)hydrogel was prepared based on zwitterionic material sulfobetaine methacrylate(SBMA)and natural polysaccharide,sodium alginate(SA).The PSBMA network is covalently crosslinked while the SA network is ionically crosslinked by Ca2+.The hybrid crosslinked double network structure endows the DN hydrogel with excellent mechanical properties(E=0.19±0.01 MPa,σ=0.73±0.03 MPa),fast self-recovery ability as well as excellent fatigue resistance.Moreover,the results show that the PSBMA/SA-Ca2+DN hydrogel is biocompatible and resists the absorption of non-specific proteins and adhesion of microorganisms,such as cells and algae,exhibiting outstanding antifouling properties.These unique characteristics of PSBMA/SA-Ca2+DN hydrogel make it a promising candidate for biomedical application,such as artificial connective tissues,implantable devices,and underwater equipment.     

高强度耐低温纳米纤维素/聚乙烯醇导电复合水凝胶制备及其在柔性传感中的应用

纳米纤维素具有大长径比、较高的弹性模量与比表面积及丰富的表面官能团,是一种优良的纳米增强材料。首先以纳米纤维素(CNFs)为分散介质辅助分散MXene纳米片层,制备CNF-MXene纳米复合物,并通过FTIR与XPS分析CNFs与MXene的相互作用。以此复合物为增强填料,聚乙烯醇(PVA)为基底,制备CNF-MXene/PVA复合水凝胶,进一步通过KOH溶液处理,提高复合水凝胶的力学性能,并赋予复合水凝胶优异的离子导电性。该复合水凝胶表现出优异的力学性能,其拉伸强度与断裂伸长率分别达到255.9 kPa与1098.2%,还具有高电导率(2.38 S/m)、一定的抗冻性能与灵敏的应变/压力响应性。基于该复合水凝胶组装的应变/压力柔性传感器,由于具有极低的检测极限质量(100 mg)与极快的响应时间(225 ms),可以监控脉搏跳动与喉咙发声微小震动引起的压力变化。因此,该复合水凝胶基柔性传感器非常有希望应用于未来新一代可穿戴电子、人机交互等领域。      

磺胺嘧啶银/聚乙烯醇水凝胶复合材料的制备及性能表征

采用e-Beam电子辐射和冻融循环相结合的方法制备了磺胺嘧啶银(SD-Ag)/聚乙烯醇(PVA)水凝胶。研究了制备工艺对PVA水凝胶的性能的影响。通过拉伸性能测试、吸水率检测、SEM和FT-IR等表征,考察了PVA浓度(占总质量5%~15%)、冻融与辐射处理等对PVA水凝胶拉伸强度、断裂伸长率、吸水性、凝胶含量和微观结构等的影响。结果表明:随着PVA浓度增大,PVA水凝胶的拉伸强度提高。当PVA浓度为15%、辐射剂量为25kGy时,单独辐射、辐射后冻融及冻融后辐射三种工艺制备的PVA水凝胶拉伸强度分别为0.023 MPa、0.048MPa、0.028MPa,吸水率分别为为95%、45%、63%,说明经冻融处理的水凝胶力学强度提高,吸水率有所下降。然后,选择适当的制备工艺并在PVA水凝胶中加入SD-Ag,考察了SD-Ag/PVA水凝胶的抑菌性能,抑菌活性测试结果显示,随着SD-Ag含量的增加,SD-Ag/PVA水凝胶的抑菌效果增强,而且其对革兰式阴性菌(大肠杆菌)的抑菌效果优于其对革兰式阳性菌(金黄色葡萄球菌)的抑菌效果。     

Facile preparation of low swelling,high strength,self-healing and pH-responsive hydrogels based on the triple-network structure

A polyacrylic acid(PAA)/gelatin(Gela)/polyvinyl alcohol(PVA)hydrogel was prepared by copolymerization,cooling,and freezing/thawing methods.This triplenetwork(TN)structure hydrogel displayed superior mechanical properties,low swelling ratio and self-healing properties,The superior mechanical properties are attributed to the triple helix association of Gela and PVA crystallites by reversible hydrogen bonding.The characterization results indicated that the fracture stress and the strain were 808 kPa and 370% respectively,while the compression strength could reach 4443 kPa and the compressive modulus was up to 39 MPa under the deformation of 90%.The hydrogen bonding in PVA contributed to maintain and improve the self-healing ability of hydrogels.Every type of hydrogels exhibited a higher swelling ratio under alkaline conditions,and the swelling ratios of PAA,PAA/PVA and PAA/Gela hydrogels were 27.71,12.30 and 9.09,respectively.The PAA/Gela/PVA TN hydrogel showed the lowest swelling ratio(6.57)among these hydrogels.These results indicate that the novel TN hydrogels possess good environmental adaptability and have potential applications in the biomedical engineering and sensor field.     

Mechanical properties of nanohydroxyapatite reinforced poly(vinyl alcohol) gel composites as biomaterial

Nanohydroxyapatite reinforced poly(vinyl alcohol) gel (nano-HA/PVA gel) composites has been proposed as a promising biomaterial, especially used as an articular cartilage repair biomaterial. In this paper, nano-HA/PVA gel composites were prepared from mixing nano-HA particles modified by silicon coupling agent, with physiological saline solution (PSS) of PVA by freezing-thawing method. The effects of various factors on the mechanical properties of nano-HA/PVA gel composites were evaluated. It was shown that the mechanical behavior of nano-HA/PVA gel composites was similar to that of natural articular cartilage, which held special viscoelastic characteristics. The tensile strength and tensile modulus of the composites improved correspondingly with the increase of freezing-thawing times and concentration of PVA solution. The more concentration of PVA solution, the higher influence degree of concentration on the tensile strength of composites is. The tensile strength and tensile modulus of nano-HA/PVA hydrogel composites increased first and then decreased with the rising nano-HA content of the composites. The tensile modulus of the composites improved remarkably with the increase of elongation ratio.     

聚乙烯醇水凝胶功能化改性研究进展

PVA水凝胶化学性质稳定、无毒、生物相容性好、耐生物老化、吸水量高及易于加工,广泛应用于固定化载体、药物释放、组织工程等领域。综述了当前国内外聚乙烯醇水凝胶的制备方法最新研究进展,详细介绍了国内外关于聚乙烯醇水凝胶的力学性能、溶胀性能、细胞亲和性、智能化等改性方法的研究进展。最后展望了未来聚乙烯醇水凝胶功能化改性的研究方向和前景。     

Development of a PVA Hydrogel for Bioprosthetic Heart Valve Stent and Other Medical Applications

Polyvinyl alcohol (PVA) hydrogel (15%w/w) was processed by freezing and thawing from one through six thermal cycles to obtain wide range of mechanical properties. The materials were tested under uniaxial tension and results show that matching mechanical properties to that of porcine aortic root can be achieved. A fatigue machine for elastomer materials and tissues was built and fatigue test on PVA sample was carried out. The test results show that the PVA has good fatigue property. The stent prototype was designed and successfully made by mold casting method. Some potential medical applications are discussed.     

细菌纤维素/聚乙烯醇双网络复合水凝胶的制备与性能研究

利用冷冻-解冻法制备了细菌纤维素（BC）/聚乙烯醇（PVA）双网络复合水凝胶,研究不同BC含量及循环周期对BC/PVA复合水凝胶力学性能和溶胀特性的影响,结果表明,随着BC含量的增多,复合水凝胶的含水率、平衡溶胀比、拉伸强度和压缩强度与普通的PVA水凝胶相比均有一定程度的提高;综合考虑,当BC含量为4%时,各项性能均达到最佳值;随着循环次数的增多,水凝胶内部的物理交联点增多,导致水凝胶的含水率下降,拉伸强度和压缩强度则有明显的上升趋势。SEM观察的结果与之前的分析是一致的。     

Swelling and mechanical behaviors of carbon nanotube/poly(vinyl alcohol) hybrid hydrogels

In this paper, carbon nanotubes (CNTs) were added into poly(vinyl alcohol) (PVA) hydrogels to modify their mechanical properties. A series of CNT/PVA hybrid hydrogels were prepared by freezing/thawing method. The mechanical and swelling properties of all hybrid hydrogels are better than those of the original PVA hydrogel. Especially, for CNTP-0.5 specimen with 0.5% w/w CNTs, its tensile modulus, tensile strength and strain at break are increased by 78.2%, 94.3% and 12.7%, respectively. And its swelling behavior is different from that of the pure PVA hydrogel. Its final swelling ratios at room temperature and 310 K are increased by 35.7% and 44.9%, respectively.     

Properties of hydrogels synthesized by freezing and thawing aqueous polyvinyl alcohol solutions and their applications

The hydrogel synthesized by freezing a polyvinyl alcohol (PVA) aqueous solution and thawing it slowly has high water content, excellent mechanical properties of high tensile strength, elongation and good shape recovery by elasticity. The PVA used had a degree of polymerization of 2500 and a degree of saponification of 99.5 mol%. The solution was obtained by dissolving 7.5 g of PVA in 80 g of water, this was frozen at –50°C for 3 h and then warmed up to room temperature over 10h. This freezing–thawing process was repeated once again and a hydrogel was synthesized. The hydrogel had a water content of about 90 wt%. Its tensile strength was 0.6 MPa and the elongation at break was 130%. The shape of the hydrogel which was deformed by an external force recovered in a short time when it was released from the force. This recovery had good persistence and repeatability. Applying these properties a strain sensor and a gas pressure sensor were tested. Furthermore, a PVA hydrogel rod containing polyacrylic acid was used as a bending actuator. This hydrogel had the ability to deform when direct current was applied.     

Development of artificial articular cartilage

The present study describes the development of artificial articular cartilage on the basis of mimicking structural gel properties and mechanical gel properties of natural articular cartilage. It is synthesized from PVA/Si nanocomposite containing 20% Tetra ethoxy silane (TEOS) by sol-gel method. Mechanical strength of Poly(vinyl alcohol), PVA is improved up to 35 MPa. Manufacturing method is adopted considering colloidal stability of nano silica particle in PVA sol at specific pH = 1. An adhesive is also prepared from PVA/Si nanocomposite containing 40% TEOS for firm attachment of artificial articular cartilage on underlying bone with high bond strength.