Preparation and Characterization of pH-Sensitive Polyvinyl Alcohol Hydrogel for Cancer Therapy

Hydrogel has emerged as an excellent carrier platform for smart drug delivery and effective cancer treatment due to its high water content, good biocompatibility and sufficient mechanical properties. In this work,the DOX-loaded polyvinyl alcohol( PVA)hydrogel was prepared by freeze-thawing technique. The swelling test and the mechanical properties of the pure PVA hydrogels were performed. In addition, the in vitro drug release profiles were examined and the in vitro antitumor efficiency against He La cells was also estimated. The results indicated that the resulting PVA hydrogels contained significant amounts of water and possessed good mechanical properties,and DOX-loaded PVA hydrogel exhibited a sustained and p H-responsive DOX release. The MTT assays also demonstrated that the released DOX could effectively inhibit the proliferation of He La cells. Thus,the cross-linked PVA hydrogel can be further developed as a promising platform for cancer therapy.

A Polyvinyl Alcohol/Acrylamide Hydrogel with Enhanced Mechanical Properties Promotes Full-Thickness Skin Defect Healing by Regulating Immunomodulation and Angiogenesis Through Paracrine Secretion

Hydrogel-based tissue-engineered skin has attracted increased attention due to its potential to restore the structural integrity and functionality of skin.However,the mechanical properties of hydrogel scaffolds and natural skin are substantially different.Here,we developed a polyvinyl alcohol(PVA)/acrylamide based interpenetrating network(IPN)hydrogel that was surface modified with polydopamine(PDA)and termed Dopa-gel.The Dopa-gel exhibited mechanical properties similar to native skin tissue and a superior ability to modulate paracrine functions.Furthermore,a tough scaffold with tensile resistance was fabricated using this hydrogel by three-dimensional printing.The results showed that the interpenetration of PVA,alginate,and polyacrylamide networks notably enhanced the mechanical properties of the hydrogel.Surface modification with PDA endowed the hydrogels with increased secretion of immunomodulatory and proangiogenic factors.In an in vivo model,Dopa-gel treatment accelerated wound closure,increased vascularization,and promoted a shift in macrophages from a proinflammatory M1 phenotype to a prohealing and anti-inflammatory M2 phenotype within the wound area.Mechanistically,the focal adhesion kinase(FAK)/extracellular signal-related kinase(ERK)signaling pathway may mediate the promotion of skin defect healing by increasing paracrine secretion via the Dopa-gel.Additionally,proangiogenic factors can be induced through Rho-associated kinase-2(ROCK-2)/vascular endothelial growth factor(VEGF)-mediated paracrine secretion under tensile stress conditions.Taken together,these findings suggest that the multifunctional Dopa-gel,which has good mechanical properties similar to those of native skin tissue and enhanced immunomodulatory and angiogenic properties,is a promising scaffold for skin tissue regeneration.

Intrinsic conductive cellulose nanofiber induce room-temperature reversible and robust polyvinyl alcohol hydrogel for multifunctional self-healable biosensors

Polyvinyl alcohol(PVA)hydrogels are widely used for flexible sensors by adding various conductive substances due to their excellent mechanical properties and self-healing properties.However,most of the conductive substances added to PVA hydrogel sensors are currently complicated to prepare,costly,and environmentally unfriendly.Herein,to overcome this challenge,we successfully prepared intrinsic conductive cellulose nanofiber(G-CNF)by simply applying sulfuric acid and a low-energy water bath with heat treatment,and obtained a powerful multifunctional self-healing PGC hydrogel biosensor using dynamic chemical cross-linking of PVA and borax with glycerol and G-CNF.The obtained PGC hydrogels have excellent mechanical properties(strain:950%),good adhesion ability,robust self-healing properties,and room-temperature reversibility,due to the presence of conductive networks and hydrogen bonds within PGC hydrogel.Especially,PGC hydrogels with the graphene structured G-CNF have a fast response to various signals and good stability with gauge factor(GF)values up to 1.83,as well as a sensitive response to temperature(temperature coefficient of resistance(TCR)up to 1.9),which can be designed as a variety of biosensors,such as human motion monitoring,information encryption/transmission,and real-time temperature monitoring biosensors.Thus,PGC hydrogels as multifunctional self-healing hydrogel biosensors pave the way for the development of flexible biosensors in wearable devices,human–computer interaction,and artificial-related applications.

Fabrication and Characterization of One Interpenetrating Network Hydrogel Based on Sodium Alginate and Polyvinyl Alcohol

One interpenetrating network hydrogel based on sodium alginate (SA) and polyvinyl alcohol (PVA) was synthesized by combining the raw materials of PVA and SA with the double physical crosslinking methods of freezing thawing and Ca2+ crosslinking. The PVA-SA composite hydrogel have been characterized by scanning electron microscopy for surface morphology, infrared spectroscopy for investigating the chemical interactions between PVA and SA, X-ray diffraction for studying the PVA-SA composite structure property and thermal gravimetric for understanding the PVA-SA composite thermal stability. The swelling behavior and the degradation rate of the PVA-SA composite hydrogel were studied in simulated gastrointestinal fluid. Using bovine serum albumin (BSA) and salicylic acid as the model drugs, the release behavior of the PVASA composite hydrogel on macromolecular protein drugs and small molecule drug were evaluated. The results showed that the water absorption and degradation ability of the PVA-SA composite hydrogel was much better compared to the pure SA hydrogel or pure PVA hydrogel. The hydrogel exhibited remarkable pH sensitivity and the network was stable in the simulated intestinal fluid for more than 24 h. With the advantages such as mild preparation conditions, simple method, less reagent and none severe reaction, the PVA-SA composite hydrogel is expected to be a new prosperous facile sustained drug delivery carrier.

Ethosomes-Silk Fibroin/Polyvinyl Alcohol Composite Hydrogel Transdermal Drug Delivery System : Preparation and Characterization

One key of constructing ideal transdermal drug delivery system(TDDS)is enhancing the percutaneous rate of drugs without sacrificing compatibility.Ethosomes(Eths)have excellent transdermal performance as well as good biocompatibility,and thus been widely used as drug carrier.Hydrogel has good 3-dimensional mesh structure which is convenience for drugs release and storage.In this study,Eths were introduced into silk fibroin(SF)/polyvinyl alcohol(PVA)composite hydrogel to construct a novel TDDS through a green process.The Ethsomes(Eths)-SF/PVA composite hydrogel TDDS showed good mechanical properties(stress:(0.236±0.032)MPa;strain:(65.74±2.45)%).Also,skin fibroblasts can grow and proliferate well on this TDDS,indicating that this material has a good cytocompatibility.Furthermore,with doxorubicin hydrochloride(Dox)as a model drug loaded in ethosomes,in vitro studies showed that this TDDS was able to transdermally release Dox efficiently.Our data suggested this novel system had a good potential for application in TDD,though further evaluative study still needed to carry out.

The Preparation and Cytocompatibility of Injectable Thermosensitive Chitosan/Poly(vinyl alcohol) Hydrogel

In order to investigate the strength,structure and cell cytocompatibility of injectable thermosensitive chitosan(CS)/poly(vinyl alcohol)(PVA)composite hydrogel,chitosan hydrochloride solution was transferred to a neutral pH and mixed with different proportions of PVA,then the gelation time and strength of these different hydrogels were tested and spatial structures were observed under a scanning electron microscopy(SEM)after freeze-drying.The cytocompatibility of the hydrogels was evaluated through cytotoxi...

羟基磷灰石-聚乙烯醇/胶原-壳聚糖-明胶复合水凝胶修复兔骨软骨缺损

背景:关节骨软骨缺损是目前骨科医生面临的难题,传统修复方法难以取得满意疗效,以羟基磷灰石-聚乙烯醇为基础的复合水凝胶材料是目前研究的一个方向。目的:制备羟基磷灰石-聚乙烯醇/胶原-壳聚糖-明胶复合水凝胶,表征其物理学特征,验证其植入体内后的组织相容性及细胞黏附增殖能力,探讨其对兔骨软骨缺损的修复效果。方法:利用3D打印技术制备圆柱状多孔聚乳酸支架(孔径分别为1.2,1.4,1.6,1.8 mm),再将聚乙烯醇及羟基磷灰石混合乳液灌入聚乳酸支架中,经过冻融及二氯甲烷溶解后制成羟基磷灰石-聚乙烯醇水凝胶。然后将胶原-壳聚糖-明胶混合液灌入羟基磷灰石-聚乙烯醇水凝胶中,利用京尼平进行交联,最后经乙醇清洗及冷冻干燥制成羟基磷灰石-聚乙烯醇/胶原-壳聚糖-明胶复合水凝胶,表征4组水凝胶的物理学特征,筛选性能最优的水凝胶进行后续实验。将羟基磷灰石-聚乙烯醇水凝胶、胶原-壳聚糖-明胶复合水凝胶分别植入SD大鼠皮下,苏木精-伊红与Masson染色观察材料表面的细胞黏附生长状况。在15只兔双侧膝关节股骨滑车制作骨软骨缺损(直径5 mm、深6 mm)模型,左侧植入复合水凝胶(实验组),右侧未植入任何材料(对照组),Micro-CT及组织学检测来评估其对骨软骨缺损的修复效果。结果与结论:①综合孔隙率、含水率、力学测试及扫描电镜结果,得出孔径1.2 mm的羟基磷灰石-聚乙烯醇/胶原-壳聚糖-明胶复合水凝胶更符合天然软骨的一般特性,用于后续实验;②苏木精-伊红与Masson三色染色显示,随着材料植入大鼠皮下时间的延长,两种材料周边黏附的细胞均明显增多,其中胶原-壳聚糖-明胶植入后的细胞增殖状况更好,可见大量细胞长入其形成的网状结构,且网状结构也逐渐降解;③在兔骨软骨缺损实验中,至术后8周时,Micro-CT检查显示实验组植入的材料和周围骨-软骨整合良好,其表面及内部均有部分骨长入,对照组软骨及软骨下层仍然存在明显的缺损,未形成有效修复;苏木精-伊红与甲苯胺蓝染色显示,实验组植入复合水凝胶4-8周后即与周围骨软骨发生整合,随着时间的延长材料表面逐渐有新生软骨形成,至12周时缺损处大部分被新生软骨覆盖,软骨下层也出现良好的骨长入;对照组至术后12周虽然深层骨缺损大部分修复、浅层的软骨及软骨下骨缺损也有一定程度修复,但主要被纤维组织及部分纤维软骨替代;④结果表明,羟基磷灰石-聚乙烯醇/胶原-壳聚糖-明胶复合水凝胶材料可仿生天然软骨的结构和功能,在动物实验中能有效修复骨软骨缺损。

Improvement of poly(vinyl alcohol)/poly(vinylpyrrolidone) blended hydrogel by radiation crosslinking

A series of polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) blended hydrogel with kappa-carrageenan (KC) were prepared by radiation crosslinking with electron beam to improve the properties of hydrogel as wound dressing. The properties of the blended hydrogels were evaluated in terms of gel fraction, swelling behavior, gel strength and water evaporation from hydrogel. Gel fraction of PVA/PVP was saturated at 50 kGy and the achievcd gel fraction was 70%～80%. However, obtained hydrogel was very fragile and produced many bubbles at a dose of 50kGy and above, hence 1%～5% KC were added to give toughness. The rate of gel formation and the toughness of the blended hydrogel were raised after mixing KC. The PVA/PVP/KC blended hydrogel irradiated showed satisfactory properties for wound dressing, it did not produce bubble during irradiation, and it could retard the water evaporation.

焦磷酸三聚氰胺与聚乙烯醇分子之间的氢键相互作用提高聚乙烯醇水凝胶薄膜的阻燃性能

文章通过聚乙烯醇(PVA)与硼酸(H_(3)BO_(3))交联制备成水凝胶薄膜,添加焦磷酸三聚氰胺(MPP)提高PVA/MPP复合水凝胶薄膜的阻燃性能,当添加20 wt%MPP时,PVA阻燃性能达到UL-94 V-0级,MPP的加入可有效降低水凝胶薄膜的热释放速度(HRR)和发烟量。实验结果表明,MPP与PVA分子之间的氢键相互作用可以保持材料的力学性能,提高材料的阻燃性能。PVA/MPP水凝胶膜的阻燃机理是气相与凝聚相阻燃机理的协同作用,MPP分解为三聚氰胺和磷酸,然后三聚氰胺转化为N_(2)和CO_(2),磷酸促进PVA水凝胶形成连续致密的炭层,阻碍了与外界的氧气和热量交换。

聚乙烯醇/角蛋白/碳纳米管自愈合导电水凝胶的构建

为了进一步提高聚乙烯醇水凝胶的力学性能和导电灵敏性,本文以聚乙烯醇(PVA)为原料,以羊毛角蛋白(KE)和三氯化铝(AlCl_(3))为交联剂,添加碳纳米管(CNT)作为导电载体,制备出具有互穿双网络结构的自愈合导电水凝胶。通过扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)等测试手段对PVA/KE/CNT复合水凝胶进行测试分析。结果表明,AlCl_(3)中的Al^(3+)与角蛋白中的—COOH、—OH配位络合促使角蛋白间相互交联形成团簇,同时AlCl_(3)中的Al^(3+)也与PVA中的—OH交联形成紧密结构,增强了水凝胶的强度和韧性,CNT被两种交联结构紧紧包裹并赋予水凝胶导电性能。CNT的加入使复合水凝胶的韧性增加,添加质量分数为4%和5%的CNT可明显提升材料的强度;所制备的水凝胶都具有较好的自愈合性能,在一定范围内的自愈合性能与愈合时长成正比,12 h的愈合时长效果最佳;加入CNT使水凝胶电阻下降,添加质量分数为2%~5%的CNT后水凝胶电阻分别为8.98、4.56、3.81、3.12 kΩ。这种力学性能、自愈性能和导电性能均良好的水凝胶与人体运动检测应用具有天然的柔韧匹配性,在电子皮肤和柔性传感器领域有很好的应用前景。

阿仑膦酸钠/壳聚糖/聚乙烯醇复合水凝胶膜的制备与表征

背景:骨质疏松症是牙种植治疗的高风险因素,制备缓释阿仑膦酸钠的组织工程支架应用于骨质疏松患者口腔种植手术是当前口腔骨组织工程研究热点。目的:制备阿仑膦酸钠/壳聚糖/聚乙烯醇复合水凝胶膜,表征其缓释性能。方法:(1)采用物理交联法制备不同质量比(壳聚糖与聚乙烯醇的质量比分别为3∶7、5∶5、7∶3)的壳聚糖/聚乙烯醇复合水凝胶膜与单纯的壳聚糖、聚乙烯醇水凝胶膜,通过表征水凝胶膜的形貌、水接触角、力学性能、溶胀率与细胞相容性筛选适宜的水凝胶膜作为阿仑膦酸钠的载体。(2)制备含0,0.4,1.2,2.0 mg/L阿仑膦酸钠的单纯壳聚糖/聚乙烯醇复合水凝胶膜,将大鼠骨髓间充质干细胞分别与4组水凝胶膜共培养,通过CCK-8法与CD44免疫荧光染色检测水凝胶膜的细胞相容性。将载药壳聚糖/聚乙烯醇复合水凝胶膜浸泡于PBS中,采用紫外可见分光光度法检测复合水凝胶膜的药物释放性能。结果与结论:(1)表征结果显示,随着水凝胶膜中聚乙烯醇质量的增加,水凝胶膜的结构密度增加、孔隙率减少,水接触角(均在90°以内)、断裂伸长率与抗压强度增大,平衡溶胀率降低,对大鼠骨髓间充质干细胞的增殖均无影响,单纯壳聚糖水凝胶膜可促进大鼠骨髓间充质干细胞的黏附,3∶7、5∶5比例复合水凝胶膜不影响大鼠骨髓间充质干细胞的黏附,单纯聚乙烯醇水凝胶膜、7∶3比例复合水凝胶膜抑制大鼠骨髓间充质干细胞的黏附,综合以上结果,选择5∶5复合水凝胶膜作为阿仑膦酸钠的载体。(2)CCK-8检测结果显示,含0.4,1.2 mg/L阿仑膦酸钠组复合水凝胶膜无细胞毒性;CD44免疫荧光染色结果显示,含0.4 mg/L阿仑膦酸钠组复合水凝胶膜不影响大鼠骨髓间充质干细胞的黏附,含1.2,2.0 mg/L阿仑膦酸钠组复合水凝胶膜抑制大鼠骨髓间充质干细胞的黏附;含0.4,1.2,2.0 mg/L阿仑膦酸钠的壳聚糖/聚乙烯醇复合水凝胶膜在最初6 h内爆发性释放阿仑膦酸钠,此后均匀稳定地释放阿仑膦酸钠,释放时间达96 h以上。(3)结果表明,5∶5比例的壳聚糖/聚乙烯醇复合水凝胶膜具有良好的理化性能、细胞相容性,可以作为阿仑膦酸钠的缓释载体。

海藻酸钠/聚乙烯醇pH指示水凝胶的制备及其对鲜切哈密瓜的新鲜度指示

为制备能稳定且灵敏指示鲜切果蔬新鲜度的指示器,该研究以海藻酸钠和聚乙烯醇为基材,复配甲基红和溴百里酚蓝为指示剂,制备pH显色水凝胶。首先以指示剂添加量、交联剂浓度以及交联时间为影响因素进行单因素试验,以水凝胶的变色灵敏度和力学性能为指标,对水凝胶制备工艺进行优化;然后,对最优工艺制备的水凝胶进行结构表征和性能测定;最后,将其用于鲜切哈密瓜的新鲜度监测。结果表明,指示剂添加量为5%,交联剂质量浓度为7 g/L,交联时间为18 h的条件下制备的水凝胶结构完整,内部呈多孔结构,具有较好的硬度和弹性,在pH 3~11内有良好的颜色响应。将其应用到鲜切哈密瓜的新鲜度指示中发现,在4℃贮藏3 d时,哈密瓜从新鲜转变为次新鲜,此时水凝胶从黄绿色变为橙色。因此,该研究所制备的水凝胶在鲜切果蔬的新鲜度指示中具有较好的应用前景,有助于提高鲜切果蔬的安全性和消费者体验。

功能性聚乙烯醇基水凝胶材料的制备及性能研究

将具备聚集诱导发光性质的四苯乙烯结构单元接枝到聚乙烯醇(PVA)侧链得到本体改性的PVA材料,将含有硼酸结构的抗氧化单体与水溶性单体共聚得到水溶性抗氧化高分子聚合物,将这两种水溶性高分子材料物理混合,构建基于硼酸酯动态键的具有本征聚集诱导发光及抗氧化功能的自愈合水凝胶体系,利用FTIR,~1H NMR,SEM等方法考察了水凝胶的微观结构、荧光性能、机械性能及抗氧化性能。实验结果表明,两种水溶性高分子材料通过硼酸酯动态键可快速形成可注射水凝胶,且此水凝胶同时具有聚集诱导发光及抗氧化性能,有望用于荧光传感、药物控释等领域。

含铈功能离子液体导电水凝胶的制备及应用

目的:开发制备方法简单、力学性能强和导电性能好的水凝胶。方法:在聚乙烯醇(PVA)水凝胶中掺杂含铈类离子液体,用万能试验机和LCR数字电桥测试其性能。结果:在水凝胶中加入含铈类离子液体后电导率有了显著的提升,但过量的含铈类离子液体会使其力学性能下降。这表明可以通过控制含铈类离子液体的浓度来实现电导率和力学性能之间的平衡。结论:复合水凝胶中含铈类离子液体浓度越高,导电性能越好,适量的铈类离子液体同时也可以提高水凝胶的机械性能。综上所述,0.02 mol的含铈类离子液体与水凝胶以1∶100配制成的复合水凝胶平衡了导电性能和力学性能之间的关系。

基于纤维素膜的聚乙烯醇基抗溶胀水凝胶柔性传感材料的制备及性能研究

目前,基于水凝胶的柔性可穿戴传感器受到了人们广泛的关注。然而传统的水凝胶在水环境中的膨胀,限制了其应用。文中以聚乙烯醇(PVA)为基体,通过缩醛反应将4-乙炔基苯甲醛引入网络中,成功地制备了具有良好力学性能的抗溶胀水凝胶。该水凝胶通过破坏PVA分子链与水分子之间的氢键,降低溶胀的驱动力,π-π堆积增强链间相互作用减小孔隙度,抵抗水分子的渗透,使得溶胀率维持在5%。同时网络交联密度增加,改善了分子链间的间距,赋予水凝胶更高的韧性(断裂应力=1.4 MPa,断裂伸长率=528%)。考虑到生物相容性以及水环境的应用,使用无毒纤维素膜与水凝胶构建出一种用于人体动作监测的柔性应变传感器,拓展了可穿戴电子设备的潜在应用。

软骨修复用聚乙烯醇/壳聚糖复合水凝胶的制备及体外性能研究

以聚乙烯醇和壳聚糖为原料,利用冻融循环法,通过调节聚乙烯醇和壳聚糖的配比、冻融循环次数以及搅拌时间,采用正交试验制备出多组复合水凝胶,进行综合性能评价。结果表明:采用15%聚乙烯醇+1.5%壳聚糖混合搅拌4h,冻融循环5次制备的复合水凝胶具有较强的抗拉强度,适宜的含水率和溶胀率以及良好的血液相容性,对细胞无毒性且适合细胞生长,是一种具有应用前景的软骨修复组织工程材料。

CMC-PVA-β-CD三元复合水凝胶的制备

以羧甲基纤维素(CMC)、聚乙烯醇(PVA)、β-环糊精(β-CD)为原料,在碱性条件下与环氧氯丙烷(ECH)发生交联反应,制备具有高溶胀性能的CMC-PVA-β-CD三元复合水凝胶,并研究了CMC,PVA,ECH,β-CD添加量对水凝胶溶胀性能、力学性能的影响。结果表明:加入20.0 mL水,0.52 g CMC,0.20 g PVA,1.2 mL ECH,0.24 gβ-CD时,水凝胶溶胀率最高,为2 040.62 g/g,压缩应力为7.90 kPa。与PVA-CMC二元水凝胶相比,CMC-PVA-β-CD三元水凝胶的压缩应力和结晶度均有提高。该三元复合水凝胶具有较高的溶胀率和良好的力学性能,在生物医药、消毒杀菌领域具有很高的应用价值。

梯度多孔结构和力学性能的聚乙烯醇-单宁酸水凝胶

关节软骨损伤具有进展迅速、难以自愈的特点,水凝胶有望用于该疾病的治疗。基于软骨的分层结构和性能特征,制备了聚乙烯醇-单宁酸梯度水凝胶。扫描电镜观察发现,该水凝胶具有梯度渐变多孔结构,孔密度从水凝胶顶部到底部逐渐增加,孔径为100~300μm;力学试验结果表明,水凝胶的压缩性能呈现与天然软骨相似的梯度变化规律,压缩模量由顶部(0.32 MPa)逐渐增加至底部(0.64 MPa)。傅里叶红外光谱和共振光散射分析表明,单宁酸梯度分布并与聚乙烯醇形成分子间氢键,促进了梯度多孔结构形成和力学性能强化。

棉织物的聚乙烯醇/壳聚糖水凝胶抗菌整理

为提高棉织物的抗菌性能,将聚乙烯醇与壳聚糖溶液共混,以戊二醛为交联剂,制备抗菌水凝胶预聚液,通过浸渍整理制备了水凝胶复合织物。采用扫描电子显微镜、傅里叶红外光谱仪、热失重分析仪、万能材料拉力机等对整理前后棉织物进行测试与表征。结果表明:聚乙烯醇/壳聚糖水凝胶在棉织物表面形成一层均匀的水凝胶膜;改性棉织物的断裂强度和断裂伸长率略有提高,热稳定性降低,抗菌性能显著提高,对大肠埃希菌和金黄葡萄球菌的抑菌率高达99.9%。

高强度双网络结构木基复合凝胶的制备及性能

以木材为原料,通过脱基质处理获得木材纤维骨架,在其多孔结构中利用原位聚合法构建以聚乙烯醇(PVA)/聚丙烯酰胺(PAM)为双网络结构填充相的高强度木基复合凝胶。通过调控PVA及PAM在复合凝胶体系中的质量比,系统研究制备所得木基复合凝胶的宏/微观形貌、力学性能、光学性能及表面化学性能等变化规律。结果表明:在聚丙烯酰胺/木材纤维骨架中引入少量PVA,通过构建双网络结构,能够有效提升木基复合凝胶的力学性能,其最大拉伸强度可达16.47 MPa,断裂伸长率约为11.61%。将木基复合凝胶作为柔性基材组装构建传感器件,电导率为1.8 S/m,发现木基传感器在多种形变下均表现出稳定可重复的相对电流信号变化。