聚乙烯醇硫酸钾水凝胶电机械化学行为研究

通过将交联聚乙烯醇硫酸酯化的方法制备了一种新型电刺激响应性聚乙烯醇硫酸钾(PVSK)智能水凝胶,并探讨了溶液离子强度和pH对PVSK水凝胶的溶胀吸水率、机械性能以及电机械化学行为的影响.结果表明,制备的PVSK水凝胶的平衡溶胀比随NaCl溶液离子强度的增大而减小,在pH2.39～10.83范围内基本不受溶液pH的影响;经不同离子强度和pH的NaCl溶液充分溶胀的PVSK水凝胶具有良好的机械性能,在非接触的直流电场作用下,该水凝胶向电场负极弯曲,凝胶的弯曲速度和弯曲偏转量随外加电场强度的增加而增大,随NaCl溶液离子强度的增大出现临界最大值,但不随溶液pH(2.08～10.53)的改变而改变;在循环电场作用下,PVSK水凝胶的电机械化学行为具有良好的可逆性.     

明胶水凝胶电刺激响应行为的研究

制备了戊二醛交联的明胶水凝胶 ,并研究了其吸水率、力学性能和电刺激响应行为 .结果表明 ,在NaCl溶液中 ,明胶水凝胶的平衡溶胀比随NaCl溶液的浓度增大而减小 ,经 0 0 1mol LNaCl溶液充分溶胀的明胶水凝胶膜其弹性模量为 4.2 9kPa ,抗张强度为 5 11kPa ,断裂伸长率为 110 %.在NaCl溶液中于非接触的直流电场作用下 ,明胶水凝胶向电场负极弯曲 ,凝胶的弯曲速度和弯曲偏转程度随外加电场的增大而增大 ,随NaCl溶液离子强度的增大出现临界最大值 .在周期性电场作用下 ,其弯曲响应行为具有良好的可逆性 .通过聚电解质凝胶弯曲理论初步解释了其弯曲机理 .     

可生物降解的pH敏感水凝胶的合成及其溶胀性能研究

采用明胶和聚乙烯醇为原料,制备了戊二醛交联、明胶／聚乙烯醇配比不同的水凝胶,并用FTIR和SEM对产物进行了表征。研究了凝胶的溶胀动力学,结果表明,原料配比对各种凝胶的溶胀速率影响不大,而对平衡溶胀比与原料配比有关,室温下凝胶的平衡溶胀比在300％～500％之间。pH敏感性研究表明,几种凝胶均表现出明显的pH响应性,当溶胀介质的pH值在明胶等电点附近时,水凝胶的溶胀比达到最小值,凝胶的溶胀-消溶胀动力学曲线呈“W”形,即该凝胶具有形状记忆功能。     

紫外光共聚交联制备GelMA/PEGDA水凝胶

为避免物理交联明胶基水凝胶的热不稳定性,以及化学方法交联明胶基水凝胶存在的毒性,本文采用丙烯酰化的方法将甲基丙烯酸酐(MA)与明胶反应,在明胶分子链上引入双键结构,并且实现了紫外光照射引发甲基丙烯酰胺基明胶(GelMA)与聚乙二醇双丙烯酸酯(PEGDA)共聚交联制备水凝胶。研究了不同的MA加入量对明胶修饰度的影响,并对GelMA/PEGDA交联水凝胶理化性质进行了测试和分析。结果表明:体系中PEGDA含量增加,能释放更多的自由基,增加交联反应的活性和程度,使水凝胶形成更加致密的三维网络结构。并且GelMA/PEGDA交联水凝胶在37℃比GelMA交联水凝胶更加稳定。GelMA/PEGDA交联水凝胶将来有望成为组织工程的支架材料。     

组织工程用水凝胶材料

综述了目前用于组织工程支架材料的水凝胶,包括胶原和明胶、透明质酸盐、海藻酸盐,琼脂糖和壳聚糖等天然水凝胶,聚丙烯酸及其衍生物、聚氧化乙烯及其衍生共聚物、聚乙烯醇、聚磷腈和合成多肽等合成水凝胶,并介绍了可注射性组织工程水凝胶。     

聚乙烯醇/海藻酸钠互穿网络水凝胶结构与性能研究

采用天然高分子海藻酸钠(SA)与聚乙烯醇(PVA)复合,通过化学交联法制备PVA/SA互穿网络水凝胶。SA的加入减弱了PVA分子间的氢键作用,而随SA含量增加,SA分子与PVA分子间的氢键作用增强。同时凝胶网络由致密变得疏松,网孔增大,出现微相分离的"核壳"结构。由于交联后的SA与PVA分子的Tg较接近,水凝胶仅有一个Tg,两相仍为部分相容。应变及频率扫描曲线中低应变区的储能模量远大于损耗模量,其网络松弛因子n值接近0,证明该凝胶具有较完整的网络结构,并表现为弹性。适量的SA可提高凝胶的力学及溶胀性能。     

食用/工业明胶的凝胶及LF-NMR弛豫特性的比较

该文研究了食品/工业明胶浓度、混合比例及蔗糖或NaCl对体系的黏度、凝冻强度及LF-NMR弛豫特性的影响。结果发现,与食用明胶相比,工业明胶的凝冻强度与黏度较低。随着明胶浓度的增加,体系的黏度、凝胶强度均相对增大;结合水弛豫时间T_(21)、自由水弛豫时间T_(22)及自由水比例S_(22)均减小,而结合水比例S_(21)增大。随着工业明胶含量的增多,混合体系的黏度与凝冻强度均线性降低,T_(21)、T_(22)及S_(21)均线性增大,S_(22)线性减小;相同蔗糖或NaCl浓度下,食用明胶体系的黏度、凝冻强度最大,混合明胶体系次之,而工业明胶体系的最小;随着蔗糖浓度的增加,体系的黏度均增大,食用、混合体系的凝冻强度增大,而工业明胶变化较小;各体系的T_(22)、S_(22)均减小,S_(21)增大,工业明胶的T_(21)增大,而食用明胶、混合明胶体系的T_(21)变化不大。随着NaCl浓度的增加,各体系的凝冻强度均相对降低,而T_(21)、T_(22)、S_(21)均相对增大,S_(22)减小。     

聚乙烯醇磷酸酯水凝胶电刺激响应行为的研究

以脲为催化剂,将聚乙烯醇(PVA)磷酸酯化制成聚乙烯醇磷酸酯,再经戊二醛交联制备了一种新型的聚乙烯醇磷酸酯水凝胶.研究了水凝胶的溶胀性能,力学性能和电刺激响应行为.结果表明,该凝胶在NaCl水溶液中其平衡溶胀率随NaCl溶液的离子强度增大而减小.在离子强度为0~0.2的NaCl水溶液中,其弹性模量为0.300~0.356 MPa,抗张强度为91.5~137.8 kPa,断裂伸长率为32.0%~37.5%,且均随离子强度的增大而增大.在去离子水和NaCl水溶液中于非接触直流电场作用下,凝胶向电场负极弯曲,弯曲速度和应变随外加电压的增大而增大,并随NaCl离子强度的增大于0.005处出现极大值.在循环电场作用下,聚乙烯醇磷酸酯水凝胶的电刺激响应行为具有良好的可逆性.     

磺化明胶水凝胶的制备及其电场响应性能

采用明胶为原料,以甲基丙烯酸缩水甘油酯和亚硫酸氢钠为改性剂,在明胶分子链上引入极性基团磺酸基,制得新型磺化明胶水凝胶。采用红外光谱(FT-IR)、X射线光电子能谱(XPS)和扫描电镜(SEM)对其组成和结构进行了表征。通过动态黏弹谱仪(DMA)测定水凝胶的储能模量,探讨不同外加电场作用下该水凝胶的电场响应性能。随着明胶水凝胶中S元素的原子百分比的增大,在外加电场下,胶体的电场响应能力增强。当外加电场为1.6kV/mm、明胶水凝胶中S的原子百分比为1.59%时,水凝胶对电场作用的响应最明显,储能模量的增加率为31.86%。     

Hofmeister效应辅助的蛋白质基水凝胶应变传感器

以酪蛋白酸钠和明胶为原料, 通过简单的在硫酸铵溶液中浸泡的方法, 借助Hofmeister效应制备了一种强韧导电的酪蛋白酸钠/明胶水凝胶, 克服了蛋白质基水凝胶柔软、 易碎的问题. 测试结果表明, 该水凝胶具有优异的机械性能, 最大拉伸应力为3.55 MPa, 最大拉伸应变为1375%; 水凝胶的最大电导率为0.0954 S/cm, 导电灵敏因子为0.53. 用该水凝胶制备的传感器对不同大小及不同速率的应变均具有分辨能力, 能够监测人体不同部位的运动, 且传感器的信号传输具有稳定性和准确性, 表明该水凝胶是监测人体健康和运动的理想材料. 该水凝胶还具有良好的形状记忆性能. 这一策略为制备全天然蛋白质基水凝胶开辟了新的思路, 扩展了水凝胶在生物医学和电子传感等相关领域的应用前景.     

Study on Biological Safety of Polyvinyl Alcohol/Collagen Hydrogel as a Tissue Substitute (II)

Physically crosslinked polyvinyl alcohol/collagen composite hydrogels were prepared by a cyclic freezing-drying technique. The biological properties of the hydrogels, including hemolysis, anaphylaxis, pyrogen and acute systemic toxicity tests and implantation in-vivo, were investigated. The hemolysis test suggested that the polyvinyl alcohol/collagen, with a hemolysis index of 1.19%, did not have an obvious hemolysis reaction. There was no toxicosis or death cases observed in the acute systemic toxicity test, and the hydrogel showed no anaphylaxis or pyrogen response. The composite hydrogel showed a good histological compatibility in the in-vivo study. The results indicated that the polyvinyl alcohol/collagen composite hydrogels have promising applications for pharmaceutical and biomedical fields.     

聚皂凝胶对直流电场作用的响应

研究了三种聚皂凝胶在直流电场下的响应．这三种凝胶在直接接触电场下,在阳极端发生消溶涨,而在非直接接触电场下形状发生显著的弯曲这些响应均随电场电压的升高而增强．聚皂凝胶在电场下产生响应的驱动力,除了因离子迁移产生的渗透压差外,疏水相互作用也是驱动力之一.     

Hybrid hydrogels based on cross-linked polyacrylic acid and polyvinyl alcohol as electrically controlled artificial muscles

A procedure was developed for preparing hybrid hydrogel specimens of preset configuration from cross-linked polyacrylic acid and polyvinyl alcohol. The specimens exhibit higher mechanical characteristics compared to hydrogels of cross-linked polyacrylic acid. Hydrogel specimens fabricated in the form of elastic rings demonstrate an electromechanical response, contraction on passing electric current through their cross section. This effect is more pronounced for the specimens swollen in a sodium sulfate solution than for those swollen in distilled water. The results obtained show that the hydrogels can be used as a linearly operating mechanical force generator (artificial muscle).     

亲水/疏水半互穿网络凝胶在直流电场作用下的响应

研究了一种亲水 疏水型半互穿网络水凝胶 (PAAc QPVPDgels)对直流电场的刺激应答 .该凝胶中的疏水型N 十二烷基聚 (4 乙烯吡啶 )溴化盐 (QPVPD)高分子链与亲水型聚丙烯酸水凝胶 (PAAc)网络通过物理缠绕复合 .由于疏水力和亲水力的共同作用 ,在接触电场下 ,该凝胶在阳极端发生消溶胀 ,疏水相互作用对消溶胀有一定的影响 ;在非接触电场下 ,该凝胶在弱碱性溶液中迅速向阴极方向弯曲 ,在弱酸性溶液中首先发生消溶胀 ,然后向阳极方向弯曲     

pH-敏感的疏水型凝胶在直流电场中的刺激响应

合成了不同疏水链长的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与 4 ,4′ 二 (甲基丙烯酰胺基 )偶氮苯交联共聚的聚电解质凝胶 .该凝胶在非接触电场中发生消溶胀 ,但疏水侧链较长的凝胶在发生消溶胀之前经历了一个溶胀过程 .凝胶在电场中首先弯向阴极 ,随着时间的延长或电压的升高弯向阴极 ;并出现弯曲的方向或弯曲的程度的波动 .当撤去电场后 ,凝胶又能恢复到初始的形态 .凝胶的这些性质既与电渗、电扩散及电解有关 ,亦与凝胶的疏水相互作用有关     

Flexible,stretchable and conductive PVA/PEDOT:PSS composite hydrogels prepared by SIPN strategy

Stretchable conductive hydrogels have received significant attention due to their possibility of being utilized in wearable electronics and healthcare devices. In this work, a semi-interpenetrating polymer network (SIPN) strategy was employed to fabricate a set of flexible, stretchable and conductive composite hydrogels composed of polyvinyl alcohol (PVA) in the presence of glutaraldehyde as the crosslinker, HCl as the catalyst and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) as the conductive medium. The results from FTIR, Raman, SEM and TGA indicate that a chemical crosslinking network and interactions of PVA and PEDOT:PSS exist in the SIPN hydrogels. The swelling ratio of hydrogels decreased with increasing content of PEDOT:PSS. Due to the chemical crosslinking network and interactions of PVA and PEDOT:PSS, PVA networks semi-interpenetrated with PEDOT:PSS exhibited excellent tensile and compression properties. The tensile strength and elongation at breakage of the composite hydrogels with 0.14 wt% PEDOT:PSS were 70 KPa and 239%, respectively. The compression stress of the composite hydrogels with 0.14 wt% PEDOT:PSS at a strain of 50% was about 216 KPa. The electrical conductivity of the hydrogels increased with increasing PEDOT:PSS content. The flexible, stretchable and conductive properties endow the composite hydrogel sensor with a superior gauge factor of up to 4.4 (strain: 100%). Coupling the strain sensing capability to the flexibility, good mechanical properties and high electrical conductivity, we consider that the designed PVA/PEDOT:PSS composite hydrogels have promising applications in wearable devices, such as flexible electronic skin and sensitive strain sensors.     

淀粉-丙烯酸钠接枝共聚物的固体高分辨核磁共振研究

运用固体高分辨核磁共振技术,通过测量13C魔角旋转/交叉极化(CP/MAS)谱、1H自旋-晶格弛豫时间T1及旋转坐标系中的自旋-晶格弛豫时间T1ρ,对一系列淀粉-丙烯酸钠接枝共聚物的相结构进行了研究,并与淀粉、均聚丙烯酸钠及两者共混物的实验结果进行了比较.结果表明,接枝共聚导致了淀粉结晶度的明显降低;在共混物和接枝共聚物中,淀粉和聚丙烯酸钠组分都具有纳米尺度的相容性,由于接枝的效应,接枝共聚物中两个组分表现出比共混物更高的相容水平.     

Preparation and characterization of PVA/SA/HA composite hydrogels for wound dressing

A composite hydrogel based on, by introducing, polyvinyl alcohol, sodium alginate, and hyaluronic acid was fabricated using CaCl₂ as a cross-linker. The physical properties including morphology, water vapor transmission rate, and hydrophilicity were investigated. All PVA/SA/HA composite hydrogels with different compositions had highly homogeneous and interconnected pores, and the morphologies of the PVA/SA/HA hydrogels ranged from fibrous structure to irregular structure with increasing content of SA. The introduction of sodium alginate enhanced the hydrophilicity and water vapor transmission capacity of the hydrogel; however, the hydrophilicity of the composite hydrogels decreased with the increasing cross-linker content.     

高强度聚乙烯醇/聚苯胺/聚吡咯/TiO2导电杂化水凝胶的制备与性能

本文以聚乙烯醇(PVA)、苯胺(ANI)、吡咯(Py)及钛酸丁酯(TBOT)为原料,通过溶胶-凝胶法、原位氧化聚合法及冷冻-融溶法一步得到聚乙烯醇/聚苯胺/聚吡咯/TiO 2(PVA/PANI/PPy/TiO 2)杂化水凝胶。结果表明,该杂化水凝胶具有优异的力学性能和导电性能。当n(ANI)∶[KG-*3/5]n(Py)=8∶[KG-*3/5]2(TBOT体积为100μL)时,其压缩强度高达2.45 MPa。同时,在外加电源的作用下,该凝胶能够使灯泡发光。当n(ANI)∶[KG-*3/5]n(Py)=2∶[KG-*3/5]8(TBOT体积为150μL)时,杂化水凝胶的电导率(0.25 S/m)最好。该杂化水凝胶有望广泛地应用在柔性可穿戴电子器件、安全离子电池、传感器和生物器件等领域。     

Fabrication of polyvinyl alcohol/chitosan oligosaccharide hydrogel: physicochemical characterizations and in vitro drug release study

Abstract

Hydrogel composites from polyvinyl alcohol and chitosan have been developed by various researchers as a function of their composition for various medical applications. Although, the solubility of chitosan in acidic solvents may limit its wide bioengineering applications. In this article, we demonstrate that polyvinyl alcohol-chitosan oligosaccharide (water soluble) to develop cross-linked hydrogel network using chemical cross linker. X ray diffraction, Fourier transform infrared spectroscopy, and wettability study of these hydrogels were also performed. Lomefloxacin drug was loaded into the hydrogels and its release profile was studied.