PVA改性PAMPS-PAM超高力学性能双网络水凝胶的制备

采用紫外光引发聚合制备了聚乙烯醇(PVA)改性的聚(2-丙烯酰胺基-2-甲基丙磺酸)-聚丙烯酰胺(PAMPS-PAM)双网络(DN)水凝胶.测定并比较了PVA改性前后PAMPS-PAM双网络水凝胶的溶胀动力学;通过扫描电子显微镜(SEM)观察了单网络水凝胶的结构;测定PVA改性前后PAMPS-PAM双网络水凝胶的压缩及拉伸性能.结果表明,经PVA改性后的PAMPS-PAM双网络水凝胶有较高的溶胀比;0.82%PVA用量的PAMPS-PAM双网络水凝胶在90%压缩形变率下仍保持完整、最大拉伸应力达到0.5 MPa,大幅提高PAMPS-PAM双网络水凝胶的力学性能.     

聚乙二醇对PAMPS/PAM双网络水凝胶性能的影响

采用紫外光引发聚合制备了聚乙二醇(PEG)改性的聚(2-丙烯酰胺-2-甲基丙磺酸)/聚丙烯酰胺(PAMPS/PAM)双网络水凝胶.测定并比较了PEG改性前后双网络水凝胶的溶胀动力学以及单网络水凝胶中丙烯酰胺(AM)的吸收量;用扫描电子显微镜(SEM)观察了单网络水凝胶的结构;测定PEG改性前后双网络水凝胶的压缩及拉伸性能.结果表明,经PEG改性后的双网络水凝胶有较高的溶胀比;改性后单网络水凝胶更易吸收AM;改性后双网络水凝胶压缩形变率达到90%以上、拉伸形变率是未改性双网络水凝胶的2倍.     

智能水凝胶在生物医学领域中的研究进展

水凝胶是最常用的生物材料之一。它们在化学和结构上的多样性使其能够在广泛的场景中使用,目前 水凝胶材料在生物医药领域主要用于药物输送、癌症治疗和伤口愈合等。聚合物网络是水凝胶的核心组成部分,赋予水凝胶最独特的功能和性质。在分子层面上可以控制水凝胶的连接方式和聚合物的网络结构。因此,在材料研发的初期,了解聚合物网络的连接方式、结构、功能和特性,选择合适的聚合物对于制备特定功能的水凝胶至关重要。本文首先概述了水凝胶的凝胶机理和影响凝胶的因素,在分子层面上可以控制聚合物网络的形成,从而制备临床上需要的水凝胶。最后介绍了水凝胶在临床医学上的应用,展望了水凝胶材料的未来发展趋势。     

基于壳聚糖/聚丙烯酸/纳米银的高强抗菌水凝胶

首先以丙烯酸(AA)和壳聚糖(CS)为单体、N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,通过光聚合法制备了CS/PAA双网络水凝胶,然后将Ag~+以硝酸银的形式分散在水凝胶中并通过紫外光辐照获得CS/PAA/纳米银复合水凝胶,并对复合水凝胶的抗菌性能进行研究。采用红外光谱对其结构进行表征,研究单体含量对水凝胶力学性能以及溶胀行为的影响。结果表明,当丙烯酸质量分数为20%,壳聚糖质量分数为5%的情况下,水凝胶的拉伸性能最优。此外,纳米银的引入有效提高了水凝胶的抗菌性能。     

双网络凝胶吸附剂的构建及其去除水中污染物的应用

近年来,随着工业的迅速发展,水污染危机是世界面临的主要威胁之一,开发新型环境功能材料和技术,实现水体污染物的高效去除是目前研究热点。双网络水凝胶(Double Network hydrogels)是具有三维网络结构的高分子聚合物,其机械性能优越,具备较高的强度,可以承受高水平的拉伸和压缩变形。低溶胀率使水凝胶可以容纳大量水并保持稳定的形态和网络结构。此外,由于其独特的交联方式,它还具有快速的自修复性能和显著的抗疲劳性能。具备众多优点的双网络水凝胶是一种有着巨大潜力的吸附材料,在水处理领域引起广泛关注。本文综述了双网络凝胶吸附剂的物化特性及其分类,以及近年来双网络凝胶吸附剂去除水体中重金属、抗生素和染料等污染物的应用进展。通过该综述,为双网络凝胶吸附剂的深入开发以及在水质净化中的工程应用提供新思路、新方法和新技术。     

基于壳聚糖物理网络的高强韧双网络水凝胶的构建、调控与应用

双网络水凝胶由两个具有相反物理性质的交联网络构成, 硬而脆的第一网络在变形过程中断裂耗散能量, 从而增韧凝胶. 当第一网络为具有重建能力的物理网络时, 双网络水凝胶表现出优异的抗软化和机械稳定性. 目前双网络水凝胶第一物理网络类型单一、结构和力学调控繁琐, 因而其开发和应用受到限制. 针对上述问题, 作者发展了硬而脆的壳聚糖物理网络构建的新策略, 壳聚糖的网络类型、结构和物理性质均能简便调控, 然后将其作为第一网络成功地制备了多种高强韧且结构性能可灵活调控的双网络水凝胶, 在抗冻敷料、生物医用、柔性电子和可穿戴设备等领域具有重要的应用价值. 构建壳聚糖基双网络水凝胶的策略操作简单、普适通用, 能够有力促进高强韧水凝胶的开发、功能化及应用.     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

基于均苯三甲酸与4-羟基吡啶的超分子水凝胶

以均苯三甲酸和对羟基吡啶为原料,采用简便方法合成了一种新的凝胶因子,并采用1H NMR、IR和元素分析确认其结构.红外光谱中2849和1894cm-1处出峰证明羧基与吡啶基间形成了氢键.在凝胶化过程中,凝胶因子可自组装形成纤维状网络结构.随着凝胶因子浓度的增加,纤维搭接逐渐致密,凝胶网络密度逐渐增大,可冻结水含量逐渐增加.因此,通过改变凝胶因子浓度可有效控制凝胶的结构及性能.该凝胶因子在较低浓度下形成的超分子水凝胶在100℃下也能够稳定存在.     

基于均苯三甲酸与对羟基吡啶的超分子水凝胶

以均苯三甲酸和对羟基吡啶为原料, 采用简便方法合成了一种新的凝胶因子, 并采用1H NMR、IR和元素分析确认其结构. 红外光谱中2849和1894 cm－1处出峰证明羧基与吡啶基间形成了氢键. 在凝胶化过程中, 凝胶因子可自组装形成纤维状网络结构. 随着凝胶因子浓度的增加, 纤维搭接逐渐致密, 凝胶网络密度逐渐增大, 可冻结水含量逐渐增加. 因此, 通过改变凝胶因子浓度可有效控制凝胶的结构及性能. 该凝胶因子在较低浓度下形成的超分子水凝胶在100 ℃下也能够稳定存在.     

高强度双网络水凝胶的增韧机理

双网络水凝胶(DN凝胶)是由具有很强的结构非对称性的两种聚合物形成的特殊的聚合物互穿网络。相对于单一聚合物网络(SN凝胶)而言,DN凝胶的机械强度和韧性都有惊人的提高,其拉伸断裂应力和断裂应变分别能达到1~10 MPa和1000%~2000%、韧性(撕裂能)可以达到102~103J·m-2。DN凝胶性能的提高,主要是由强对称结构的第一重网络(刚而脆)与第二重网络(软而韧)相互缠结和互穿的结果。对DN凝胶断裂过程和增韧本质的理解是设计下一代具有理想机械性能的DN凝胶的关键所在。一些DN凝胶表现出大的滞后、屈服、细颈和软化现象,而这些现象用经典的Lake-Thomas断裂理论是没有办法解释的。根据DN凝胶的滞后和细颈等实验现象,Brown和Tanaka等提出了"破坏区"理论来解释DN凝胶超乎寻常的高韧性。最近,龚剑萍等提出的"牺牲键"理论也已经很好地应用于设计和制备具有新型微纳米结构的高韧性DN凝胶。本文着重阐释了DN凝胶的增韧机理,总结了这一领域的最新研究成果,并讨论各种因素对凝胶韧性的影响,最后对DN凝胶增韧机理存在的问题和研究方向进行了展望。     

Mechanically tough and recoverable hydrogels via dual physical crosslinkings

Development of functional tough hydrogels with new network structures and energy dissipation mechanisms has great promise for many applications. Here, a new type of physical hydrogel crosslinked by hydrophobic association and hydrogen bonds was synthesized by a facile micellar copolymerization of hydrophobic methyl acrylate (MA) monomers and hydrophilic N-hydroxyethyl acrylamide (HEAA) monomers in the presence of Tween80 micelles. Strong hydrophobic association between inner MA and Tween80 and hydrogen bonds between external polyHEAA and Tween80 provide two distinct crosslinkers to construct mechanically tough and recoverable network. Mechanical properties of polyHEAA-MA@Tween80 hydrogels strongly depended on network components (HEAA, MA; Tween80 concentrations). At optimal conditions, the hydrogels can achieve fracture stress of 700 kPa, fracture strain of 1687 mm/mm, elastic modulus of 195 kPa, and tearing energy of 1598 J/m². Due to the reversible nature of physical interactions, polyHEAA-MA@Tween80 hydrogels can achieve fast stiffness/toughness recovery of 60%/33% without any external stimuli and resting time at room temperature. This work demonstrates a new design strategy to fabricate a new a single-network hydrogel with high mechanical and self-recovery properties by incorporating both hydrophobic association and hydrogen bonds in the network, which may provide alternative viewpoint for the design of multifunctional tough hydrogels. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1294–1305     

A Double Network Hydrogel with High Mechanical Strength and Shape Memory Properties

Double network (DN) hydrogels as one kind of tough gels have attracted extensive attention for their potential applications in biomedical and load-bearing fields. Herein, we import more functions like shape memory into the conventional tough DN hydrogel system. We synthesize the PEG-PDAC/P(AAm-co-AAc) DN hydrogels, of which the first network is a well-defined PEG (polyethylene glycol) network loaded with PDAC (poly(acryloyloxyethyltrimethyl ammonium chloride)) strands, while the second network is formed by copolymerizing AAm (acrylamide) with AAc (acrylic acid) and cross-linker MBAA (N, N'-methylenebisacrylamide). The PEG-PDAC/P(AAm-co-AAc) DN gels exhibits high mechanical strength. The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m³, respectively. Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network, the PEG-PDAC/P(AAm-coAAc) DN hydrogels use P(AAm-co-AAc), a weak polyelectrolyte, as the second network. The AAc units serve as the coordination points with Fe³⁺ ions and physically crosslink the second network, which realizes the shape memory property activated by the reducing ability of ascorbic acid. Our results indicate that the high mechanical strength and shape memory properties, probably the two most important characters related to the potential application of the hydrogels, can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.     

单宁作为共引发剂和交联剂制备高伸长率水凝胶

以过硫酸铵为引发剂(APS)、杨梅综合单宁(TA)作为共引发剂和交联剂,通过自由基聚合制备了高伸长率水凝胶(TIC-gel)。通过红外光谱(FT-IR)、核磁共振(~1 H-NMR)和浸泡尿素的方法研究了TA在TIC-gel中形成化学交联的机理。通过拉伸、压缩测试和流变学测试系统地分析了TIC-gel的力学性能和影响因素。结果表明:相比于传统化学交联水凝胶(PAM-MBA-gel),利用TA制备的凝胶具有高伸长率(2 250%)和高韧性(3.51 MJ/m3)。利用这一新的形成交联的方法所得的凝胶即使在高浓度时也能形成均匀的结构,可以很好地分散应力,为TIC-gel的高伸长率作出贡献。     

Ultrastrong and Tough Supramolecular Hydrogels from Multiurea Linkage Segmented Copolymers with Tractable Processablity and Recyclability

Strong and tough synthetic hydrogels have received ever‐increasing interests due to their potential applications as load‐bearing structural materials. However, strong, tough, and recyclable hydrogels in different forms that can be generated by different methods according to various practical applications still remain an intrinsic bottleneck. A simple one‐pot synthesis of multiurea linkage segmented linear copolymers with easy recyclability, hybridization, and processability, including compression molding, solution casting, and spinning methods, to yield ultrastrong and tough hydrogel films or stretchable hydrogel fibers with diameters ranged from macro‐, micro‐, to nanoscale, is reported here.     

强韧型自愈合水凝胶的研究进展

水凝胶作为一种由大量水和与众不同的三维网状结构构成的智能软材料,已经广泛应用于许多领域,如药物输送、软骨修复、废物处理及电子设备等。然而,水凝胶不良的机械性能及自愈合性极大地限制了它们的潜在应用。目前已报道的韧性水凝胶通常不具有或只有很弱的自修复性,而自修复水凝胶通常机械性能非常弱。因此,研发具有高效自修复性能和优异机械性能的水凝胶材料,无论是从学术角度还是工业角度都是非常重要的。本文总结了近些年来强韧型自愈合水凝胶的最新研究进展,从其制备方法、性能等方面进行了简要介绍,并对未来的发展前景进行了展望。     

Highly stretchable,self-adhesive,and self-healable double network hydrogel based on alginate/polyacrylamide with tunable mechanical properties

A number of synthetic hydrogels suffer from low mechanical strength. Despite of the recent advances in the fabrication of tough hydrogels, it is still a great challenge to simultaneously construct high stretchability, and self-adhesive and self-healing capability in a hydrogel. Herein, a new type of double network hydrogel was prepared based on irreversible cross-linking of polyacrylamide chains and Schiff-base reversible cross-linking between glycidyl methacrylate-grafted ethylenediamine and oxidized sodium alginate (OSA). The combination of both cross-linkings and their synergistic effect provided a novel hydrogel with high strength, stretchable, rapid self-healing, and self-adhesiveness to different material. Besides, the hydrogels with diverse OSA content could maintain their original shapes after loading–unloading tensile test. The resulting hydrogel has a great potential in various fields for supporting and load-bearing substance.     

pH敏感型聚谷氨酸/透明质酸基互穿网络医用水凝胶的制备及表征

生物材料是推动生物医学领域日新月异变化的基石,医用水凝胶作为重要成员,近年来表现出蓬勃发展的态势。文章介绍了一种新型可注射的、以生物相容性方法交联的聚谷氨酸(Poly (γ-glutamic acid), PGA)/透明质酸(Hyaluronic acid, HA)复合水凝胶。研究首先采用EDC/NHS方法合成了酪胺(Tyramine,Ty)接枝聚谷氨酸的PGA-Ty前体大分子及半胱胺(Cysteamine, CA)修饰透明质酸的HA-CA前体大分子。两种前体大分子的结构分别使用核磁和红外进行了确证。得到的两种前体大分子在低浓度双氧水和辣根过氧化物酶(Horseradish Peroxidase, HRP)的共同作用下,于水相中交联得到互穿网络(Interpenetrating Network, IPN)水凝胶。实验对IPN水凝胶样品的系列性能,如平衡含水量、内部形貌、酶降解速率以及力学性能等进行了测试,并选取了盐酸四环素为药物模型对凝胶的体外药物释放行为、体外抗菌效果进行了测评。凝胶材料的细胞毒性及凝胶支架对细胞3D培养的效果证明其生物相容性优异,体外包埋的细胞经72h培养,未表现出明显细胞毒性。系列数据证明,该种水凝胶可以设计成为pH敏感型的药物控释载体材料,并因其良好的生物相容性,也有作为细胞支架、创伤辅料等其它生物医用材料的潜力。     

Preparation of interpenetrating polymer network composed of poly(ethylene glycol) and poly(acrylamide) hydrogels as a support of enzyme immobilization

Poly(ethylene glycol)(PEG)‐based interpenetrating polymeric network (IPN) hydrogels were prepared for the application of enzyme immobilization. Poly(acrylamide)(PAAm) was chosen as the other network of IPN hydrogel and different concentration of PAAm networks were incorporated inside the PEG hydrogel to improve the mechanical strength and provide functional groups that covalently bind the enzyme. Formation of IPN hydrogels was confirmed by observing the weight per cent gain of hydrogel after incorporation of PAAm network and by attenuated total reflectance/Fourier transform infrared (ATR/FTIR) analysis. Synthesis of IPN hydrogels with higher PAAm content produced more crosslinked hydrogels with lower water content (WC), smaller M_c and mesh size, which resulted in enhanced mechanical properties compared to the PEG hydrogel. The IPN hydrogels exhibited tensile strength between 0.2 and 1.2 MPa while retaining high levels of hydration (70–81% water). For enzyme immobilization, glucose oxidase (GOX) was immobilized to PEG and IPN hydrogel beads. Enzyme activity studies revealed that although all the hydrogels initially had similar enzymatic activity, enzyme‐immobilizing PEG hydrogels lost most of the enzymatic activity within 2 days due to enzyme leaching while IPN hydrogels maintained a maximum 80% of the initial enzymatic activity over a week due to the covalent linkage between the enzyme and amine groups of PAAm. Copyright © 2008 John Wiley & Sons, Ltd.     

A transparent sericin-polyacrylamide interpenetrating network hydrogel as visualized dressing material

High transparent and biocompatible hydrogel dressing with bioactivity is attractive for clinical skin repair. Here we report a high optically transparent interpenetrating network (IPN) hydrogel that was fabricated by sericin and polyacrylamide. The hydrogels possess pH-dependent degradation as well as high porosity and porous structures with different sized diameters and distribution. Moreover, the swelling behaviors, degradation dynamics, and mechanical strength can be flexibly regulated by adjusting the content of sericin. In addition, the hydrogel system is compatible with hosting cells owing to its excellent cell-adhesive capability, effectively promoting cell attachment, proliferation and long-term survival. Together, our study demonstrates that the sericin-polyacrylamide interpenetrating network hydrogel may serve as a visualized dressing material for real-time monitoring of wounds.     

大孔PAMPS/PVA半互穿网络型水凝胶的制备及其性能研究

以PEG6000为成孔剂, 合成了大孔聚(2-丙烯酰胺-2-甲基丙磺酸)/聚乙烯醇半互穿网络型(s-IPN)水凝胶. 红外分析表明, PVA与PAMPS之间形成了较强的氢键, 使得PVA分子上的C—O伸缩振动吸收峰移向了低波数处. X射线衍射分析发现, 当PVA用量较高时, 由于部分的PVA结晶, 使得凝胶的半互穿网络结构不均匀. 电镜分析结果表明, 没有使用成孔剂的凝胶表面成褶皱形, 不存在任何孔洞结构; 而以PEG6000为成孔剂的凝胶表面存在相互贯穿的大孔结构. 研究了该水凝胶的溶胀性能, 结果表明, 该水凝胶的平衡溶胀度在116至320之间; 而成孔剂PEG6000的加入能较大幅度提高凝胶的溶胀速率, 凝胶在240 min之内就能达到溶胀平衡. 对凝胶抗压缩性能的研究表明, 当PVA用量为9.1% (w)时, 凝胶的抗压缩强度最大, 可达12.0 MPa; 而成孔剂的加入会在一定程度削弱凝胶的抗压缩强度. 该凝胶具有较好的电场敏感性, 研究发现, 将吸去离子水达到溶胀平衡的凝胶放入施加有电场的0.2 mol•L－1 NaCl溶液中时, 凝胶迅速偏向阳极. 而PVA和成孔剂PGE6000的用量均对凝胶的偏转速度以及最大偏转角存在较大的影响.