无机纳米复合水凝胶*

近年来,纳米材料由于具有诸多奇特效应而备受关注。将无机纳米粒子与高分子水凝胶复合,可以很大程度地改善传统水凝胶的使用性能,因而成为近年来水凝胶研究领域的热点课题之一。纳米材料的形貌多姿多彩,相同材质不同形貌的纳米材料对复合材料性能有着不同的作用。本文从不同形貌（层状、管状及球状等）的无机纳米材料对复合水凝胶性能影响出发,以无机纳米粒子的形貌分类,综述了当前无机纳米复合水凝胶的研究进展。     

纳米复合水凝胶体系的设计合成与结构功能一体化构筑

纳米复合水凝胶(NC-Gels)因兼具有机相及无机相的优点,且具有独特的结构特征和理化性能,近年来已成为水凝胶领域的研究重点,在智能器件、生物医药、组织工程等领域有着广泛的应用前景.基于有机/无机杂化原理,通过交联点的结构与功能性设计和凝胶网络的可控构筑,获得了一系列力学性能优异并具有多重响应甚至智能化响应的NC-Gels,并提出了以有机微球或功能化杂化微球分别为交联点构建纳米复合水凝胶(OC-Gels)和杂化水凝胶(H-Gels)的新方法,探索了其在生物医学和智能传感领域等的初步应用.     

有机-无机纳米复合水凝胶*

本文综述了近年来有机-无机纳米复合水凝胶领域的研究进展。针对无机成分的不同种类及复合形式,本文将目前已见报道的有机-无机纳米复合水凝胶划分为三类,分别为层状硅酸盐纳米插层复合水凝胶、粘土交联纳米复合水凝胶和二氧化硅纳米杂化复合水凝胶。阐述了三类纳米复合水凝胶的发展趋势,特别就它们的合成方法进行了详细归纳与总结。在此基础上,介绍了纳米无机成分对复合水凝胶的性能增强机理,并就三者之间的增强差异进行了说明。     

载银离子PLGA-PEG-PLGA温度敏感水凝胶的制备及体外抗菌性能

利用聚乙二醇(PEG 1000)引发乙交酯和 D,L-丙交酯开环共聚合, 制备了聚丙交酯乙交酯(PLGA)三嵌段共聚物(PLGA-PEG-PLGA)温敏水凝胶材料; 利用核磁共振氢谱( ¹H NMR)确定了产物的结构及组成. 通过还原硝酸银的方法制备银纳米粒子(AgNPs), 并将其与PLGA-PEG-PLGA三嵌段共聚物水凝胶混合, 制得新型AgNPs/PLGA-PEG-PLGA复合水凝胶; 对该复合水凝胶的相关性能进行了表征. AgNPs/PLGA-PEG-PLGA复合水凝胶仍然具有温敏性能, 随着温度升高可发生溶胶-凝胶的相转变; 还可以持续释放银纳米粒子, 从而发挥抗菌性能. 体外细胞实验结果表明, AgNPs/PLGA-PEG-PLGA复合水凝胶具有良好的生物相容性, 未见明显细胞毒性, 是具有应用前景的新型复合水凝胶.     

黏土基纳米复合水凝胶

介绍了一种以黏土为交联剂的新型纳米复合水凝胶, 重点阐述了水凝胶的结构特点, 制备方法及其特有的力学性能, 自修复性能, 透明度和溶胀性。     

芳纶增强MXene-聚丙烯酸-无定型碳酸钙复合水凝胶的制备及性能

传统水凝胶存在机械性能和可加工性差的缺点,本研究制备了芳纶增强MXene-聚丙烯酸-无定型碳酸钙(ANF/MXene-PAA-ACC)复合水凝胶,并研究了其相关力学与物理性能。首先,通过氟化锂和盐酸刻蚀法,结合超声剥离工艺制备了二维MXene单层纳米片,将其应用到PAA-ACC复合水凝胶中。为了提高MXene-PAA-ACC的力学性能,进一步通过加入芳纶,制备了ANF/MXene-PAA-ACC复合水凝胶。采用扫描电镜和万能力学试验机对复合水凝胶的表观形貌、力学性能、自修复和粘附性等物理性能进行了表征和测试。结果表明：与PAA-ACC水凝胶相比,ANF/MXene-PAA-ACC水凝胶的可加工性、力学性能、粘附性、自修复性都得到了提高。     

丝素蛋白纤维/聚N-异丙基丙烯酰胺复合水凝胶的性能

以丝素蛋白纤维为填充材料,采用自由基聚合的方法制备复合聚N-异丙基丙烯酰胺(PNIPPAm)水凝胶,研究复合水凝胶的黏弹性能、溶胀性能和反复溶胀-收缩性能。结果表明:丝素蛋白纤维的加入改善了复合水凝胶的力学性能,其平衡溶胀率不仅与温度有关,而且与丝素蛋白纤维的含量有关。此外,处在表面的丝素蛋白纤维与水凝胶之间存在间隙,在反复溶胀-收缩过程中可以作为输水通道,有利于水分子进出,提高了PNIPPAm水凝胶对温度的响应速率并使其溶胀-收缩重复性更好。     

石墨烯基水凝胶的研究进展

石墨烯具有独特的导电、导热和力学性能,既能够自组装为电化学性能优良的石墨烯水凝胶,又可以与小分子和聚合物进行复合制备多功能性复合水凝胶,大幅度地拓展了传统水凝胶的应用范围。本文主要分为四部分来综述近些年来石墨烯基水凝胶的研究进展。第一部分简要介绍了石墨烯的研究背景和石墨烯基水凝胶的研究意义。第二部分主要根据石墨烯基水凝胶的组成将其分为石墨烯水凝胶、石墨烯/小分子和石墨烯/聚合物复合水凝胶三类,分别介绍了它们的制备方法、形成机理和凝胶性能。其中,对石墨烯/小分子复合水凝胶的介绍以石墨烯基超分子水凝胶为主,而对石墨烯/聚合物复合水凝胶的介绍以智能型水凝胶为主。第三部分主要介绍了石墨烯基水凝胶在超级电容器、水处理、控释药物、微流体开关、催化剂载体等方面的应用和发展。最后,对该领域所面临的挑战进行了总结和展望。     

基于Pickering乳液的磁性高强水凝胶的制备及性能表征

合成了一种磁性Fe3O4纳米颗粒稳定的水包油(O/W)Pickering乳液并以其作为交联剂,在适宜条件下引发单体丙烯酰胺聚合来制备了一种新型的磁性高强复合水凝胶.采用X射线衍射(XRD)及场发射扫描电子显微镜(SEM)分别对磁性Fe3O4纳米颗粒和复合水凝胶的结构进行了表征,结果表明Pickering乳胶粒子较均匀地分布在复合凝胶网络中.溶胀性能测试及溶胀动力学分析表明复合水凝胶具有良好的溶胀性能,能够吸收自身干重100倍左右的水,其溶胀过程不遵循Fickian扩散模型;拉伸测试表明该水凝胶具有优异的力学性能,其拉伸强度能够达到150 kPa左右,断裂伸长率能够达到300%左右,并且当其承受的应力释放后能快速地恢复到初始形态.磁性能测试的结果显示该水凝胶具有良好的磁性.     

纳米复合水凝胶在人工软骨中的研究进展

纳米复合水凝胶(nanocomposite hydrogels,NC hydrogels)作为人工软骨修复材料有很大的应用价值和吸引力.由于NC水凝胶具有与天然软骨细胞外基质(extracellular matrix,ECM)相似的结构,以及较好的力学性能、刺激响应性等优势,是软骨修复的理想支架材料.本综述详细介绍了用...     

Strong and Injectable Hydrogels Based on Multivalent Metal Ion-Peptide Cross-linking

Injectable hydrogels are ideal biomaterials for delivering cells, growth factors and drugs specifically to localized lesions and subsequent controlled release. Many factors can affect the efficacy of injectable hydrogels. To avoid potential damage to encapsulated cells or drugs, injectable hydrogels should be highly dynamic so that they can undergo shear-thinning at low strain rates and rapidly reform after injection. However, dynamic hydrogels are often mechanically weak, leading to the leakage of encapsulated cells or drugs. Here we demonstrated a convenient method to improve the mechanical strength without jeopardizing the dynamic properties of hydrogels by using metal ion-peptide crosslinkers containing multiple metal ion-ligand bonds. We showed that the dynamic properties of the hydrogels correlated with the intrinsic dynamics of the metal-ligand bonds and were not affected by the formation of multivalent binding. Yet, the mechanical stability of the hydrogels was significantly improved due to the increased thermodynamic stability of the crosslinkers. We further showed that the drug release rates were slowed down by the formation of multivalent crosslinkers. Our results highlight the importance of ligand valency to the mechanical response of hydrogels and provide a universal route to rationally tune the dynamic and mechanical properties of injectable hydrogels.     

医用水凝胶力学性能的研究进展

水凝胶是一类由亲水性聚合物链通过多种交联机制而形成的三维网络结构,具有良好的生物相容性、降解性及可调节的力学性能,广泛用于医药领域。针对不同的临床应用场景,水凝胶需要具备不同的力学性能,但目前尚无统一、系统的量化评价标准,无法针对不同临床应用需求特异性地调节水凝胶性能,限制了此类制剂应用。本文系统总结了医用水凝胶的临床应用及相应的力学性能要求、力学性能的表征手段及调节方法,并对医用水凝胶的发展现状进行总结和展望,希望为医用水凝胶力学性能的研究和发展提供理论基础。     

Mussel-Inspired Adhesive,Antibacterial, and Stretchable Composite Hydrogel for Wound Dressing

Hydrogels have attracted extensive attention in the field of biomedicine because of their similar structure to extracellular matrix (ECM) and good biocompatibility. However, the adhesiveness, mechanical properties, and antibacterial properties of conventional hydrogels are not satisfactory. In this study, multifunctional chitosan/polydopamine/polyacrylamide (CS/PDA/PAM) hydrogels are prepared through a nature-inspired strategy. The catechol group of polydopamine (PDA) component endows CS/PDA/PAM hydrogels with tissue adhesion and self-healing properties. The introduction of chitosan (CS) not only greatly improves antibacterial ability, but also enhances the mechanical properties of CS/PDA/PAM hydrogels. Skin wound healing experiments show that CS/PDA/PAM hydrogels could accelerate skin tissue regeneration and promote wound healing. Therefore, CS/PDA/PAM hydrogels have great potential in the application of new wound dressings.     

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。     

Nanocomposite smart hydrogels with improved responsiveness and mechanical properties: A mini review

Responsive hydrogels have the ability to change their volume, transparency, or other properties in response to external chemical and/or physical stimuli. The responsiveness properties including responsive rate and degree, as well as mechanical properties such as Young's modulus, toughness, breaking strength, and breaking strain are crucial parameters of the smart hydrogels that determine the scope of hydrogel applications such as soft actuators, artificial muscles, and tissue engineering scaffolds. In this paper, the development of the nanocomposite smart hydrogels, which can achieve both improved responsiveness and mechanical properties, is reviewed. First, the fabrication approaches for building the nanocomposite networks by doping organic or inorganic nanomaterials via crosslinking or blending strategies are introduced. Then, the mechanisms used to improve both responsiveness and mechanical properties of nanocomposite responsive hydrogels are discussed. Finally, the perspectives as well as current challenges of such nanocomposite responsive hydrogels are addressed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1306–1313     

Recent developments of polysaccharide-based double-network hydrogels

Polysaccharides possessing distinctive properties, such as biocompatibility, biodegradability, and nontoxicity, are promising matrices for hydrogels. However, the polysaccharides-based hydrogels have poor mechanical properties, which is a major limitation for their applications. In recent years, researches on double-network (DN) hydrogels with outstanding mechanical properties have gained increasing attention. Therefore, the main research orientation is to combine the benefits of both materials and broaden their applications in various fields. This paper reviews the recent progress of polysaccharide-based DN (PDN) hydrogels that show great advantages in mechanical, physiochemical properties, biocompatibility, biodegradability and so on. The preparation, structure, and unique properties of different PDN hydrogels are discussed in detail. Moreover, we summarize the applications of PDN hydrogels in biomedical and energy storage and conversion fields. This research progress is breaking through the limitations of PDN hydrogels and opening a new avenue for their future development.     

Bioresponsive DNA-co-polymer hydrogels for fabrication of sensors

Bioresponsive hydrogels that include DNA within a non-DNA network (DNA-co-polymer hydrogels) constitute a group of soft materials possessing selective recognition ability hosted by the included DNA structure. They are furthermore characterized by the changes to the hydrogel properties which follow the recognition of the biological analyte. Such hydrogels can be synthesized with desired recognition ability through the selection of particular nucleotide sequence that is recognizing or binding ions, small molecules, biomolecules or parts of larger entities. The binding of the label-free analyte triggers a response of the hydrogel, such as changes in its swelling volume, mass, optical or mechanical properties. The hydrogel response is mediated by changes in network parameters such as charge density, crosslinking density or a combination of these associated with the interaction with the analyte. Bioresponsive DNA polymer hydrogels have found wide application in biosensors due to their versatile nature.     

水凝胶流变学研究概况

水凝胶具有良好的生物相容性和生物可降解性,其结构呈三维网状结构,与细胞外基质相似,在药物释放和组织工程等领域具有广阔的应用前景,被广泛地用于生物制药、生物材料和医学等领域。流变学可以描述材料的流动特性和力学性能,水凝胶的粘弹响应对材料内部结构的变化也非常敏感,因此流变行为被视为研究水凝胶的一种重要方法。本文综述了流变学方法在水凝胶研究中的应用,介绍了水凝胶流变学的研究方法,讨论了影响水凝胶流变学特征的因素,并展望了水凝胶流变学的发展前景。     

Preparation of Injectable Composite Hydrogels by Blending Poloxamers with Calcium Carbonate-Crosslinked Sodium Alginate

The effects of calcium carbonate-crosslinked sodium alginate on poloxamer hydrogels have been investigated. The mechanical strength, degradability, and thermal stability of hydrogels were characterized. The chemical and physical crosslinking in the composite hydrogels has resulted in an improvement of the compressive strength and elasticity of the hydrogels. These mixed hydrogels showed improved mechanical properties, elasticity, and stability as well as environmental responsiveness and injectability.