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.     

Reinforced Supramolecular Hydrogels from Attapulgite and Cyclodextrin Pseudopolyrotaxane for Sustained Intra‐Articular Drug Delivery

Injectable hydrogels for nonsteroidal anti‐inflammatory drugs’ (NSAIDs) delivery to minimize the side effects of NSAIDs and achieve long‐term sustained release at the targeted site of synovial joint are attractive for osteoarthritis therapy, but how to improve its mechanical strength remains a challenge. In this work, a kind of 1D natural clay mineral material, attapulgite (ATP), is introduced to a classical cyclodextrin pseudopolyrotaxane (PPR) system to form a reinforced supramolecular hydrogel for sustained release of diclofenac sodium (DS) due to its rigid, rod‐like morphology, and unique structure, which has great potential in tissue regeneration, repair, and engineering. Investigation on the interior morphology and rheological property of the obtained hydrogel points out that the ATP distributed in PPR hydrogel plays a role similar to the “reinforcement in concrete” and exhibits a positive effect on improving the mechanical properties of PPR hydrogel by regulating their interior morphology from a randomly distributed style to the well‐ordered porous frame structure. The hybrid hydrogels demonstrate good shear‐thinning and thixotropic properties, excellent biocompability, and sustained release behavior both in vitro and in vivo. Furthermore, preliminary in vivo treatment in an acute inflammatory rat model reveals that the ATP hybrid hydrogels present sustained anti‐inflammatory effect.     

Hybrid Hydrogels Assembled from Phenylalanine Derivatives and Agarose with Enhanced Mechanical Strength

A roadblock for supramolecular hydrogels is their poor mechanical properties. Herein, to enhance the mechanical strength of supramolecular hydrogels, agarose(AG) was incorporated into the low molecular weight hydrogelator(G1). The results of scanning electron microscopy(SEM), circular dichroism(CD) and Fourier transform infrared spectroscopy(FTIR) prove that G1 gelators can self-assemble into cross-linked network together with AG. The mechanical properties of the gels are characterized by a rotary rheometer and the mechanical properties of the hybrid hydrogels(Hgel) can be significantly improved and may be further tuned by changing the ratio of the two components. For example, the elastic modulus of Hgel Ⅱ[m(G1):m(AG)=7:3] is about 2 times higher than that of G1 hydrogel. The results demonstrate that the mechanical property of hybrid supramolecular hydrogels can be adjusted through the formation of a cross-linked network.     

Viscoelastic and fractal characteristics of a supramolecular hydrogel hybridized with clay nanoparticles

The supramolecular hydrogels derived from low-molecular-mass gelators represent a unique class of soft matters and have important potential applications in biomedical fields, separation technology and cosmetic science. However, they suffer usually from weak mechanical and viscoelastic properties. In this work, we carry out the in situ hybridization of clay nanoparticles (Laponite RD) into the supramolecular hydrogel formed from a low-molecular-mass hydrogelator, 2,6-di[N-(carboxyethyl carbonyl)amino]pyridine (DAP), and investigate the viscoelastic and structural characteristics of resultant hybrid hydrogel. It was found that a small concentration of Laponite RD could lead to a significant increase in the storage modulus, loss modulus or complex viscosity. Compared with neat DAP hydrogel, the hybrid hydrogel has a greater hydrogel strength and a lower relaxation exponent. In particular, the enhancement of the clay nanoparticles to the viscoelastic properties of the DAP hydrogel is more effective in the case of higher DAP concentration. By relating its macroscopic elastic properties to a scaling fractal model, such a hybrid hydrogel was confirmed to be in the strong-link regime and to have a more complex network structure with a higher fractal dimension when compared with neat DAP hydrogel.     

Ion-induced white-light-emitting polymeric hydrogels with high mechanical strength and reversible stimuli-responsive properties

We have developed a facile strategy to fabricate model multicolor hydrogels via a straightforward mixing process of poly acrylonitrile-grafted methacrylamide (PANMAM), polymethacrylic acid (PMAA) and doped lanthanide (Eu/Tb) and zinc ions to form the interpenetrating dual-polymer gel networks. The hydrogels exhibit excellent tunability of multi-spectrum emission colors (including white light) by simply varying the stoichiometry of metal ions. Furthermore, taking the advantage of different metal ion response mechanisms, we have demonstrated the reversible acidity/alkalinity stimuli-responsive behaviors of white-light-emitting hydrogel (WLE gel). Meanwhile, the unique cross-linked network formed through hydrogen-bonding, metal-ligand coordination and ionic interaction is introduced to achieve favorable mechanical strength of hydrogels. These properties enable the possibility in obtaining fluorescent patterns on hydrogels, which are promising candidate for encrypted information with improved security.     

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.     

Injectable supramolecular hybrid hydrogels formed by MWNT‐grafted‐poly(ethylene glycol) and α‐cyclodextrin

Poly(ethylene glycol)‐grafted‐multiwalled carbon nanotube (MWNT‐g‐PEG) was synthesized by a coupling reaction and formed inclusion complexes (ICs) after selective threading of the PEG segment of the MWNT‐g‐PEG through the cavities of α‐cyclodextrins (α‐CDs) units. The polypseudorotaxane structures of the as‐obtained hydrogels were confirmed by ¹H NMR, X‐ray diffraction and DSC analyses. The complexation of the PEG segments with α‐CDs and the hydrophobic interaction between the MWNT resulted in the formation of supramolecular hybrid hydrogels with a strong network. Thermal analysis showed that the thermal stability of the hydrogel was substantially improved by up to 100 °C higher than that of native hydrogel. The resultant hybrid hydrogels were found to be thixotropic and reversible, and could be applied as a promising injectable drug delivery system. The mechanical strength of the hybrid hydrogels was greatly improved in comparison with that of the corresponding native hydrogels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3145–3151, 2010     

高强度PAMPS-PAAm互穿网络凝胶及其溶胀性能

通过考察不同单体浓度或离子强度下凝胶的力学性能和溶胀特性,对聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)与聚丙烯酰胺(PAAm)形成的互穿网络凝胶的高强度性能和作用机理进行了研究.结果表明:PAMPS-PAAm互穿网络凝胶的力学强度对c(AMPS)存在一个最佳值(1 mol/L),且随c(AAM)的增大而显著增大(0.5～4 mol/L).当c(AMPS)=1 mol/L、c(AAM)＝4 mol/L时,互穿网络凝胶的最大抗压强度达6.46 MPa;改变凝胶体系内水的离子强度,PAMPS-PAAm凝胶在0.25 mol/kg离子强度时的抗压强度与纯水状态下相比增加了29%.     

Preparation and characterization of sodium carboxymethylcellulose/poly(N-isopropylacrylamide)/clay semi-IPN nanocomposite hydrogels

A new kind of pH-/temperature-responsive semi-interpenetrating polymer network hydrogels based on linear sodium carboxymethylcellulose (CMC) and poly(N-isopropylacrylamide) (PNIPA) cross-linked by inorganic clay (CMC/PNIPA/Clay hydrogel) was prepared. The temperature- and pH-responsive behaviors, the mechanical properties of these hydrogels were investigated. The CMC/PNIPA/Clay hydrogels exhibited a volume phase transition temperature around 32 °C with no significant deviation from the conventional PNIPA hydrogels. The swelling ratio of the CMC/PNIPA/Clay hydrogels gradually decreased with increasing the contents of clay. The influence of pH value on swelling behaviors showed that there is a maximum swelling ratio at pH 5.9. Moreover, the CMC/PNIPA/Clay hydrogels exhibited excellent mechanical properties with high tensile stress and elongation at break in excess of 1200%.     

电场敏感的智能性水凝胶*

电场敏感水凝胶是一类在电刺激下可以溶胀、收缩或弯曲的智能性水凝胶,其主要特点是可以将电能转化为机械能。本文对近年来已见报道的电场敏感水凝胶的研究进行了较为详细的综述。同时,对电场敏感水凝胶的响应机理、影响水凝胶响应性的因素以及其在能量转换装置、人工肌肉等方面的应用也作了相应的介绍。     

Fabrication of novel supramolecular hydrogels with high mechanical strength and adjustable thermosensitivity

An effective strategy was developed to fabricate the supramolecular hydrogels with high mechanical strength and adjustable thermosensitivity in aqueous systems, in which physical hydrogel precursors were first formed by the inclusion complexation of Pluronic F68/poly(epsilon-caprolactone) block copolymer end-capped with acryloyl groups with alpha-cyclodextrin (alpha-CD) and subsequently in situ UV photo-cross-linking was carried out. In this way, strong supramolecular hydrogels with elastic moduli greater than 100 000 Pa could be created, which is an order of magnitude higher than that previously achieved with related supramolecular hydrogels. Moreover, the stimuli-responsive property of these hydrogels could be tailored by changing the molar feed ratio of alpha-CD to the macromer. By X-ray diffraction and thermogravimetric analyses, the polypseudorotaxane structure of the inclusion complexes in as-obtained hydrogels was confirmed.     

Mussel-inspired chemistry in producing mechanically robust and bioactive hydrogels as skin dressings

The development of hydrogels as skin dressings demonstrates a great potential in real life applications. To achieve this, the hydrogel has to conquer its natural poor mechanical strength, and to prolong its lifetime, antifatigue and self-healing properties originating from dynamic interactions are also required. As skin dressings, the hydrogel needs to maintain its ductility while pursuing the above mentioned properties. In this work, poly(ethylene glycol) diacrylate is used to produce skin dressings by reinforcing poly(ethylene glycol) diacrylate/alginate double network hydrogels with a crosslinker from mussel-inspired chemistry, which is 3,4-dihydroxy-l-phenylalanine. This crosslinking methodology significantly improved mechanical strength of the hydrogel, with 11,200% increase in compressive failure strength; it endowed the hydrogel with outstanding antifatigue and training strengthening properties that makes its mechanical strength increasing in a 50 cycles compressive test; the hydrogel showed excellent self-healing properties that in rheological characterization; it also displayed enhanced storage modulus after withstanding a shear strain up to 1100%; meanwhile, the hydrogel exhibited extreme ductility with an elastic modulus of only 10.90–16.53 kPa. 3,4-dihydroxy-l-phenylalanine also renders the hydrogel its inherent antioxidant activity, conductivity, and bioadhesiveness. Together with the highly transparent appearance, the hydrogels possess a great potential and practibility in the fields of skin dressings.     

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.     

纳米颗粒增强的手性超分子水凝胶成骨性能

手性超分子水凝胶能够仿生细胞外手性微环境,在组织工程中具有特殊的意义,但其强度和稳定性较低,仍然面临着巨大的挑战.本文将无机羟基磷灰石纳米颗粒(HAP)引人到苯丙氨酸衍生物手性超分子水凝胶(LPF)中以改善其力学性能和生物功能.圆二色光谱和扫描电子显微镜结果显示,HAP掺入后LPF组装手性发生反转.与纯LPF水凝胶相比...     

A Hybrid Supramolecular Polymeric Hydrogel with Rapid Self‐Healing Property

A hybrid supramolecular polymeric hydrogel is conveniently constructed via host–guest interaction of a host cyclodextrin polymer (poly‐CD) with a guest α‐bromonaphthalene polymer (poly‐BrNp) and mixing with 6‐thio‐β‐cyclodextrin (β‐SH‐CD) modified gold nanoparticles (GPCDs) in aqueous solution. According to the dynamic oscillatory data, the hydrogel exhibits markedly enhanced stiffness compared with the GPCD‐free one (both G′ and G“ values are almost twice as high as those of the original GPCD‐free hydrogel) due to the introduction of the inorganic gold nanoparticles. This hybrid supramolecular polymeric hydrogel has a rapid and excellent self‐healing property (only about 1 min, and the G′ and G” of the self‐healed hydrogel almost turned back to their original levels after 1 hour) in air (without adding any solvent or additive).     

A simple route to interpenetrating network hydrogel with high mechanical strength

A simple two-step method was introduced to improve the hydrogel mechanical strength by forming an interpenetrating network (IPN). For this purpose, we synthesized polyacrylate/polyacrylate (PAC/PAC), polyacrylate/polyacrylamide (PAC/PAM), polyacrylamide/polyacrylamide (PAM/PAM) and polyacrylamide/poly(vinyl alcohol) (PAM/PVA) IPN hydrogels. The PAC/PAC IPN and PAC/PAM IPN hydrogels showed compressive strength of 70 and 160 kPa, respectively. For the PAM/PAM IPN and PAM/PVA IPN hydrogels, they exhibited excellent tensile strength of 1.2 and 2.8 MPa, and elongations at break of 1750% and 3300%, respectively. A strain relaxation was also observed in the case of PAM series IPN hydrogels. From FTIR, TGA and SEM measurements, we confirmed that physical entanglement, hydrogen bonds and chemical crosslinking played major roles in improving hydrogel strength and toughening. The two-step technique contributes to the understanding of ideal networks, provides a universal strategy for designing high mechanical strength hydrogels, and opening up the biomedical application of hydrogels.     

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 .     

Supramolecular hydrogel formed by glucoheptonamide of l-lysine: simple preparation and excellent hydrogelation ability

We describe the simple preparation of new l-lysine derivatives with a gluconic or glucoheptonic group, their hydrogelation properties, and the thermal and mechanical properties of the supramolecular hydrogels. The l-lysine derivatives with a gluconic group have no hydrogelation ability, while the l-lysine-glucoheptonamide derivatives functioned as hydrogelators. Their hydrogelation abilities increased with the decreasing length of the spacer between the l-lysine segment and the glucoheptonic group. The compound, which has no spacer, formed a supramolecular hydrogel at 0.05 wt % in pure water. The thermal stability and high mechanical strength of the supramolecular hydrogels based on this compound significantly depended on the aqueous solutions. Electron microscopy and FTIR studies demonstrated that the hydrogelators created a three-dimensional network through hydrogen bonding and hydrophobic interactions in the supramolecular hydrogel. In addition, it was found that hydrophobic interactions played an important role in the thermal stability of the supramolecular hydrogel.     

Hybrid supramolecular hydrogels induced by Au nanoparticles protected with MPEG-b-PCL copolymers with α-cyclodextrin

To fabricate supramolecular hydrogel hybridised with well-dispersed gold nanoparticles (AuNPs), water-soluble AuNPs protected with methoxy poly(ethylene glycol)-b-poly(?-caprolactone) (MPEG-b-PCL) self-assembled monolayers (MPEG-b-PCL/AuNPs) were synthesised and used as guest molecules to interact with α-cyclodextrin (α-CD) in aqueous solutions. Transmission electron microscopy measurement results showed that the diameter of the AuNPs produced was about 6–10 nm with a narrow particle size distribution, and stained MPEG-b-PCL/AuNPs micelles made in water clearly displayed the formation of a core-shell structure with a single gold core per micelle. X-ray diffraction measurement results confirmed that there existed the characteristic peaks of both AuNPs and polypseudorotaxanes formed via the inclusion complexation of MPEG-b-PCL moieties with α-CD in as-obtained hydrogels. UV–visible spectra displayed that the same surface plasma resonance absorption peaks appeared at 526 nm for both aqueous dispersion of MPEG-b-PCL/AuNPs and resultant hybrid hydrogel with α-CD. Rheological measurements showed that the hybrid hydrogel has a lower mechanical strength and viscosity, and a relatively prolonged gelation time in comparison with the corresponding native hydrogel. The mechanical strength of the hydrogel nanocomposites could be tailored by modulating the concentration of MPEG-b-PCL/AuNPs and α-CD as well as the composition of MPEG-b-PCL/AuNPs.     

Hybrid Hydrogels Toughened by Chemical Covalent Bonding and Physical Electrostatic Interactions

Polystyrene nanoparticles with negative charges(n-PSs) were synthesized using styrene(St) and sodium styrene sulfonate(NaSS) as initial materials by surfactant-free emulsion polymerization. Subsequently, a hybrid hydrogel was prepared using acrylamide(AAm) and methacryloyloxyethyltrimethyl ammonium chloride(DMC) as co-monomers with N,N'-methylenebisacrylamide(MBA) as a chemical crosslinker and n-PSs as a physical electro-static interaction agent. The resulting hybrid hydrogels exhibited excellent tensile strength and elongation at break. The tensile stress of hybrid hydrogels was seven times greater than that of hydrogels without n-PSs. The elongation at break of hydrogels reached 700%, which was much higher compared to those of the hydrogels without n-PSs. Furthermore, swelling measurements of the hydrogels indicate that there is an overshoot in the swelling process and the extent of overshoot decreases with the increasing n-PSs. Therefore, the work presented here provides a method for improving the mechanical properties of hydrogels via the introduction of polymeric nanoparticles.